EP1129160B1 - Detergents aqueux pour lave-vaisselle - Google Patents

Detergents aqueux pour lave-vaisselle Download PDF

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Publication number
EP1129160B1
EP1129160B1 EP99927840A EP99927840A EP1129160B1 EP 1129160 B1 EP1129160 B1 EP 1129160B1 EP 99927840 A EP99927840 A EP 99927840A EP 99927840 A EP99927840 A EP 99927840A EP 1129160 B1 EP1129160 B1 EP 1129160B1
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Prior art keywords
weight
water
compositions according
cleaning compositions
soluble
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EP99927840A
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German (de)
English (en)
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EP1129160A1 (fr
Inventor
Jürgen Härer
Bernd Richter
Karl-Heinz Maurer
Christian Nitsch
Matthias Sunder
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3726—Polyurethanes
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/06—Phosphates, including polyphosphates
    • 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
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions

Definitions

  • the present invention relates to liquid means for cleaning dishes in a domestic dishwasher.
  • the invention relates to water-based liquid dishwashing detergents for machine dishwashing.
  • liquid detergent compositions which comprise 14 to 35% by weight of sodium tripolyphosphate, 0.1 to 50% by weight of a potassium and / or ammonium salt of an inorganic or organic acid, water and optionally surfactants, solubilizers, sequestering agents, Contains persalts and other ingredients.
  • Linear viscoelastic automatic dishwashing detergent compositions are also described in the European patent application EP 446,761 (Colgate).
  • the compositions disclosed herein contain up to 2% by weight of a long chain fatty acid or salt thereof, 0.1 to 5% by weight of surfactant, 5 to 40% by weight of water soluble builder, and up to 20% by weight of chlorine bleach and a polycarboxylate thickener wherein the ratio of potassium to sodium ions in the compositions should be 1: 1 to 45: 1.
  • compositions disclosed herein contain a polyacrylate thickener which forms a gel matrix with water, surfactant, bleach, builder and water.
  • Gelled automatic dishwashing detergents are also disclosed in the European patent application EP 611,206 (Colgate). These compositions contain 1 to 12% by weight of a liquid nonionic surfactant, 2 to 70% by weight of builder, as well as enzymes and a stabilizing system composed of swelling substances and hydroxypropylcellulose.
  • Viscoelastic, thixotropic Geschirtherapiesmittel with 0.001 to 5 wt .-% surfactant and enzymes and an enzyme stabilization system of boric acid and polyhydroxy compounds are described in the international patent application WO93 / 21299 (Procter & Gamble).
  • the agents disclosed herein also contain from 0.1% to 10% by weight of one or more thickeners.
  • Aqueous dishwashing detergents for automatic dishwashing are also disclosed in the European patent application EP 716 681 (Unilever).
  • the agents disclosed in this document contain 5 to 40% by weight of a sodium potassium phosphate and optionally a polymer which acts as a thickener. According to the information in this document, a K + / Na + ratio of 0.5 to less than 1.5 must be observed for the advantageous properties of the product and the agents must be free of alkali metal silicates.
  • the European patent application EP 352 174 discloses in its examples the preparation of two suspensions which are blended with a surfactant-containing solution to form a liquid detergent containing sodium tripolyphosphate, glycerol / isopropanol and high levels of surfactants.
  • non-acidic binder in the context of the present application characterizes binders which do not belong to the class of surfactants.
  • Water-soluble binders in the sense of the present application are binders which are completely filled with water at room temperature, i. without miscibility, are miscible.
  • liquid binder refers to the state of aggregation of the binder at 25 ° C and 1013.25 mbar. Substances which only melt or soften at relatively high temperatures are therefore not usable in the context of the present invention.
  • Water-soluble builders are used in the compositions of the invention especially for binding calcium and magnesium.
  • Usual builders in the frame The invention preferably in amounts of from 22.5 to 45 wt .-%, preferably from 25 to 40 wt .-% and in particular from 27.5 to 35 wt .-%, each based on the detergent composition, are present, are the low molecular weight Polycarboxylic acids and their salts, the homopolymeric and copolymeric polycarboxylic acids and their salts, the carbonates, phosphates and sodium and potassium silicates. Trisodium citrate and / or pentasodium tripolyphosphate and silicatic builders from the class of alkali disilicates are preferably used for the cleaning agents according to the invention.
  • the potassium salts are preferable to the sodium salts because they often have a higher water solubility.
  • Preferred water-soluble builders are, for example, tripotassium citrate, potassium carbonate and the potassium water glasses.
  • Particularly preferred detergent compositions contain as water-soluble builders phosphates, preferably alkali metal phosphates with particular preference of pentasodium or Pentakaliumtriphosphat (sodium or potassium tripolyphosphate).
  • phosphates preferably alkali metal phosphates with particular preference of pentasodium or Pentakaliumtriphosphat (sodium or potassium tripolyphosphate).
  • Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO 3 ) n and orthophosphoric H 3 PO 4 in addition to higher molecular weight representatives.
  • the phosphates combine several advantages: they act as alkali carriers, prevent limescale deposits and also contribute to the cleaning performance.
  • Sodium dihydrogen phosphate, NaH 2 PO 4 exists as a dihydrate (density 1.91 gcm -3 , melting point 60 °) and as a monohydrate (density 2.04 gcm -3 ). Both salts are white powders which are very soluble in water and which lose their water of crystallization when heated and at 200 ° C into the weak acid diphosphate (disodium hydrogen diphosphate, Na 2 H 2 P 2 O 7 ), at higher temperature in sodium trimetaphosphate (Na 3 P 3 O 9 ) and Maddrell's salt (see below).
  • NaH 2 PO 4 is acidic; It arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed.
  • Potassium dihydrogen phosphate primary or monobasic potassium phosphate, potassium biphosphate, KDP
  • KH 2 PO 4 is a white salt of density 2.33 gcm -3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO 3 ) x ] and is readily soluble in water.
  • Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HPO 4 , is a colorless, very slightly water-soluble crystalline salt. It exists anhydrous and with 2 moles (density 2.066 gcm -3 , loss of water at 95 °), 7 moles (density 1.68 gcm -3 , melting point 48 ° with loss of 5 H 2 O) and 12 moles water ( Density 1.52 gcm -3 , melting point 35 ° with loss of 5 H 2 O) becomes anhydrous at 100 ° C and, upon increased heating, passes into the diphosphate Na 4 P 2 O 7 .
  • Disodium hydrogen phosphate is prepared by neutralization of phosphoric acid with soda solution using phenolphthalein as an indicator.
  • Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K 2 HPO 4 , is an amorphous, white salt that is readily soluble in water.
  • Trisodium phosphate, tertiary sodium phosphate, Na 3 PO 4 are colorless crystals which have a density of 1.62 gcm -3 as dodecahydrate and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P 2 O 5 ) have a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P 2 O 5 ) have a density of 2.536 gcm -3 .
  • Trisodium phosphate is readily soluble in water under alkaline reaction and is prepared by evaporating a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH.
  • Tripotassium phosphate (tertiary or tribasic potassium phosphate), K 3 PO 4 , is a white, deliquescent, granular powder of density 2.56 gcm -3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction. It arises, for example, when heating Thomasschlacke with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over the corresponding sodium compounds in the detergent industry.
  • Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 O 7 , exists in anhydrous form (density 2.534 gcm -3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1.815-1.836 gcm -3 , melting point 94 ° with loss of water) , For substances are colorless, in water with alkaline reaction soluble crystals.
  • Na 4 P 2 O 7 is formed on heating of disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying.
  • the Decahydrate complexes heavy metal salts and hardness agents and therefore reduces the hardness of the water.
  • Potassium diphosphate (potassium pyrophosphate), K 4 P 2 O 7 , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm -3 , which is soluble in water, the pH being 1% Solution at 25 ° 10.4.
  • Sodium and potassium phosphates in which one can distinguish cyclic representatives, the sodium or Kaliummetaphosphate and chain types, the sodium or potassium polyphosphates. In particular, for the latter are a variety of names in use: hot or cold phosphates, Graham's salt, Kurrolsches and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.
  • pentasodium triphosphate Na 5 P 3 O 10 (sodium tripolyphosphate)
  • sodium tripolyphosphate sodium tripolyphosphate
  • n 3
  • 100 g of water dissolve at room temperature about 17 g, at 60 ° about 20 g, at 100 ° around 32 g of the salt water-free salt; after two hours of heating the solution to 100 ° caused by hydrolysis about 8% orthophosphate and 15% diphosphate.
  • pentasodium triphosphate In the preparation of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dehydrated by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.).
  • Sodium tripolyphosphate may be included in the compositions of the invention, but it is also possible to dispense with its use and to use other water-soluble builders, in particular potassium phosphates.
  • the content of sodium tripolyphosphate according to the invention in preferred compositions is between 0 and 20% by weight, more preferably between 0 and 15% by weight.
  • Pentakaliumtriphosphat, K 5 P 3 O 10 (potassium tripolyphosphate), for example, in the form of a 50 wt .-% solution (> 23% P 2 O 5 , 25% K 2 O) in the trade.
  • the potassium polyphosphates are widely used in the detergents and cleaners industry.
  • Potassium tripolyphosphate is in the context of the present invention, a particularly preferred builders, which is used in preferred compositions in amounts of 15 to 40 wt .-%.
  • Particularly preferred agents contain from 20 to 35% by weight of potassium tripolyphosphate; in particular, contents of from 22.5 to 30% by weight are preferred.
  • the detergent compositions according to the invention contain 10 to 50% by weight of one or more non-surfactant, water-soluble, liquid binders from the group of polyethylene glycols and polypropylene glycols, glycerol, glycerol carbonate, ethylene glycol, propylene glycol and propylene carbonate.
  • Polyethylene glycols which can be used according to the invention are polymers of ethylene glycol which correspond to general formula I H- (O-CH 2 -CH 2 ) n -OH (I) n, where n can assume values between 1 (ethylene glycol, see below) and about 16.
  • n can assume values between 1 (ethylene glycol, see below) and about 16.
  • polyethylene glycols are, for example, under the trade name Carbowax ® PEG 200 (Union Carbide), Emkapol ® 200 (ICI Americas), Lipoxol ® 200 MED (Huls America), polyglycol ® E-200 (Dow Chemical), Alkapol ® PEG 300 (Rhone -Poulenc), Lutrol ® E300 (BASF) and the corresponding trade names with higher numbers.
  • PEG 400 is used with particular preference, which may optionally be mixed with other binders mentioned above and below.
  • Preferred agents have a content of PEG 400 which may be from 0 to 40% by weight, preferably from 5 to 30% by weight and in particular from 10 to 20% by weight.
  • Glycerin is a colorless, clear, heavy-bodied, odorless sweet-tasting hygroscopic liquid of density 1.261 that solidifies at 18.2 ° C.
  • Glycerol was originally a by-product of fat saponification but is now technically synthesized in large quantities. Most technical processes are based on propene, which is processed into glycerol via the intermediates allyl chloride, epichlorohydrin. Another technical process is the hydroxylation of allyl alcohol with hydrogen peroxide at the WO 3 contact via the step of the glycide.
  • glycerol is a particularly preferred binder.
  • the content of preferred aqueous detergent compositions of glycerol is 10 to 40 wt .-%, preferably 15 to 35 wt .-% and in particular 20 to 30 wt .-%, each based on the composition.
  • Glycerol carbonate is accessible by transesterification of ethylene carbonate or dimethyl carbonate with glycerol, as by-products of ethylene glycol or methanol incurred. Another synthetic route is based on glycidol (2,3-epoxy-1-propanol), which is converted under pressure in the presence of catalysts with CO 2 to glycerol carbonate. Glycerine carbonate is a clear, easily agitated liquid with a density of 1.398 gcm -3 , which boils at 125-130 ° C (0.15 mbar).
  • Ethylene Glycol (1,2-Ethanediol, "Glycol”) is a colorless, viscous, sweet-tasting, highly hygroscopic liquid that is miscible with water, alcohols and acetone and has a density of 1.113.
  • the solidification point of ethylene glycol is -11.5 ° C, the liquid boils at 198 ° C.
  • ethylene glycol is recovered from ethylene oxide by heating with water under pressure. Promising manufacturing processes can also be built on the acetoxylation of ethylene and subsequent hydrolysis or on synthesis gas reactions.
  • 1,3-Propanediol trimethylene glycol
  • 1,0597 solidifies at -32 ° C and boils at 214 ° C.
  • the preparation of 1,3-propanediol succeeds from acrolein and water with subsequent catalytic hydrogenation.
  • 1,2-propanediol (propylene glycol), which is an oily, colorless, almost odorless liquid, density 1.0381, which solidifies at -60 ° C and boils at 188 ° C.
  • 1,2-Propanediol is prepared from propylene oxide by water addition.
  • 1,2-Propanediol is also a preferred binder to be used in the context of the present invention.
  • mixtures of 1,2-propanediol and PEG or of 1,2-propanediol and glycerol or mixtures of 1,2-propanediol and PEG and glycerol are preferred binder mixtures in the context of the present invention.
  • Propylene carbonate is a water-bright, easily agitated liquid, with a density of 1.2057 gcm -3 , the melting point is -49 ° C, the boiling point at 242 ° C. Also propylene carbonate is industrially accessible by reaction of propylene oxide and CO 2 at 200 ° C and 80 bar.
  • Preferred amounts employing the non-surfactant, water-soluble, liquid binder (s) are within a narrower range such that preferred detergent compositions comprise the non-surfactant, water-soluble, liquid, or non-surfactant surfactant (s) (n) binders in amounts of 15 to 45 wt .-%, preferably from 20 to 40 wt .-% and in particular from 25 to 35 wt .-%, each based on the detergent composition.
  • the detergent compositions according to the invention may optionally contain from 0.05 to 5% by weight of one or more surfactants.
  • the detergent compositions preferably contain as surfactants nonionic and / or anionic surfactants, preferably anionic surfactants, particularly preferably anionic surfactants from the group of the sulfates and sulfonates, with particular preference for the sulfonate surfactants.
  • nonionic surfactants are the alkoxylated alcohols, the alkylpolyglycosides, the fatty acid hydroxylamides and block copolymers of ethylene oxide and propylene oxide.
  • alkoxylated alcohols the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferably the longer-chain alcohols for the purposes of the present invention.
  • alcohols preferably the longer-chain alcohols for the purposes of the present invention.
  • n moles of ethylene oxide and one mole of alcohol form a complex mixture of addition products of different degrees of ethoxylation.
  • a further embodiment consists in the use of mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide.
  • the substance class of "closed" alcohol ethoxylates reach, which can also be used in the context of the invention.
  • Very particularly preferred for the purposes of the present invention are highly ethoxylated fatty alcohols or mixtures thereof with end-capped fatty alcohol ethoxylates.
  • surfactants the skilled worker ensures that the required foam properties - generally low foaming - are complied with.
  • Alkylpolyglycosides are surfactants which can be obtained by the reaction of sugars and alcohols according to the relevant processes of preparative organic chemistry, wherein, depending on the nature of the preparation, a mixture of monoalkylated, oligomeric or polymeric sugars is obtained.
  • Preferred alkylpolyglycosides can be alkylpolyglucosides, the alcohol being particularly preferably a long-chain fatty alcohol or being a mixture of long-chain fatty alcohols and the degree of oligomerization of the sugars being between 1 and 10.
  • Fatty acid polyhydroxylamides are acylated reaction products of the reductive amination of a sugar (glucose) with ammonia, the long-chain fatty acid methyl esters or long-chain fatty acid chlorides used as the acylating agent generally being long-chain fatty acids.
  • 794-808 is described.
  • Carbon chain lengths of C 6 to C 12 in the fatty acid radical are preferably used.
  • anionic surfactants preference is given to using those of the sulfonate and sulfates type.
  • the surfactants of the sulfonate type are preferably C 9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C 12-18 -monoolefins having terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products into consideration.
  • alkanesulfonates which are obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfo fatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids are suitable.
  • Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
  • C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are preferred.
  • 2,3-alkyl sulfates which, for example, according to the U.S. Patents 3,234,258 or 5,075,041 are manufactured and can be obtained as commercial products from Shell Oil Company under the name DAN ®, are suitable anionic surfactants.
  • Preferred detergent compositions contain the surfactant (s) in amounts of 0.1 to 4 wt .-%, preferably from 0.15 to 3 wt .-% and in particular from 0.2 to 2 wt .-%, each based on the detergent composition.
  • the detergent compositions of the present invention contain enzymes or enzyme preparations to improve cleaning performance on certain soils.
  • the detergent compositions enzymes and / or enzyme preparations preferably protease (s) and / or amylase (s), in amounts of 1 to 5 wt .-%, preferably from 1.5 to 4.5 and in particular from 2 to 4 wt .-%, in each case based on the detergent composition, added to increase the performance of the detergents or to ensure under mild conditions, the cleaning performance in the same quality.
  • Suitable enzymes are, in particular, those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Particularly suitable are bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus derived enzymatic agents. Preferably, subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used.
  • Enzyme mixtures for example from protease and amylase or protease and lipase or protease and cellulase or from cellulase and lipase or from protease, amylase and lipase or protease, lipase and cellulase, but in particular cellulase-containing mixtures are of particular interest.
  • Peroxidases or oxidases have also proved suitable in some cases.
  • the enzymes may be adsorbed to carriers and / or embedded in encapsulants to protect against premature degradation.
  • proteases include lipases, amylases, cellulases and proteases.
  • Preferred proteases are, for. B. BLAP ® 140 from. Biozym, Optimase ® -M-440 and Opticlean ® -M-250 from. Solvay enzyme; Maxacal ® CX and Maxapem ® or Esperase ® from. Gist Brocades or Savinase ® from. Novo.
  • Particularly suitable cellulases and lipases are Celluzym ® 0.7 T and Lipolase ® 30 T of Messrs. Novo Nordisk.
  • liquid enzyme preparations are particularly preferred in the context of the present invention.
  • Such liquid enzyme concentrates are either based homogeneously on a propylene glycol / water base or heterogeneously as a slurry, or are present in a microencapsulated structure.
  • Preferred liquid proteases are Savinase ® L, Durazym ® L, Esperase ® L, and Everlase® ® from. Novo Nordisk, Optimase.RTM ® L, Purafect ® L, Purafect ® OX L, Properase.RTM ® L from. Genencor International, and BLAP ® L of the company. Biozym Ges.mbH.
  • Preferred amylases are Termamyl ® L, Duramyl ® L, and BAN ® from. Novo Nordisk, Maxamyl ® WL and Purafect ® HPAM L from. Genencor International.
  • Preferred lipases are Lipolase ® L, Lipolase ® ultra L and Lipoprime ® L from. Novo Nordisk and Lipomax® ® L from. Genencor International.
  • liquid products e.g. Products such as the products designated by SL or LCC Novo Nordisk be used.
  • the commercial liquid enzyme preparations mentioned contain, for example, 20 to 90% by weight of propylene glycol or mixtures of propylene glycol and water.
  • Detergent compositions preferred in the context of the present invention are characterized in that they contain one or more liquid amylase preparations and / or one or more liquid protease preparations in amounts of from 0.1 to 10% by weight, preferably from 0, 2 to 7.5 wt .-% and in particular from 0.5 to 4 wt .-%, contained.
  • the liquid detergent compositions according to the invention may contain viscosity regulators or thickeners for adjusting a possibly desired higher viscosity.
  • viscosity regulators or thickeners for adjusting a possibly desired higher viscosity.
  • all known thickening agents can be used, ie those based on natural or synthetic polymers.
  • Naturally derived polymers which are used as thickening agents are, for example, agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin and casein.
  • Modified natural products come mainly from the group of modified starches and celluloses, examples which may be mentioned here carboxymethylcellulose and other cellulose ethers, hydroxyethyl and propylcellulose and core flour ethers.
  • a large group of thickeners which find wide use in a variety of applications, are the fully synthetic polymers such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes.
  • Thickeners from said substance classes are widely available commercially and are sold for example under the trade name Acusol ® -820 (methacrylic acid (stearyl alcohol 20 EO) ester-acrylic acid copolymer, 30% in water, Rohm & Haas), Dapral ® -GT- 282-S (alkyl polyglycol ethers, Akzo), DEUTEROL ® polymer-11 (dicarboxylic acid copolymer, Schoner GmbH) deuteron ® -xg (anionic heteropolysaccharide based on ⁇ -D-glucose, D-mannose, D-glucuronic acid, Schoner GmbH ) deuteron ® -XN (nonionic polysaccharide Schoner GmbH), DICRYLAN ® -Verdicker-O (ethylene oxide adduct, 50% solution in water / isopropanol, Pfersse Chemie), EMA ® -81 and EMA ® -91 (ethylene-maleic
  • a preferred polymeric thickener is xanthan gum, a microbial anionic heteropolysaccharide produced by Xanthomonas campestris and some other species under aerobic conditions and having a molecular weight of from 2 to 15 million daltons.
  • Xanthan is formed from a chain of ⁇ -1,4-linked glucose (cellulose) with side chains.
  • the structure of the subgroups consists of glucose, mannose, glucuronic acid, acetate and pyruvate, the number of pyruvate units determining the viscosity of the xanthan gum.
  • Xanthan can be described by the following formula:
  • thickeners are polyurethanes or modified polyacrylates, which, based on the total agent, for example, in amounts of 0.1 to 5 wt .-% can be used.
  • Polyurethanes are prepared by polyaddition from dihydric and higher alcohols and isocyanates and can be described by the general formula III in which R 1 is a low molecular weight or polymeric diol radical, R 2 is an aliphatic or aromatic group and n is a natural number.
  • R 1 is preferably a linear or branched C 2-12 -alk (en) yl group, but may also be a radical of a higher-valent alcohol, thereby forming crosslinked polyurethanes which are different from differ from the above formula I characterized in that the rest of R 1 further -O-CO-NH groups are bonded.
  • TDI 2,4- and 2,6-toluene diisocyanate
  • MDI C 6 H 4 -CH 2 -C 6 H 4
  • thickener based on polyurethane are, for example, under the names Acrysol ® PM 12 V (mixture of 3-5% modified starch and 14-16% polyurethane resin in water, Rohm & Haas), Borchigel ® L75-N (non-ionic polyurethane dispersion, 50% in water, Borchers), Coatex ® BR-100-P (PUR-dispersion, 50% in water / butyl glycol, Dimed), Nopco ® DSX-1514 (polyurethane dispersion, 40% in water / Butyltrigylcol, Henkel-Nopco), thickener QR 1001 (20% polyurethane emulsion in water / Digylcolether, Rohm & Haas) and Rilanit ® VPW-3116 (polyurethane dispersion, 43% in water, Henkel) available.
  • Acrysol ® PM 12 V mixture of 3-5% modified starch and 14-16% polyurethane resin in
  • Modified polyacrylates which can be used in the context of the present invention are derived, for example, from acrylic acid or methacrylic acid and can be described by the general formula IV in the R 3 is H or a branched or unbranched C 1-4 -alk (en) yl radical, X is NR 5 or O, R 4 is an optionally alkoxylated branched or unbranched, possibly substituted C 8-22 -alk (s ) ylrest, R 5 is H or R 4 and n is a natural number.
  • such modified polyacrylates are esters or amides of acrylic acid or of an ⁇ -substituted acrylic acid.
  • Preferred among these polymers are those in which R 3 is H or a methyl group.
  • R 3 is H or a methyl group.
  • the designation of the radicals bound to X represents a statistical mean value which, in individual cases, can vary with regard to chain length or degree of alkoxylation.
  • Formula II merely indicates formulas for idealized homopolymers. In the context of the present invention, however, it is also possible to use copolymers in which the proportion of monomer units which satisfy the formula II is at least 30% by weight. For example, it is also possible to use copolymers of modified polyacrylates and acrylic acid or salts thereof which still have acidic H atoms or basic -COO groups.
  • modified polyacrylates are polyacrylate-polymethacrylate copolymers which satisfy the formula IVa in which R 4 is a preferably unbranched, saturated or unsaturated C 8-22 -alkenoyl radical, R 6 and R 7 independently of one another are H or CH 3 , the degree of polymerization n is a natural number and the degree of alkoxylation a is a natural number between 2 and 30, preferably between 10 and 20.
  • Products of the formula IVa are commercially available for example under the name Acusol ® 820 (Rohm & Haas) in the form of 30 wt .-% strength dispersion in water available.
  • R 4 is a stearyl radical
  • R 6 is a hydrogen atom
  • R 7 is H or CH 3
  • the degree of ethoxylation a is 20.
  • Detergent compositions preferred in the context of the present invention are characterized in that they additionally contain from 0.1 to 5% by weight, preferably from 0.2 to 4% by weight, particularly preferably from 0.3 to 3% by weight and in particular 0, 5 to 1.5 wt .-%, of a polymeric thickener, preferably from the group of polyurethanes or modified polyacrylates, with particular preference of thickeners of formula IV in the R 3 is H or a branched or unbranched C 1-4 -alk (en) yl radical, X is NR 5 or O, R 4 is an optionally alkoxylated branched or unbranched, possibly substituted C 8-22 -alk (s ) yl radical, R 5 is H or R 4 and n is a natural number.
  • the viscosity of the compositions according to the invention can be measured by customary standard methods (for example Brookfield LVT-II viscosimeter at 20 rpm and 20 ° C., spindle 3) and is preferably in the range from 500 to 5000 mPas.
  • Preferred detergent compositions have viscosities of from 1000 to 4000 mPas, values between 1300 and 3000 mPas being particularly preferred.
  • the pH of the undiluted products according to the invention is preferably in the range from 6 to 11, particularly preferably between 7 and 10 and in particular between 7.5 and 9.
  • compositions according to the invention may contain further ingredients which further improve the performance and / or aesthetic properties of the detergent compositions.
  • preferred detergent compositions furthermore comprise one or more substances from the group of bleaches, bleach activators, electrolytes, nonaqueous solvents, pH adjusters, fragrances, dyes and enzyme stabilizers.
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • bleaching agents from the group of organic bleaching agents can be used.
  • Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide.
  • peroxyacids examples of which include the alkyl peroxyacids and the aryl peroxyacids.
  • Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimidoperoxycaproic acid [phthaloiminoperoxyhexanoic acid (PAP )], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinates, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diper
  • chlorine or bromine releasing substances can be used.
  • suitable chlorine or bromine releasing materials are, for example, heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium.
  • DICA dichloroisocyanuric acid
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.
  • bleach activators may be incorporated into the detergent compositions.
  • bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy- 2,5-dihydrofuran.
  • TAED tetraacet
  • bleach catalysts can be incorporated into the moldings.
  • These substances are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.
  • organic cobuilders it is possible in particular to use polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders (see below) and phosphonates in the dishwasher detergents according to the invention.
  • Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.
  • the acids themselves can also be used.
  • the acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of cleaning agents.
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
  • polymeric polycarboxylates for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol.
  • the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The against polystyrenesulfonic acids measured molar masses are generally much higher than the molecular weights specified in this document.
  • Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution.
  • the content of (co) polymeric polycarboxylates in the compositions is preferably 0 to 5% by weight, in particular 0.5 to 2.5% by weight.
  • phosphonates are, in particular, hydroxyalkane or aminoalkanephosphonates.
  • hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B.
  • the builder used here is preferably HEDP from the class of phosphonates.
  • the aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, especially if the agents also contain bleach, it is preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
  • the content of preferred detergent compositions in phosphonates is 0 to 3 wt .-%, preferably 0.1 to 2.5 wt .-% and in particular 0.2 to 2 wt .-%.
  • electrolyte a wide variety of different salts can be used. Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. From a manufacturing point of view, the use of NaCl or MgCl 2 in the compositions according to the invention is preferred.
  • the proportion of electrolytes in the inventive compositions is usually 0.5 to 5 wt .-%.
  • Non-aqueous solvents which can be used in addition to the non-surfactant, water-soluble, liquid binders in the inventive compositions, for example, from the group of monohydric or polyhydric alcohols or alkanolamines, provided they are miscible in the specified concentration range with water.
  • the solvents are selected from ethanol, n- or i-propanol, butanols and ethanolamines.
  • Non-aqueous solvents may be used in the detergent compositions of the invention in amounts between 0.5 and 10 wt .-%, but preferably below 5 wt .-% and in particular below 3 wt .-%.
  • pH adjusting agents may be indicated.
  • Can be used here are all known acids or alkalis, unless their use is not for technical application or environmental reasons or for reasons of consumer protection prohibited.
  • the amount of these adjusting agents does not exceed 5% by weight of the total formulation.
  • the agents according to the invention can be dyed with suitable dyes.
  • Preferred dyes the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the agents and to light and none pronounced substantivity to dishware, especially plastics, in order not to stain them.
  • the detergent compositions of the invention can also - if they contain enzymes - also substances are added that stabilize the enzymes and thus prevent loss of activity.
  • These substances are derived, for example, from the group of shorter-chain carboxylic acids, hydroxycarboxylic acids, dicarboxylic acids, boron compounds, in particular boric acid, Ca salts or polyfunctional amines such as mono-, di- or triethanolamine.
  • Preferred detergent compositions according to the invention have a content of boron compounds, in particular boric acid.
  • Particularly preferred agents contain 0.5 to 3 wt .-% boric acid, in particular 1 to 2 wt .-%, each based on the total agent.
  • compositions according to the invention can be carried out by simple mixing in continuous or discontinuous processes.
  • the water-soluble builders are dissolved in water for preparation and stirred vigorously in a mixer.
  • Optional components may also be added in this process stage, wherein in particular the addition of surfactants vioscosity regulators is recommended at this time if the agents according to the invention are to contain these substances.
  • the aqueous solution may be heated to 30 to 50 ° C in order to accelerate the homogeneous distribution.
  • non-surfactant water-soluble binder and other optional ingredients such as dyes, electrolytes and the like. admixed, wherein temperature-labile substances such as perfume and / or enzymes are advantageously stirred only after cooling. If desired, the resulting product can be further diluted with water.
  • the total water content of the products according to the invention may vary depending on the amount of builders and non-surfactant, water-soluble, liquid binders.
  • the water content is below 40 wt .-%, preferably below 35 wt .-% and in particular below 30 wt .-%, each based on the total agent, wherein water content above 5 wt .-%, preferably above 10 Wt .-% and in particular above 15 wt .-% are preferred.
  • E1 to E5 were prepared, whose composition is given in Table 1: ⁇ b> Table 1: ⁇ / b> aqueous dishwashing detergent (% by weight) E1 E2 E3 E4 E5 Potassium triphosphate (50% solution) 64.0 24.0 60.0 - 60.0 Natnumtriphosphat - 20.0 - - - tripotassium - - - 25.0 - potassium carbonate - - 10.0 25.0 - potassium silicate - - 10.0 - - Na- SKS® -6 ex Hoechst - - - - 5.0 Thickener * 1.0 1.0 1.0 1.2 1.2 glycerin 30.0 30.0 - 15.0 30.85 1,2-propanediol - - 15.0 15.0 - enzymes ** 2.5 2.5 3.0 3.0 1.
  • compositions E1 to E5 were in a household dishwasher (Miele G 590 with universal program) against the following washing conditions a commercial dishwashing detergent tested in powder form: 55 ° C / 16 ° d water hardness measured in the main rinse (ie "hard conditions").
  • the dosage for both the commercial powder and for the aqueous products of the invention was 25 g each.
  • compositions according to the invention Contaminants from milk, minced meat on porcelain plates, minced meat in glass bowls, egg yolk and oat flakes, the compositions according to the invention with the powdered cleaner comparable cleaning performance.
  • these performances were consistently better than those of the comparative example V.
  • the storage stability of the agents was checked by the composition E1.
  • the cleaning performance was determined on various soils (dried minced meat, egg yolk, egg / milk, oatmeal and starch mix) with freshly prepared product under the above conditions (dishwasher, dosage, water hardness, temperature). Additional amounts of product E1 were stored for 4 weeks at room temperature (E1 ') and at 40 ° C (E1 ") The cleaning performance is shown in the following table, with a visual rating ranging from 0 (no purification) to 10 (complete) Cleaning).
  • the table shows that even after four weeks of storage, the funds show no performance losses, but maintain their high level of performance.
  • the storage stability, a high degree of cleaning performance and the preservation of the original enzyme activity are ensured by the agents according to the invention.

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Claims (14)

  1. Compositions aqueuses liquides d'agent de nettoyage pour le lavage de vaisselle en machine, contenant, outre d'autres constituants d'agent de nettoyage à utiliser facultativement,
    a) 20 à 50% en poids d'un ou de plusieurs builders solubles dans l'eau et
    b) 10 à 50% en poids d'un ou de plusieurs liants non tensioactifs, solubles dans l'eau, liquides du groupe formé par les polyéthylèneglycols et les polypropylèneglycols, le glycérol, le carbonate de glycérol, l'éthylèneglycol, le propylèneglycol et le carbonate de propylène
    c) 1 à 5% en poids d'enzymes et/ou de préparations enzymatiques.
  2. Compositions d'agent de nettoyage selon la revendication 1, caractérisées en ce qu'elles contiennent comme builders solubles dans l'eau des phosphates, de préférence des phosphates de métal alcalin, en préférant en particulier le triphosphate pentasodique ou pentapotassique (tripolyphosphate de sodium ou de potassium).
  3. Compositions d'agent de nettoyage selon l'une quelconque des revendications 1 à 2, caractérisées en ce qu'elles contiennent 15 à 40% en poids, de préférence 20 à 35% en poids et en particulier 22,5 à 30% en poids de tripolyphosphate de potassium.
  4. Compositions d'agent de nettoyage selon l'une quelconque des revendications 1 à 3, caractérisées en ce qu'elles sont exemptes de phosphates de sodium.
  5. Compositions d'agent de nettoyage selon l'une quelconque des revendications 1 à 4, caractérisées en ce qu'elles contiennent comme liant non tensioactif, soluble dans l'eau, liquide, du glycérol en des quantités de 10 à 40% en poids, de préférence de 15 à 35% en poids et en particulier de 20 à 30% en poids, à chaque fois par rapport à la composition.
  6. Compositions d'agent de nettoyage selon l'une quelconque des revendications 1 à 5, caractérisées en ce qu'elles contiennent en outre 0,05 à 5% en poids d'un ou de plusieurs agents tensioactifs non ioniques et/ou anioniques, de préférence d'un ou de plusieurs agents tensioactifs anioniques, de manière particulièrement préférée d'un ou de plusieurs agents tensioactifs anioniques du groupe formé par les sulfates et les sulfonates, en préférant en particulier les agents tensioactifs de type sulfonate.
  7. Compositions d'agent de nettoyage selon l'une quelconque des revendications 1 à 6, caractérisées en ce qu'elles contiennent le ou les builders solubles dans l'eau en des quantités de 22,5 à 45% en poids, de préférence de 25 à 40% en poids et en particulier de 27,5 à 35% en poids, à chaque fois par rapport à la composition d'agent de nettoyage.
  8. Compositions d'agent de nettoyage selon l'une quelconque des revendications 1 à 7, caractérisées en ce qu'elles contiennent le ou les liants non tensioactifs, solubles dans l'eau, liquides en des quantités de 15 à 45% en poids, de préférence de 20 à 40% en poids et en particulier de 25 à 35% en poids, à chaque fois par rapport à la composition d'agent de nettoyage.
  9. Compositions d'agent de nettoyage selon l'une quelconque des revendications 6 à 8, caractérisées en ce qu'elles contiennent le ou les agents tensioactifs en des quantités de 0,1 à 4% en poids, de préférence de 0,15 à 3% en poids et en particulier de 0,2 à 2% en poids, à chaque fois par rapport à la composition d'agent de nettoyage.
  10. Compositions d'agent de nettoyage selon l'une quelconque des revendications 1 à 9, caractérisées en ce qu'elles contiennent la ou les enzymes et/ou préparations enzymatiques, de préférence une ou des protéases et/ou amylases en des quantités de 1,5 à 4,5% en poids, en particulier de 2 à 4% en poids, à chaque fois par rapport à la composition d'agent de nettoyage.
  11. Compositions d'agent de nettoyage selon l'une quelconque des revendications 1 à 10, caractérisées en ce qu'elles contiennent une ou plusieurs préparations liquides d'amylase et/ou une ou plusieurs préparations liquides de protéase en des quantités à chaque fois de 0,1 à 10% en poids, de préférence de 0,2 à 7,5% en poids et en particulier de 0,5 à 4% en poids.
  12. Compositions d'agent de nettoyage selon l'une quelconque des revendications 1 à 11, caractérisées en ce qu'elles contiennent en outre 0,1 à 5% en poids, de préférence 0,2 à 4% en poids, de manière particulièrement préférée 0,3 à 3% en poids et en particulier 0,5 à 1,5% en poids, d'un épaississant polymère, de préférence du groupe formé par les polyuréthanes ou les polyacrylates modifiés en préférant en particulier les épaississants de formule IV
    Figure imgb0009
     dans laquelle R3 représente H ou un radical alkyle ou alcényle en C1 à C4 ramifié ou non ramifié, X représente N-R5 ou O, R4 représente un radical alkyle ou alcényle en C8 à C22 le cas échéant alcoxylé, ramifié ou non ramifié, éventuellement substitué, R3 représente H ou R4 et n représente un nombre naturel.
  13. Compositions d'agent de nettoyage selon l'une quelconque des revendications 1 à 12, caractérisées en ce qu'elles présentent une viscosité de 500 à 5000 mPa.s, de préférence de 1000 à 4000 mPa.s et en particulier de 1300 à 3000 mPa.s.
  14. Compositions d'agent de nettoyage selon l'une quelconque des revendications 1 à 13, contenant en outre une ou plusieurs substances du groupe des agents de blanchiment, des activateurs de blanchiment, des électrolytes, des solvants non aqueux, des agents de réglage du pH, des parfums, des colorants et des stabilisateurs enzymatiques.
EP99927840A 1998-11-12 1999-06-02 Detergents aqueux pour lave-vaisselle Expired - Lifetime EP1129160B1 (fr)

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PCT/EP1999/003813 WO2000029533A1 (fr) 1998-11-12 1999-06-02 Detergents aqueux pour lave-vaisselle

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ES2186570B1 (es) * 2001-10-02 2004-08-01 M. Jose Roldan Herrero Composicion detergente en estado pastoso para maquinas lavavajillas.
US20060069004A1 (en) * 2004-09-28 2006-03-30 The Procter & Gamble Company Method of cleaning dishware using automatic dishwashing detergent compositions containing potassium tripolyphosphate formed by in-situ hydrolysis
US20060069003A1 (en) * 2004-09-28 2006-03-30 The Procter & Gamble Company Automatic dishwashing detergent compositions containing potassium tripolyphosphate formed by in-situ hydrolysis
AR107756A1 (es) 2016-03-02 2018-05-30 Unilever Nv Composición detergente fluida y procedimiento para prepararla
AR107753A1 (es) 2016-03-02 2018-05-30 Unilever Nv Suspensión de detergente que se puede verter que comprende una fase fluida coloreada y partículas suspendidas
EP3423558B1 (fr) 2016-03-02 2019-06-26 Unilever N.V. Composition de détergent sous la forme d'une suspension
EP3426756B1 (fr) * 2016-03-11 2019-07-03 Unilever N.V. Suspension de détergent coulant comprenant des granulés de catalyseur de blanchiment

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DE3635535C2 (de) * 1986-10-18 1995-05-18 Henkel Kgaa Vorbehandlungs- oder Einweichmittel für hartnäckig angeschmutztes Geschirr und Verfahren zum Reinigen solchen Geschirrs
FR2634493B1 (fr) * 1988-07-20 1990-10-12 Rhone Poulenc Chimie Procede de preparation de formules liquides detergentes contenant du tripolyphosphate
AU667600B2 (en) * 1993-02-08 1996-03-28 Colgate-Palmolive Company, The Nonaqueous gelled automatic dishwashing composition containing enzymes
US5372740A (en) * 1993-09-03 1994-12-13 Lever Brothers Company, Division Of Conopco, Inc. Homogeneous liquid automatic dishwashing detergent composition based on sodium potassium tripolyphosphate

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