EP1129160A1 - Wässrige geschirrreinigungsmittel - Google Patents
Wässrige geschirrreinigungsmittelInfo
- Publication number
- EP1129160A1 EP1129160A1 EP99927840A EP99927840A EP1129160A1 EP 1129160 A1 EP1129160 A1 EP 1129160A1 EP 99927840 A EP99927840 A EP 99927840A EP 99927840 A EP99927840 A EP 99927840A EP 1129160 A1 EP1129160 A1 EP 1129160A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- detergent compositions
- water
- compositions according
- soluble
- 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.)
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Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3726—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- 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
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/06—Phosphates, including polyphosphates
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2003—Alcohols; Phenols
- C11D3/2065—Polyhydric alcohols
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
- C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
Definitions
- the present invention relates to liquid agents for cleaning dishes in a household dishwasher.
- the invention relates to water-based liquid dishwashing detergents for automatic dishwashing.
- Machine dishwashing detergents for household use are usually offered in the form of powders or, more recently, moldings (tablets).
- the supply form of a liquid has so far only been of minor importance in the market in this sector.
- liquids have advantages in terms of dosage and aesthetic product advantages that should not be underestimated, which make this offer form interesting.
- liquid detergent compositions which contain 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 contains surfactants, solubilizers, sequestering agents, persalts and other ingredients.
- Linear viscoelastic detergent compositions for machine dishwashing are also described in 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 polycar Contain boxylate thickeners, the ratio of potassium to sodium ions in the compositions should be 1: 1 to 45: 1.
- compositions disclosed herein contain a polyacrylate thickener that forms a gel matrix with water, surfactant, bleach, a builder, and water.
- Gel-like machine dishwashing detergents are also described in 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 stabilization system which is composed of swelling substances and hydroxypropyl cellulose.
- Viscoelastic, thixotropic dishwashing detergents with 0.001 to 5% by weight of surfactant as well as enzymes and an enzyme stabilization system made of boric acid and polyhydroxy compounds are described in international patent application WO93 / 21299 (Procter & Gamble).
- the agents disclosed here also contain 0.1 to 10% by weight of one or more thickeners.
- Aqueous dishwashing detergents for machine dishwashing are also described in 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 is mandatory for the advantageous properties of the product and the agents must be free from alkali silicates.
- the invention therefore relates to liquid aqueous detergent compositions for machine dishwashing, which, in addition to other detergent ingredients which can be used optionally
- non-surfactant binder characterizes binders that do not belong to the class of the surfactants.
- Water-soluble binders in the sense of the present application are binders which are completely, i.e. without miscibility gap, are miscible.
- liquid binder refers to the physical state of the binder at 25 ° C. and 1013.25 mbar. Substances that melt or soften only at higher temperatures can therefore not be used in the context of the present invention.
- Water-soluble builders are used in the compositions according to the invention primarily for binding calcium and magnesium.
- Common builders The invention is preferably present in amounts of 22.5 to 45% by weight, preferably 25 to 40% by weight and in particular 27.5 to 35% by weight, based in each case on the detergent composition, 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 silicate 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, since they often have a higher solubility in water.
- 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 for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate).
- phosphates preferably alkali metal phosphates with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate).
- Alkali metal phosphates is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HPO 3 ) n and orthophosphoric acid 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 cleaning performance.
- Sodium dihydrogenphosphate, NaH 2 PO 4 exists as a dihydrate (density 1.91 like- 3 , melting point 60 °) and as a monohydrate (density 2.04 like " 3 ). Both salts are white powders which are very easily soluble in water Heat the crystal water and lose it at 200 ° C into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na 2 H 2 P 2 O ? ), At a higher temperature into sodium trimetaphosphate (Na 3 P 3 O g ) and Maddrell's salt (see below). NaH 2 PO 4 is acidic, it is formed when phosphoric acid is adjusted to pH 4.5 with sodium hydroxide solution and the mash is sprayed in.
- Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH 2 PO 4 , is a white salt with a density of 2.33 and 3 , has a melting point of 253 ° [decomposes to form potassium polyphosphate (KPO 3 ) and is easily soluble in water.
- Sodium hydrogen phosphate (secondary sodium phosphate), Na 2 HPO 4 , is a colorless, very easily water-soluble crystalline salt. It exists in anhydrous and with 2 mol. (Density 2.066 Gernkogel 3, loss of water at 95 °), 7 mol. (Density 1.68 Gernkogel 3, melting point 48 ° with loss of 5 H2O) and 12 mol. Water ( Density 1.52 - 3 , melting point 35 ° with loss of 5 H 2 O), becomes anhydrous at 100 ° and changes to the diphosphate Na 4 P 2 O_ when heated more. Disodium hydrogen phosphate is prepared by neutralizing 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 easily soluble in water.
- Trisodium phosphate, tertiary sodium phosphate, Na 3 PO 4 are colorless crystals which, as dodecahydrate, have a density of 1.62 - 3 and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P 2 O 5) 5) have a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P 2 O a density of 2.536 Gernkogel.
- 3 Trisodium phosphate is readily soluble in water with an alkaline reaction and is produced by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH.
- Tripotassium phosphate (tertiary or tribasic potassium phosphate), K 3 PO 4
- K 3 PO 4 is a white deliquescent granular powder with a density of 2.56 Gernkogel 3
- the more soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds in the cleaning agent industry.
- Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 O ?
- Water-free form (density 2.534 Gernkogel 3, melting point 988 °, 880 ° shown) and as the decahydrate (density from 1.815 to 1.836 Gernkogel 3, melting point 94 ° with loss of water).
- Substances are colorless crystals that are soluble in water with an alkaline reaction.
- Na 4 P 2 O ? arises when heating 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 hardening agents and therefore reduces the hardness of the water.
- Potassium diphosphate (potassium pyrophosphate), K 4 P 2 O ? , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 and 3 , which is soluble in water, the pH of the 1% solution at 25 ° being 10.4.
- Sodium and potassium phosphates in which one can differentiate cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's 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
- Approx. 17 g of the salt free from water of crystallization dissolve in 100 g of water at room temperature, approx. 20 g at 60 ° and 32 g at 100 °; After heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate.
- pentasodium triphosphate In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.).
- Sodium tripolyphosphate can be contained in the agents according to the invention, but it is also possible to dispense with their use and to use other water-soluble builders, in particular potassium phosphates.
- the sodium tripolyphosphate content of the agents according to the invention is in preferred agents between 0 and 20% by weight, particularly preferably between 0 and 15% by weight.
- Pentakalmm triphosphate K 5 P 3 O 10 (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% by weight solution (> 23% P 2 O 5 , 25% K ⁇ O).
- the potassium poly phosphates are widely used in the detergent and cleaning agent industry.
- Potassium tripolyphosphate is a particularly preferred builder in the context of the present invention, which is used in preferred compositions in amounts of 15 to 40% by weight.
- Particularly preferred agents contain 20 to 35% by weight of potassium tripolyphosphate, in particular contents of 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.
- the binders contained in the detergent compositions according to the invention are only required to be liquid at room temperature (and normal pressure), to mix completely with water and not to belong to the group of surfactants. From the multitude of binders that can be used, substances from the group of polyethylene glycols and polypropylene glycols, glycerol, glycerol carbonate, ethylene glycol, propylene glycol and propylene carbonate have proven to be suitable binders.
- Detergent compositions which contain these compounds as non-surfactant, water-soluble, liquid binders are preferred in the context of the present invention.
- Polyethylene glycols which can be used according to the invention are polymers of ethylene glycol which have the general formula I
- n can have values between 1 (ethylene glycol, see below) and approx. 16.
- the decisive factor when evaluating whether a polyethylene glycol can be used according to the invention is the physical state of the PEG at room temperature, ie the freezing point of the PEG must be below 25 ° C.
- the specification of the average relative molecular weight following the specification "PEG” is customary in technical terms, so that "PEG 200” characterizes a polyethylene glycol with a relative molecular weight of approximately 190 to approximately 210. According to this nomenclature in the context of the present invention Technically common polyethylene glycols PEG 200, PEG 300, PEG 400 and PEG 600 can be used.
- polyethylene glycols for example, under the trade names 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 can optionally be mixed with other of the binders mentioned above and below.
- Preferred agents have a PEG 400 content which can be 0 to 40% by weight, preferably 5 to 30% by weight and in particular 10 to 20% by weight.
- Polypropylene glycols which can be used according to the invention are polymers of propylene glycol which have the general formula II
- n values can be between 1 (propylene glycol, see below) and approx. 12.
- n values can be between 1 (propylene glycol, see below) and approx. 12.
- Glycerin is a colorless, clear, difficult to move, odorless, sweet-tasting hygroscopic liquid with a density of 1.261 that solidifies at 18.2 ° C. Glycerin was originally only 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 intermediate stages allyl chloride, epichlorohydrin. Another technical process is the hydroxylation of allyl alcohol with hydrogen peroxide at the WO 3 contact via the glycide stage.
- glycerol is a particularly preferred binder.
- the glycerol content of preferred aqueous detergent compositions is 10 to 40% by weight, preferably 15 to 35% by weight and in particular 20 to 30% by weight, in each case based on the composition.
- Glycerol carbonate can be obtained by transesterification of ethylene carbonate or dimethyl carbonate with glycerin, ethylene glycol or methanol being obtained as by-products. Another synthetic route starts from glycidol (2,3-epoxy-l-propanol), which is converted under pressure in the presence of catalysts with CO 2 to form glycerol carbonate. Glycerol is a clear, mobile liquid with a density of 1.398 Gernkogel 3, boiling 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 freezing point of ethylene glycol is -11, 5 ° C, the liquid boils at 198 ° C.
- ethylene glycol is obtained from ethylene oxide by heating with water under pressure.
- Promising manufacturing processes can also be based on the acetoxylation of ethylene and subsequent hydrolysis or on synthesis gas reactions. There are two isomers of propylene glycol, 1,3-propanediol and 1,2-propanediol.
- 1,3-propanediol is a neutral, colorless and odorless, sweet-tasting liquid with a density of 1.0597 that solidifies at -32 ° C and boils at 214 ° C.
- 1,3-Propanediol can be produced from acrolein and water with subsequent catalytic hydrogenation.
- 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.
- 2-propanediol is made from propylene oxide by adding water.
- 2-propanediol is also a preferred binder 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 particularly preferred binder mixtures in the context of the present invention.
- Propylene carbonate is a water-clear, mobile liquid, having a density of 1.2057 Gernkogel 3, the melting point is at - 9 ° C, the boiling point at 242 ° C. Large quantities of propylene carbonate can also be obtained by reacting propylene oxide and CO 2 at 200 ° C and 80 bar.
- non-surfactant (s), water-soluble ⁇ ), liquid ⁇ ) binder are used are within a narrow range, so that preferred detergent compositions or the non-surfactant (s), water-soluble ⁇ ), liquid (s) Containers 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 can optionally contain 0.05 to 5% by weight of one or more surfactants.
- the detergent compositions preferably contain nonionic and / or anionic surfactants, preferably anionic surfactants, particularly preferably anionic surfactants from the group of the sulfates and sulfonates, with particular preference given to the sulfate surfactants.
- nonionic surfactants which can be used are the alkoxylated alcohols, the alkyl polyglycosides, the fatty acid hydroxylamides and block copolymers of ethylene oxide and propylene oxide.
- alkoxylated alcohols to mean the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferably the longer-chain alcohols in the sense 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, depending on the reaction conditions.
- a further embodiment consists in using mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide.
- final etherification with short-chain alkyl groups such as preferably the butyl group, can also give the class of "closed" alcohol ethoxylates, which can also be used in the context of the invention.
- Highly preferred for the purposes of the present invention are highly ethoxylated fatty alcohols or their mixtures with end-capped fatty alcohol ethoxylates.
- surfactants the person skilled in the art makes sure that the required foam properties - generally low-foam - are maintained.
- Alkyl polyglycosides are surfactants which can be obtained by the reaction of sugars and alcohols according to the relevant methods of preparative organic chemistry, which, depending on the type of production, results in a mixture of mono-alkylated, oligomeric or polymeric sugars.
- Preferred alkyl polyglycosides can be alkyl polyglucosides, the alcohol being particularly preferably a long-chain fatty alcohol or 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, whereby long-chain fatty acids, long-chain fatty acid methyl esters or long-chain fatty acid chlorides are generally used as acylating agents.
- Secondary amides are formed when reducing with methylamine or ethylamine instead of with ammonia, such as. B. in S ⁇ FW-Journal, 119, (1993), 794-808.
- Carbon chain lengths of C 6 to C in the fatty acid residue are preferably used.
- Preferred anionic surfactants are those of the sulfonate and sulfate type.
- Preferred surfactants of the sulfonate type are C 9] 3 -alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C 12] g monoolefins with a terminal or internal double bond Sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products is considered.
- alkanesulfonates obtained from C 12 18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
- the esters of ⁇ - sulfo fatty acids for example the ⁇ - sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
- the alk (en) yl sulfates are the alkali and, in particular, the sodium salts of the sulfuric acid semiesters of C 12 -C lg fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ] 0 -C 20 - Oxo alcohols and those half esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
- the C ] 2 -C 16 alkyl sulfates and C - C 15 alkyl sulfates and C ] 4 -C ] 5 alkyl sulfates are preferred from the point of view of washing technology.
- 2,3-Alkyl sulfates which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from the Shell Oil Company under the name DAN®, are also suitable anionic surfactants.
- Preferred detergent compositions contain the surfactant (s) in amounts of 0.1 to 4% by weight, preferably 0.15 to 3% by weight and in particular 0.2 to 2% by weight, in each case based on the detergent composition.
- the detergent compositions according to the invention can contain enzymes or enzyme preparations to improve the cleaning performance of certain contaminants as further ingredients.
- the detergent compositions can contain enzymes and / or enzyme preparations, preferably protease (s) and / or amylase (s), in amounts of 1 to 5% by weight, preferably 1.5 to 4.5% by weight and in particular 2 to 4% by weight .%, in each case based on the detergent composition, are added in order to increase the performance of the detergents or to guarantee the same quality of cleaning performance under milder conditions.
- Particularly suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases obtained from Bacillus lentus are preferably used.
- Enzyme mixtures for example of protease and amylase or protease and lipase or protease and cellulase or of cellulase and lipase or of protease, amylase and lipase or protease, lipase and cellulase, but especially mixtures containing cellulase are of particular interest.
- Peroxidases or oxidases have also proven to be suitable in some cases.
- the enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition.
- proteases include lipases, amylases, cellulases and proteases.
- Preferred proteases are e.g. B. BLAP ® 140 from Biozym, Optimase ® -M-440 and Opticlean®-M-250 from Solvay Enzymes; 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 basis or heterogeneously as a slurry, or they have a microcapacity structure.
- Preferred amylases are Termamyl L, Duramyl ® L, and BAN ® from. Novo Nordisk, Maxamyl ® WL and Purafect ® HP On 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 Novo Nordisk products labeled SL or LCC are 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 0.1 to 10% by weight, preferably 0, 2 to 7.5 wt .-% and in particular from 0.5 to 4 wt .-%, contain.
- liquid detergent compositions according to the invention can contain viscosity regulators or thickeners in order to set a possibly higher viscosity. All known thickeners can be used here, that is to say those based on natural or synthetic polymers.
- Polymers derived from nature that are used as thickeners are, for example, agar agar, carrageenan, tragacanth, acacia, alginates, pectins, polyoses, guar flour, carob bean flour, starch, dextrins, gelatin and casein.
- Modified natural products come primarily from the group of modified starches and celluloses, examples include carboxymethyl cellulose and other cellulose ethers, hydroxyethyl and propyl cellulose and core meal ether.
- thickeners that are widely used in a wide 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 the substance classes mentioned are widely available commercially and are sold, for example, under the trade names Acusol®-820 (methacrylic acid (stearyl alcohol-20-EO) ester-acrylic acid copolymer, 30% in water, Rohm & Haas), Da ⁇ ral ® -GT- 282-S (alkyl polyglycol ether, Akzo), Deuterol®-Polymer-l l (dicarboxylic acid copolymer, Schönes GmbH), Deuteron®-XG (anionic heteropolysaccharide based on ß-D-glucose, D-manose, D-glucuronic acid, Schoener GmbH), Deuteron ® -XN (non-ionic polysaccharide, Schönes GmbH), Dicrylan ® -Dickener-O (ethylene oxide adduct, 50% in water / isopropanol, Pfersse Chemie), EMA ® -81 and EMA ® -
- a preferred polymeric thickener is xanthan, a microbial anionic heteropolysaccharide produced by Xanthomonas campestris and some other species under aerobic conditions and having a molecular weight of 2 to 15 million daltons.
- Xanthan is formed from a chain with ß-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.
- Xanthan can be described by the following formula:
- thickeners which are likewise preferably to be used are polyurethanes or modified polyacrylates which, based on the total agent, can be used, for example, in amounts of 0.1 to 5% by weight.
- Polyurethanes are produced by polyaddition from dihydric and higher alcohols and isocyanates and can be described by the general formula III
- R 1 is a low molecular weight or polymeric diol radical
- R 2 is an aliphatic or aromatic group
- n is a natural number.
- R 1 is preferably a linear or branched C 2 12 -alk (en) yl group, but can also be a residue of a higher alcohol, whereby cross-linked polyurethanes are formed, which differ from Distinguish the formula I given above in that further -O- CO-NH groups are bonded to the radical R 1 .
- TDI 2,4- or 2,6-toluenediisocyanate
- MDI C 6 H 4 -CH 2 -C 6 H 4
- HMDI, R 2 (CH 2 ) 6 ].
- polyurethane-based thickeners are, for example, Acrysol®PM 12 V (mixture of 3-5% modified starch and 14-16% PUR resin in water, Rohm & Haas), Borchigel ® L75-N (non-ionic PU dispersion, 50% in water, Borchers), Coatex ® BR-100-P (PUR dispersion, 50% in water / butylglycol, Dimed), Nopco® DSX-1514 (PUR dispersion, 40% in water / butyltrigylcol, Henkel-Nopco), thickener QR 1001 (20% PUR emulsion in water / digylcol ether, Rohm & Haas) and Rilanit ® VPW-3116 (PUR dispersion, 43% in water, Henkel) available.
- Acrysol®PM 12 V mixture of 3-5% modified starch and 14-16% PUR resin in water, Rohm & Haas
- Borchigel ® L75-N
- 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
- R 3 is H or a branched or unbranched C ; 4 -alk (en) yl radical, X for NR 5 or O, R 4 for an optionally alkoxylated branched or unbranched, possibly substituted C 8 22 -alk (en) yl radical, R 5 for H or R 4 and n for a natural one Number stands.
- modified polyacrylates are generally esters or amides of acrylic acid or an ⁇ - substituted acrylic acid. Preferred among these polymers are those in which R 3 represents H or a methyl group.
- the two hydrocarbon radicals which are bonded to the N atom being independent of one another can be selected from optionally alkoxylated branched or unbranched C g 22 alk (en) yl residues.
- the designation of the radicals bound to X represents a statistical mean, which can vary in individual cases with regard to chain length or degree of alkoxylation.
- Formula II only provides formulas for idealized homopolymers. However, copolymers in which the proportion of monomer units which satisfy the formula II is at least 30% by weight can also be used in the context of the present invention. For example, copolymers of modified polyacrylates and acrylic acid or salts thereof which still have acidic H atoms or basic -COO groups can also be used.
- Modified polyacrylates to be preferably used in the context of the present invention are polyacrylate-polymethacrylate copolymers which satisfy the formula IVa
- R 4 represents a preferably unbranched, saturated or unsaturated C g 22 alk (en) yl radical
- R 6 and R 7 independently of one another represent H or CH 3
- the degree of polymerization n is a natural number
- the degree of alkoxylation a is a natural number 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% by weight dispersions in water.
- R 4 is a stearyl radical
- R 6 is a hydrogen atom
- R 7 is H or CH 3 and the degree of ethoxylation a is 20.
- Preferred detergent compositions in the context of the present invention are characterized in that they additionally contain 0.1 to 5% by weight, preferably 0.2 to 4% by weight, particularly preferably 0.3 to 3% by weight and in particular 0, 5 to 1.5% by weight of a polymeric thickener, preferably from the group of the polyurethanes or the modified polyacrylates, with particular preference for thickeners of the formula TV
- R 3 represents H or a branched or unbranched C j 4 alk (en) yl radical
- X represents NR 5 or O
- R 4 represents an optionally alkoxylated branched or unbranched, possibly substituted C g 22 alk (en) yl radical
- R 5 stands for H or R 4
- n stands for a natural number.
- the viscosity of the agents according to the invention can be measured using customary standard methods (for example Brookfield viscometer LVT-II 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 1000 to 4000 mPas, values between 1300 to 3000 mPas being particularly preferred.
- the pH of the undiluted products according to the invention is preferably in a range from 6 to 11, particularly preferably between 7 and 10 and in particular between 7.5 and 9.
- the agents according to the invention can contain further ingredients which further improve the application technology and / or aesthetic properties of the detergent compositions.
- preferred detergent compositions further contain one or more substances from the group of bleaching agents, bleach activators, electrolytes, non-aqueous solvents, pH regulators, fragrances, dyes and enzyme stabilizers.
- sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
- Further bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
- Bleaches from the group of organic bleaches can also be used.
- Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide.
- organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids.
- Preferred representatives are (a) 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, ⁇ - phthalic acid [Phthaloiminoperoxy-hexanoic acid (PAP)], o-carboxybenzamidoperoxycaproic acid, N- nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperocysebacic acid
- Chlorine or bromine-releasing substances can also be used as bleaching agents.
- Suitable chlorine or bromine-releasing materials include, for example, heterocyclic N-bromo- and N-chloramides, 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-dimethylhydanthoin are also suitable.
- bleach activators can be incorporated into the detergent compositions.
- Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic 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 number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
- polyacylated alkylenediamines especially tetraacetylethylene diamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N- Acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetoxy and 2,5-diacetyloxy and 2,5-glycethylacetyl, ethylene glycol 2,5-dihydrofuran.
- TAED
- bleach catalysts can also 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 salt complexes or carbonyl complexes.
- Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can also be used as bleaching catalysts.
- Organic cobuilders which can be used in the dishwasher detergents according to the invention are, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates.
- Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function.
- these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as 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 of these.
- the acids themselves can also be used.
- the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH value of cleaning agents.
- Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.
- Polymeric polycarboxylates are also suitable as builders, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.
- the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M of the respective acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used.
- GPC gel permeation chromatography
- the measurement was made against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard.
- the against polystyrene sulfone Acid-measured molar masses are generally significantly higher than the molar masses 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 from 2000 to 10000 g mol, and particularly preferably from 3000 to 5000 g / mol, can in turn 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 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 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 agents is preferably 0 to 5% by weight, in particular 0.5 to 2.5% by weight.
- phosphonates are, in particular, hydroxyalkane or aminoalkane phosphonates.
- hydroxyalkane phosphonates l-hydroxyethane-l, l-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, the disodium salt reacting neutrally and the tetrasodium salt in an alkaline manner (pH 9).
- Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs.
- EDTMP hexasodium salt of EDTMP or as the hepta and octa sodium salt of DTPMP.
- HEDP is preferably used as the builder from the class of the phosphonates.
- the aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, especially if the agents also contain bleach, hold, be preferred to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
- the phosphonates content of preferred detergent compositions is 0 to 3% by weight, preferably 0.1 to 2.5% by weight and in particular 0.2 to 2% by weight.
- a wide number of different salts can be used as the electrolyte.
- Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. From a production 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 agents according to the invention is usually 0.5 to 5% by weight.
- Non-aqueous solvents which can be used in the agents according to the invention in addition to the non-surfactant, water-soluble, liquid binders come, for example, from the group of mono- or polyhydric alcohols or alkanolamines, provided they are miscible with water in the concentration range indicated.
- the solvents are preferably selected from ethanol, n- or i-propanol, butanols and ethanolamines.
- Non-aqueous solvents can be used in the cleaning agent compositions according to the invention in amounts between 0.5 and 10% by weight, but preferably below 5% by weight and in particular below 3% by weight.
- pH adjusting agents In order to bring the pH of the agents according to the invention into the desired range, the use of pH adjusting agents can be indicated. All known acids or alkalis can be used here, provided that their use is not prohibited for application-related or ecological reasons or for reasons of consumer protection. The amount of these adjusting agents usually does not exceed 5% by weight of the total formulation.
- the agents according to the invention can be colored with suitable dyes.
- Preferred dyes the selection of which is not difficult for the person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the compositions and to light, and none pronounced substantivity towards tableware materials, especially plastics, so as not to stain them.
- substances which stabilize the enzymes and thus prevent loss of activity can also be added to the detergent compositions according to the invention.
- These substances originate, 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% by weight of boric acid, in particular 1 to 2% by weight, in each case based on the total agent.
- the agents according to the invention can be produced by simple mixing in continuous or discontinuous processes.
- the water-soluble builders are advantageously dissolved in water and stirred intensively in a mixer.
- optional components can also be added, with the addition of surfactants and viososity regulators being recommended at this point in time if the agents according to the invention are to contain these substances.
- the aqueous solution can also be heated to 30 to 50 ° C. to accelerate the homogeneous distribution.
- the non-surfactant, water-soluble binder and further optionally contained ingredients such as dyes, electrolytes and others are subsequently mixed in, temperature-labile substances such as perfume and / or enzymes advantageously only being stirred in after cooling.
- the resulting product can be further diluted with water.
- the total water content of the products according to the invention can vary depending on the amount of builders and non-surfactant, water-soluble, liquid binders.
- the water content is below 40% by weight, preferably below 35% by weight and in particular below 30% by weight, in each case based on the total composition, water content above 5% by weight, preferably above 10 % By weight and in particular above 15% by weight are preferred.
- the agents E1 to E5 according to the invention were countered in a household dishwasher (Miele G 590 with universal program) under the following washing conditions tested a commercially available dishwashing detergent in powder form: 55 ° C / 16 ° d water hardness measured in the main wash cycle (ie "harsh conditions").
- the dosage for both the commercially available powder and for the aqueous products according to the invention was 25 g in each case.
- the agents according to the invention had comparable cleaning performance to the powdery cleaner. With the agents E3 and E4 according to the invention, these performances were consistently better than those of the comparative example V.
- the storage stability of the agents was checked on the basis of the composition El.
- the cleaning performance of various types of soiling was checked under the above. Conditions (dishwasher, dosage, water hardness, temperature) determined. Additional quantities of the product El were stored for 4 weeks at room temperature (El ') and at 40 ° C. (El ").
- the cleaning performance is given in the following table, with a visual evaluation with the values 0 (no cleaning) to 10 (complete Cleaning).
- the table shows that even after four weeks of storage, the agents do not show any loss in performance, but maintain their high level of performance. Storage stability, a high degree of cleaning performance and the preservation of the original enzyme activity are guaranteed by the agents according to the invention.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Detergent Compositions (AREA)
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19852135 | 1998-11-12 | ||
DE19852135A DE19852135A1 (de) | 1998-11-12 | 1998-11-12 | Wäßrige Geschirreinigungsmittel |
PCT/EP1999/003813 WO2000029533A1 (de) | 1998-11-12 | 1999-06-02 | Wässrige geschirrreinigungsmittel |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1129160A1 true EP1129160A1 (de) | 2001-09-05 |
EP1129160B1 EP1129160B1 (de) | 2008-03-12 |
Family
ID=7887521
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP99927840A Expired - Lifetime EP1129160B1 (de) | 1998-11-12 | 1999-06-02 | Wässrige geschirrreinigungsmittel |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP1129160B1 (de) |
AT (1) | ATE389007T1 (de) |
DE (2) | DE19852135A1 (de) |
ES (1) | ES2302381T3 (de) |
WO (1) | WO2000029533A1 (de) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017148990A1 (en) | 2016-03-02 | 2017-09-08 | Unilever N.V. | Detergent composition in the form of a suspension |
WO2017148989A1 (en) | 2016-03-02 | 2017-09-08 | Unilever N.V. | Pourable detergent suspension comprising a dyed fluid phase and suspended particles |
WO2017148985A1 (en) | 2016-03-02 | 2017-09-08 | Unilever N.V. | Pourable detergent composition |
WO2017153528A1 (en) | 2016-03-11 | 2017-09-14 | Unilever N.V. | Pourable detergent suspension comprising bleach catalyst granules |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
-
1998
- 1998-11-12 DE DE19852135A patent/DE19852135A1/de not_active Ceased
-
1999
- 1999-06-02 ES ES99927840T patent/ES2302381T3/es not_active Expired - Lifetime
- 1999-06-02 EP EP99927840A patent/EP1129160B1/de not_active Expired - Lifetime
- 1999-06-02 DE DE59914690T patent/DE59914690D1/de not_active Expired - Lifetime
- 1999-06-02 WO PCT/EP1999/003813 patent/WO2000029533A1/de active IP Right Grant
- 1999-06-02 AT AT99927840T patent/ATE389007T1/de active
Non-Patent Citations (1)
Title |
---|
See references of WO0029533A1 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017148990A1 (en) | 2016-03-02 | 2017-09-08 | Unilever N.V. | Detergent composition in the form of a suspension |
WO2017148989A1 (en) | 2016-03-02 | 2017-09-08 | Unilever N.V. | Pourable detergent suspension comprising a dyed fluid phase and suspended particles |
WO2017148985A1 (en) | 2016-03-02 | 2017-09-08 | Unilever N.V. | Pourable detergent composition |
WO2017153528A1 (en) | 2016-03-11 | 2017-09-14 | Unilever N.V. | Pourable detergent suspension comprising bleach catalyst granules |
Also Published As
Publication number | Publication date |
---|---|
DE59914690D1 (de) | 2008-04-24 |
DE19852135A1 (de) | 2000-05-18 |
ES2302381T3 (es) | 2008-07-01 |
WO2000029533A1 (de) | 2000-05-25 |
EP1129160B1 (de) | 2008-03-12 |
ATE389007T1 (de) | 2008-03-15 |
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