EP2576753B1 - Détergent pour lave-vaisselle - Google Patents

Détergent pour lave-vaisselle Download PDF

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Publication number
EP2576753B1
EP2576753B1 EP11723306.4A EP11723306A EP2576753B1 EP 2576753 B1 EP2576753 B1 EP 2576753B1 EP 11723306 A EP11723306 A EP 11723306A EP 2576753 B1 EP2576753 B1 EP 2576753B1
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EP
European Patent Office
Prior art keywords
cleaning agent
weight
acid
total weight
proportion
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EP11723306.4A
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German (de)
English (en)
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EP2576753A1 (fr
Inventor
Thomas Eiting
Dorota SENDOR-MÜLLER
Johannes Zipfel
Arnd Kessler
Thorsten Bastigkeit
Christian Nitsch
Sven Müller
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to PL11723306T priority Critical patent/PL2576753T3/pl
Publication of EP2576753A1 publication Critical patent/EP2576753A1/fr
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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
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38663—Stabilised liquid enzyme compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof

Definitions

  • the present application is directed to liquid cleaners, especially liquid automatic dishwashing detergents containing amylase preparations which are stabilized by calcium lactate.
  • hydrolytic enzymes such as proteases, amylases or lipases are part of numerous textile or dishwashing detergents because of their direct cleaning action.
  • proteases in particular serine proteases, to which the subtilases according to the invention are also calculated, are used for degrading proteinaceous soils on the items to be cleaned.
  • subtilases occupy an outstanding position due to their favorable enzymatic properties such as stability or pH optimum.
  • amylases in particular the ⁇ -amylases are widely used.
  • ⁇ -Amylases (E.C. 3.2.1.1) hydrolyze internal ⁇ -1,4-glycosidic bonds of starch and starch-like polymers.
  • Detergents and cleaning enzymes are formulated in both solid and liquid form.
  • the group of solid enzyme preparations includes, in particular, the enzyme granules consisting of several ingredients, which in turn are preferably incorporated into solid detergents and cleaners.
  • liquid or gel detergents and cleaners often contain liquid enzyme preparations, which, unlike the enzyme granules, are much less protected against external influences.
  • the JP 2006-315418 describes aqueous, liquid detergents with surfactants, amylases, organic acids, such as lactic acid, and calcium salts.
  • US3819528 discloses aqueous compositions with amylase, calcium salt and glycol.
  • the US patent US 3676374 relates to liquid enzyme-containing detergents comprising inter alia alkyl sulfonates having a desired enzyme activity upon storage.
  • a second group of known stabilizers form borax, boric acids, boronic acids or their salts or esters.
  • These include, in particular, derivatives having aromatic groups, for example ortho, meta or para-substituted phenylboronic acids, in particular 4-formylphenylboronic acid (4-FPBA) or the salts or esters of the abovementioned compounds.
  • 4-FPBA 4-formylphenylboronic acid
  • the latter compounds as enzyme stabilizers are disclosed, for example, in the international patent application WO 96/41859 A1 (Novo Nordisk ).
  • boric acids and boric acid derivatives for example, often have the disadvantage that they form unwanted by-products with other ingredients of a composition, in particular detergent ingredients, so that they are no longer available for the desired cleaning purpose or even as an impurity in the compositions concerned stay behind on the laundry. Furthermore, boric acids or borates are considered to be disadvantageous from an environmental point of view.
  • the methods for the stabilization of enzymes which have hitherto been found and described in the prior art can not be used in every detergent formulation and can not always be sufficiently adequate with regard to their stabilizing effect.
  • the object of the present application was therefore to provide an improved stabilizing agent for enzymes and an enzyme-containing cleaning agent with increased enzyme stability. It has been found that liquid, aqueous amylase preparations can be surprisingly stabilized by the addition of calcium lactate.
  • the washing or cleaning agent preparations according to the invention contain as their first essential constituent at least one amylase preparation.
  • amylases which can be used according to the invention are the ⁇ -amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae as well as the further developments of the abovementioned amylases which are improved for use in detergents and cleaners. Furthermore, for this purpose, the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).
  • Liquid detergents preferred according to the invention contain, based on their total weight, between 0.001 and 5.0% by weight, preferably between 0.01 and 4.0% by weight and in particular between 0.05 and 3.0% by weight of amylase preparations. Particular preference is given to detergents which, based on their total weight, contain between 0.075 and 2.0% by weight of amylase preparations.
  • the liquid detergents according to the invention may contain further washing- or cleaning-active enzyme.
  • the proportion by weight of all washing or cleaning active enzyme preparations in the total weight of the cleaning agent is preferably between 1.0 and 15 wt .-%, preferably between 1.5 and 12 wt .-%, particularly preferably between 2.0 and 10 wt .-% and in particular between 2.5 and 8 wt .-%.
  • the enzymes used with particular preference include in particular proteases.
  • proteases those of the subtilisin type are preferable. Examples of these are the subtilisins BPN 'and Carlsberg and their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase which can no longer be assigned to the subtilisins in the narrower sense, Proteinase K and the proteases TW3 and TW7.
  • Liquid detergents preferred according to the invention contain, based on their total weight, between 0.002 and 7.0% by weight, preferably between 0.02 and 6.0% by weight and in particular between 0.1 and 5.0% by weight of protease preparations. Particular preference is given to detergents which, based on their total weight, contain between 0.2 and 4.0% by weight of protease preparations.
  • Washing or cleaning-active amylases and proteases are generally not provided in the form of the pure protein but rather in the form of stabilized, storable and transportable preparations.
  • Such prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or added with stabilizers or further auxiliaries.
  • the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer.
  • further active ingredients for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied.
  • Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes.
  • such granules for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.
  • the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations.
  • Protease and amylase preparations preferably used according to the invention contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, more preferably between 0.4 and 20% by weight and in particular between 0.8 and 10% by weight of the enzyme protein.
  • lipases or cutinases are also usable according to the invention.
  • these include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L.
  • the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens. It is also possible to use lipases, or cutinases, whose initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii.
  • the agents according to the invention may contain cellulases.
  • Oxidoreductases for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention to increase the bleaching effect.
  • a second essential component of the cleaning agents according to the invention is the Ca 2+ ion source.
  • the organic calcium salts have been found.
  • the proportion by weight of the organic calcium salts in the total weight of the detergents according to the invention can vary within wide limits, however, such detergents have proven to be particularly stable, which, based on their total weight 0.01 to 5.0 wt .-%, preferably 0, 02 to 3.0 wt .-%, particularly preferably 0.05 to 2.0 wt .-% and in particular 0.01 to 1.0 wt .-% Ca 2+ ions of calcium salts.
  • lactic acid or a lactic acid salt are the salts of the alkali and alkaline earth metals.
  • the proportion by weight of the lactic acid or the lactic acid salt in the total weight of the cleaning agent is preferably 0.05 to 10 wt .-%, preferably 0.1 to 8.0 wt .-%, particularly preferably 0.2 to 5.0 wt. -% and in particular 0.25 to 2.5 wt .-%.
  • Liquid cleaning agent characterized in that the liquid cleaning agent contains calcium lactate, wherein the proportion by weight of the calcium lactate in the total weight of the cleaning agent preferably 0.05 to 10 wt .-%, preferably 0.1 to 8.0 wt .-%, particularly preferably 0, 2 to 5.0 wt .-% and in particular 0.25 to 2.5 wt .-%, are therefore preferred according to the invention.
  • composition of some further preferred cleaning agents according to the invention can be taken from the following tables (in% by weight): Table 1 Recipe 1 Recipe 2 Recipe 3 Recipe 4 Amylase preparation 0.001 to 5.0 0.01 to 4.0 0.05 to 3.0 0.075 to 2.0 Ca ion source 0.05 to 10 0.1 to 8.0 0.2 to 5.0 0.25 to 2.5 Lactic acid (salt) 0.05 to 10 0.1 to 8.0 0.2 to 5.0 0.25 to 2.5 water 20 to 70 20 to 70 20 to 70 20 to 70 20 to 70 Misc Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Recipe 1 Recipe 2 Recipe 3 Recipe 4 Amylase preparation 0.001 to 5.0 0.01 to 4.0 0.05 to 3.0 0.075 to 2.0 calcium lactate 0.05 to 10 0.1 to 8.0 0.2 to 5.0 0.25 to 2.5 water 20 to 70 20 to 70 20 to 70 20 to 70 Misc Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add
  • the inventive cleaning agents contain an organic solvent.
  • Preferred organic solvents are selected from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers.
  • the solvents are selected from ethanol, n- or i-propanol, butanol, glycol, propane or butanediol, glycerol, diglycol, propyl or butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, Etheylenglykolmonon-butyl ether, diethylene glycol methyl ether, di-ethylenglykolethylether , Propylenglykolmethyl-, ethyl or propyl ether, Dipropylenglykolmethyl- or ethyl ether, methoxy, ethoxy or Butoxytrigly
  • a particularly preferred organic solvent which is particularly effective in stabilizing the detergents is glycerin and 1,2-propylene glycol.
  • a second component of the cleaning agents according to the invention is a sugar alcohol (alditol).
  • the group of alditols includes noncyclic polyols of the formula HOCH 2 [CH (OH)] n CH 2 OH.
  • the alditols include, for example, mannitol (mannitol), isomalt, lactitol, sorbitol (sorbitol) and xylitol (xylitol), threitol, erythritol and arabitol.
  • the sorbitol has been found.
  • the weight proportion of the sugar alcohol in the total weight of the automatic dishwashing agent is preferably 1.0 to 10 wt .-%, preferably 2.0 to 8.0 wt .-% and in particular 3.0 to 6.0 wt .-%.
  • a third preferred constituent of the cleaning agents according to the invention is the boric acid or the boric acid derivative.
  • the boric acid are preferably used in particular the boronic acids or their salts or esters, including especially derivatives with aromatic groups, such as ortho-, meta- or para-substituted phenylboronic, in particular 4-formylphenyl-boronic acid (4-FPBA), or the Salts or esters of the compounds mentioned.
  • a particularly preferred boric acid derivative which is particularly effective with respect to the stabilization of the detergent or cleaning agent preparation is 4-formylphenylboronic acid.
  • Preferred cleaning agents according to the invention are therefore characterized in that the cleaning agent is a phenylboronic acid derivative having the structural formula in which R is hydrogen, a hydroxyl, a C 1 -C 6 alkyl, a substituted C 1 -C 6 alkyl, a C 1 -C 6 alkenyl or a substituted C 1 -C 6 alkenyl group wherein 4-formyl-phenylboronic acid is particularly preferred and the weight fraction of the phenylboronic acid derivative in the total weight of the cleaning agent preferably 0.001 to 2 wt .-%, preferably 0.01 to 1.5 wt .-% and in particular 0.1 to 1 wt .-% is.
  • the liquid detergents may contain, in addition to the ingredients described above, other substances which are active in washing or cleaning, substances from the group of surfactants, Builders, polymers, glass corrosion inhibitors, corrosion inhibitors, fragrances and perfume carriers are preferred. These preferred ingredients will be described in more detail below.
  • composition of some further preferred cleaning agents according to the invention can be taken from the following tables (in% by weight): Table 3 Recipe 1 Recipe 2 Recipe 3 Recipe 4 Amylase preparation 0.001 to 5.0 0.01 to 4.0 0.05 to 3.0 0.075 to 2.0 Ca ion source 0.05 to 10 0.1 to 8.0 0.2 to 5.0 0.25 to 2.5 Lactic acid (salt) 0.05 to 10 0.1 to 8.0 0.2 to 5.0 0.25 to 2.5 sorbitol 1.0 to 10 2.0 to 8.0 2.0 to 8.0 3.0 to 6.0 water 20 to 70 20 to 70 20 to 70 20 to 70 Misc Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Recipe 1
  • the cleaning performance of inventive enzyme-containing preparations can be significantly improved both in comparison to surfactant-free system as well as compared to systems containing alternative nonionic surfactants, for example from the group of polyalkoxylated Contain fatty alcohols.
  • nonionic surfactants having one or more free hydroxyl groups on one or both terminal alkyl radicals, the stability of the enzymes contained in the detergent or cleaning agent preparations according to the invention can be markedly improved.
  • end-capped poly (oxyalkylated) nonionic surfactants which, in accordance with the formula R 1 O [CH 2 CH 2 O] x CH 2 CH (OH) R 2 , in addition to a radical R 1 , which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 2 to 30 carbon atoms, preferably having from 4 to 22 carbon atoms, furthermore having a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R 2 having from 1 to 30 carbon atoms, where x is from 1 to 30 carbon atoms 90, preferably for values between 30 and 80 and in particular for values between 30 and 60.
  • surfactants of the formula R 1 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y CH 2 CH (OH) R 2 , in which R 1 is a linear or branched aliphatic hydrocarbon radical with 4 R 2 is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is values between 0.5 and 1.5 and y is a value of at least 15.
  • the group of these nonionic surfactants includes, for example, the C 2-26 fatty alcohol (PO) 1 - (EO) 15-40 -2-hydroxyalkyl ethers, in particular also the C 8-10 fatty alcohol (PO) 1 - (EO) 22 -2 -hydroxydecylether.
  • nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j R 2 in which R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 3 is H or a methyl, ethyl, n-propyl, isoPropyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5.
  • each R 3 in the above formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 may be different.
  • R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred.
  • R 3 H, -CH 3 or -CH 2 CH 3 are particularly preferred.
  • Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
  • each R 3 in the above formula may be different if x ⁇ 2.
  • the alkylene oxide unit in the square bracket can be varied.
  • the value 3 for x has been selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,
  • R 1 , R 2 and R 3 are as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18.
  • Particularly preferred are surfactants in which the radicals R 1 and R 2 has 9 to 14 C atoms, R 3 is H and x assumes values of 6 to 15.
  • Preferred automatic dishwashing agents according to the invention may contain, in addition to the nonionic surfactants described above, further surfactants, in particular amphoteric surfactants.
  • further surfactants in particular amphoteric surfactants.
  • the proportion of anionic surfactants in the total weight of the detergents is preferably limited.
  • preferred liquid detergents are characterized in that the detergent based on its total weight less than 5, 0 wt .-%, preferably less than 3.0 wt .-%, more preferably less than 1.0 wt .-% and in particular no Contains anionic surfactant.
  • anionic surfactants is omitted in particular to avoid excessive foaming.
  • Another preferred ingredient of detergents according to the invention are complexing agents.
  • Particularly preferred complexing agents are the phosphonates.
  • the complex-forming phosphonates comprise a number of different compounds such as, for example, diethylenetriaminepenta (methylenephosphonic acid) (DTPMP). Hydroxyalkane or aminoalkane phosphonates are particularly preferred in this application.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • 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. as the hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP used.
  • the builder used here is preferably HEDP from the class of phosphonates.
  • the aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
  • washing or cleaning compositions A which contain as phosphonates 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or diethylenetriaminepenta (methylenephosphonic acid) (DTPMP).
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • DTPMP diethylenetriaminepenta
  • the cleaning agents according to the invention may contain two or more different phosphonates.
  • Preferred cleaning agents according to the invention are characterized in that the cleaning agent contains at least one complexing agent from the group of the phosphonates, preferably 1-hydroxyethane-1,1-diphosphonate, wherein the weight fraction of the phosphonate in the total weight of the cleaning agent is preferably 0.1 and 8.0 wt .-%, preferably 0.2 and 5.0 wt .-% and in particular 0.5 and 3.0 wt .-% is.
  • the cleaning agents according to the invention preferably further comprise builder.
  • the builders include, in particular, the silicates, carbonates, organic co-builders and, where there are no ecological prejudices against their use, also the phosphates.
  • the alkali metal phosphates with particular preference of pentasodium triphosphate, Na 5 P 3 O 10 (sodium tripolyphosphate) or pentapotassium triphosphate, K 5 P 3 O 10 (potassium tripolyphosphate), have the greatest importance for the agents according to the invention.
  • preferred agents contain this phosphate (s), preferably pentakalium triphosphate, wherein the weight fraction of the phosphate in the total weight of the cleaning agent is preferably 5.0 and 40, wt. -%, preferably 10 and 30 wt .-% and in particular 12 and 25 wt .-% is.
  • s preferably pentakalium triphosphate
  • organic co-builders are polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders and phosphonates. These classes of substances are described below.
  • Useful organic builders are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or 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.
  • the free acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners.
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
  • the citric acid or salts of citric acid are used with particular preference as builder substance.
  • Another particularly preferred builder substance is methylglycine diacid (MGDA).
  • polymeric polycarboxylates for example the alkali metal salts of polyacrylic acid or of 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 molar masses measured against polystyrenesulfonic acids are generally significantly 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.
  • Oxydisuccinates and other derivatives of disuccinates are other suitable co-builders.
  • ethylenediamine-N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts.
  • glycerol disuccinates and glycerol trisuccinates are also preferred in this context.
  • preferred liquid detergents comprise at least one hydrophobically modified polymer, preferably a hydrophobically modified carboxylic acid group-containing polymer, wherein the weight fraction of the hydrophobically modified polymer in the total weight of the cleaning agent is preferably 0.1 to 10% by weight. %, preferably between 0.2 and 8.0 wt .-% and in particular 0.4 to 6.0 wt .-% is.
  • detergent-active polymers may be included in the detergent.
  • the proportion by weight of cleaning-active polymers in the total weight of mechanical cleaning agents according to the invention is preferably from 0.1 to 20% by weight, preferably from 1.0 to 15% by weight and in particular from 2.0 to 12% by weight.
  • cleaning-active polymers are preferably used sulfonic acid-containing polymers, in particular from the group of copolymeric polysulfonates.
  • These copolymeric polysulfonates contain, in addition to sulfonic acid-containing (s) monomer (s) at least one monomer from the group of unsaturated carboxylic acids.
  • unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, ⁇ -cyanoacrylic acid, crotonic acid, ⁇ -phenyl-acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof. It goes without saying that it is also possible to use the unsaturated dicarboxylic acids.
  • Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3 Methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate , Sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of said acids or their water-soluble
  • the sulfonic acid groups may be wholly or partly in neutralized form.
  • the use of partially or fully neutralized sulfonic acid-containing copolymers is preferred according to the invention.
  • the molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired end use.
  • Preferred automatic dishwashing agents are characterized in that the copolymers have molar masses of from 2000 to 200,000 gmol -1 , preferably from 4000 to 25,000 gmol -1 and in particular from 5000 to 15,000 gmol -1 .
  • the copolymers further comprise at least one nonionic, preferably hydrophobic monomer in addition to carboxyl-containing monomer and sulfonic acid-containing monomer.
  • nonionic, preferably hydrophobic monomer in addition to carboxyl-containing monomer and sulfonic acid-containing monomer.
  • nonionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 , 4-trimethylpentene-1, 2,4,4-trimethylpentene-2,3,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethlyhexene-1,3,5-dimethylhexene-1,4 , 4-dimethylhexane-1, ethylcyclohexyne, 1-octene, ⁇ -olefins having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and
  • the proportion by weight of the sulfonic acid-containing copolymers in the total weight of inventive detergents is preferably 0.1 to 15 wt .-%, preferably 1.0 to 12 wt .-% and in particular 2.0 to 10 wt .-%.
  • a further subject of the present application is a method for the automated cleaning of dishes using a machine dishwashing detergent according to the invention.
  • the dosage of the cleaning agent according to the invention in the cleaning liquor can be done for example by means of the metering chamber in the door or an additional metering in the interior of the dishwasher.
  • the cleaning agent can also be applied directly to the soiled dishes or to one of the inner walls of the dishwasher, for example the inside of the door.
  • the implementation of the method according to the invention takes place in the interior of a commercial dishwasher.
  • the cleaning program can be selected and determined in a dishwasher usually before the dishwashing process by the consumer.
  • the cleaning program of the dishwasher used in the method according to the invention comprises at least one prewash cycle and one cleaning cycle. Cleaning programs which include further cleaning or rinsing cycles, for example a rinse cycle, are preferred according to the invention.
  • the process according to the invention is particularly preferably part of a cleaning program, comprising a prewash cycle, a cleaning cycle and a rinse cycle.
  • the automatic dishwashing detergent programs may differ in terms of their duration, their water consumption and the temperature of the cleaning liquor.
  • the inventive method is preferably used in conjunction with such cleaning programs in which the wash liquor is heated in the course of the cleaning cycle.
  • the cleaning cycle in the course of which the cleaning agent according to the invention is metered into the interior of the dishwasher, is characterized in that in its course the temperature of the cleaning liquor is above 30 ° C., preferably above 40 ° C. and especially above 50 ° C increases.
  • Preferred embodiments of the automatic dishwashing process according to the invention result mutatis mutandis from the previous description of preferred embodiments of the detergent according to the invention, to which reference is made to avoid repetition at this point.
  • V1 and E1 The following two detergent formulations V1 and E1 were provided: V1 [% by weight] E1 [% by weight] potassium 18.8 8.8 sodium 5.0 5.0 sorbitol 7.2 7.2 Polycarboxylate 1) 2.5 0.4 Polycarboxylate 2) 7.5 7.5 KOH 2.4 0.7 hydroxy mixed 2.0 2.0 1,2-propylene glycol 0.9 0.9 Amylase preparation 0.75 0.75 Protease preparation 0.9 0.9 phosphonate 2.5 0.8 calcium lactate - 0.5 Misc (dye, perfume, water etc) Add 100 Add 100 1) Hydrophobically modified polycarboxylate 2) Hydrophob modified polysulfonate For both cleaning agents V1 and E1 the cleaning performance was determined according to the IKW method (Miele G 698 SC, 50 ° C normal, 21 ° dH).
  • the cleaning agent stabilized by the addition of calcium lactate in particular after storage on the stains relevant for the amylase, has clearly better cleaning results than the calcium-lactate-free cleaning agent.
  • the cleaning agent stabilized by the addition of calcium lactate in particular after storage on the stains relevant for the amylase, has clearly better cleaning results than the calcium-lactate-free cleaning agent.

Claims (9)

  1. Agent détergent liquide comprenant
    a) 20 à 70 % en poids d'eau
    b) au moins une préparation d'amylase
    c) au moins une source d'ions Ca2+
    d) de l'acide lactique ou un sel d'acide lactique,
    caractérisé en ce que l'agent détergent contient au moins un alditol, de préférence du sorbitol, dans lequel la proportion en poids de l'alditol dans le poids total de l'agent détergent est de préférence de 1,0 à 10 % en poids, préférablement de 2,0 à 8,0 % en poids et en particulier de 3,0 à 6,0 % en poids.
  2. Agent détergent liquide comprenant
    a) 20 à 70 % en poids d'eau
    b) au moins une préparation d'amylase
    c) au moins une source d'ions Ca2+
    d) de l'acide lactique ou un sel d'acide lactique,
    caractérisé en ce que l'agent détergent contient au moins un tensio-actif non ionique, au moins un tensio-actif non ionique étant choisi dans le groupe des hydroxyéthers mélangés, dans lequel la proportion en poids du tensio-actif non ionique dans le poids total de l'agent détergent est de préférence de 0,5 à 10 % en poids, préférablement de 1,0 à 8,0 % en poids et en particulier de 2,0 à 6,0 % en poids.
  3. Agent détergent liquide selon la revendication 1 ou 2, caractérisé en ce que la proportion en poids des protéines activées de la préparation d'amylase dans le poids total de l'agent détergent est comprise entre 0,001 et 5,0 % en poids, de préférence entre 0,01 et 4,0 % en poids, préférablement entre 0,5 et 3,0 % en poids et en particulier entre 0,075 et 2,0 % en poids.
  4. Agent détergent liquide selon l'une quelconque des revendications précédentes, caractérisé en ce que l'agent détergent liquide contient du lactate de calcium, la proportion en poids du lactate de calcium dans le poids total de l'agent détergent étant de préférence de 0,05 à 10 % en poids, préférablement de 0,1 à 8,0 % en poids, de manière particulièrement préférée de 0,2 à 5,0 % en poids et en particulier de 0,025 à 2,5 % en poids.
  5. Agent détergent liquide selon l'une quelconque des revendications précédentes, caractérisé en ce que l'agent détergent contient un dérivé d'acide phénylboronique ayant une structure de formule
    Figure imgb0004
     dans laquelle R représente l'hydrogène, un alcényle hydroxyle, un alkylalcényle en C1-C6, un alkylalcényle en C1-C6 substitué, un alcényle en C1-C6 ou un groupe alcényle en C1-C6 substitué, l'acide 4-formyl-phényl-boronique étant particulièrement préféré et la proportion en poids du dérivé d'acide phénylboronique dans le poids total de l'agent détergent étant de préférence de 0,001 à 2 % en poids, préférablement de 0,01 à 1,5 % en poids et en particulier de 0,1 à 1 % en poids.
  6. Agent détergent liquide selon l'une quelconque des revendications précédentes, caractérisé en ce que l'agent détergent contient au moins un agent complexant choisi parmi le groupe des phosphonates, de préférence le 1-hydroxyéthane-1,1-disphosphonate, la proportion en poids du phosphonate dans le poids total de l'agent détergent étant comprise de préférence 0,1 et 8,0 % en poids, préférablement 0,2 et 5,0 % en poids et en particulier 0,5 et 3,0 % en poids.
  7. Agent détergent liquide selon l'une quelconque des revendications précédentes, caractérisé en ce que l'agent détergent contient au moins un adjuvant du groupe des phosphates, de préférence le triphosphate pentasodique, la proportion en poids du phosphate dans le poids total de l'agent détergent étant comprise de préférence 5,0 et 40 % en poids, préférablement 10 et 30 % en poids et en particulier 12 et 25 % en poids.
  8. Agent détergent liquide selon l'une quelconque des revendications précédentes, caractérisé en ce que l'agent détergent contient au moins un polymère à modification hydrophobe, de préférence un polymère à modification hydrophobe contenant un groupe d'acide carboxylique, la proportion en poids du polymère à modification hydrophobe dans le poids total de l'agent détergent étant de préférence de 0,1 à 10 % en poids, préférablement entre 0,2 et 8,0 % en poids et en particulier de 0,4 à 6,0 % en poids.
  9. Procédé pour le lavage de la vaisselle en machine utilisant un produit de lavage de la vaisselle selon l'une quelconque des revendications précédentes.
EP11723306.4A 2010-05-27 2011-05-05 Détergent pour lave-vaisselle Not-in-force EP2576753B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL11723306T PL2576753T3 (pl) 2010-05-27 2011-05-05 Środek do maszynowego zmywania naczyń

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102010029348A DE102010029348A1 (de) 2010-05-27 2010-05-27 Maschinelles Geschirrspülmittel
PCT/EP2011/057180 WO2011147665A1 (fr) 2010-05-27 2011-05-05 Détergent pour lave-vaisselle

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Publication Number Publication Date
EP2576753A1 EP2576753A1 (fr) 2013-04-10
EP2576753B1 true EP2576753B1 (fr) 2017-07-05

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US (1) US9719055B2 (fr)
EP (1) EP2576753B1 (fr)
DE (1) DE102010029348A1 (fr)
ES (1) ES2640989T3 (fr)
HU (1) HUE036668T2 (fr)
PL (1) PL2576753T3 (fr)
WO (1) WO2011147665A1 (fr)

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DE102012200959A1 (de) 2012-01-24 2013-07-25 Henkel Ag & Co. Kgaa Enzymhaltiges Wasch- oder Reinigungsmittel
DE102012203475A1 (de) 2012-03-06 2013-09-12 Henkel Ag & Co. Kgaa Enzymhaltiges Handgeschirrspülmittel
DE102013202450A1 (de) 2013-02-14 2014-08-14 Henkel Ag & Co. Kgaa Flüssiges Wasch- oder Reinigungsmittel mit verbesserter Enzymstabilität
EP3272847B1 (fr) * 2013-09-09 2022-01-19 Ecolab USA Inc. Élimination synergique de taches par le biais d'une nouvelle combinaison de chélateurs
DE102013224250A1 (de) 2013-11-27 2015-05-28 Henkel Ag & Co. Kgaa Lipasestabilisierung in Geschirrspülmitteln

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DE68923398T2 (de) 1988-05-12 1996-01-25 Procter & Gamble Flüssige Universalwaschmittel, welche anionische und nichtionische oberflächenaktive Mittel, Gerüststoffe und proteolytisches Enzym enthalten.
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Publication number Publication date
US20130079268A1 (en) 2013-03-28
DE102010029348A1 (de) 2011-12-08
HUE036668T2 (hu) 2018-07-30
PL2576753T3 (pl) 2017-12-29
EP2576753A1 (fr) 2013-04-10
WO2011147665A1 (fr) 2011-12-01
ES2640989T3 (es) 2017-11-07
US9719055B2 (en) 2017-08-01

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