EP2358853B1 - Maschinelles geschirrspülmittel - Google Patents

Maschinelles geschirrspülmittel Download PDF

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Publication number
EP2358853B1
EP2358853B1 EP09764241.7A EP09764241A EP2358853B1 EP 2358853 B1 EP2358853 B1 EP 2358853B1 EP 09764241 A EP09764241 A EP 09764241A EP 2358853 B1 EP2358853 B1 EP 2358853B1
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EP
European Patent Office
Prior art keywords
weight
acid
dishwasher detergent
group
automatic dishwasher
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EP09764241.7A
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German (de)
English (en)
French (fr)
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EP2358853A1 (de
Inventor
Johannes Zipfel
Nadine Warkotsch
Arnd Kessler
Christian Nitsch
Dorota SENDOR-MÜLLER
Britta Strauss
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to PL09764241T priority Critical patent/PL2358853T3/pl
Publication of EP2358853A1 publication Critical patent/EP2358853A1/de
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • 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
    • 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
    • C11D3/378—(Co)polymerised monomers containing sulfur, e.g. sulfonate
    • 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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C11D1/721—End blocked ethers

Definitions

  • the present application describes automatic dishwashing detergents, automatic dishwashing processes using these dishwashing detergents, and the use of these dishwashing detergents to improve drying in automatic dishwashing.
  • Dishwashing detergents are available to the consumer in a variety of forms. In addition to the traditional liquid hand dishwashing detergents, machine dishwashing detergents are particularly important with the spread of household dishwashers. These automatic dishwashing agents are typically offered to the consumer in solid form, for example as powders or as tablets, but increasingly also in liquid form.
  • One of the major objectives of the machine cleaners manufacturers is to improve the cleaning and rinse performance of these compositions, with more emphasis being placed recently on the cleaning and rinse performance in low temperature or reduced water consumption cleaning cycles.
  • the rinse aid or rinse-active substances are integrated into the automatic dishwashing detergent ("more than 1" dishwashing detergent).
  • the automatic dishwashing detergent More than 1
  • Such a machine dishwashing detergent composition incorporating a specific surfactant for improving the rinsing properties is described in the European patent specification EP 1 524 313 B1 (Dalli ).
  • US7012052B1 (Procter & Gamble) discloses machine dishwashing detergents containing builders, enzymes, hydrophobically modified anionic polymers, and a mixture of nonionic surfactants. Also in DE4327327A1 (Henkel ) describes a machine dishwashing detergent, the builder, enzymes and contains a mixture of nonionic surfactants; Further, an acrylic / maleic acid copolymer is included. Mixtures of various nonionic surfactants and the use of these mixtures in detergents are disclosed in US Pat EP1764408A1 (Cognis ) DE19738866A1 (Henkel ) and DE4323252A1. (Handle ).
  • This application was based on the object to provide a machine dishwashing detergent with reduced deposit formation and improved drying and Klar Kunststoffeigenschaften, these improved drying and Klar Kunststoffischeneigenschaften especially in low-temperature cleaning cycles, ie in cleaning processes with Spülflottentemperaturen of 50 ° C or below should be achieved.
  • the present application relates to automatic dishwashing detergents.
  • Automatic dishwashing detergents are compositions which can be used to clean soiled dishes in a dishwasher automatic dishwashing process.
  • the automatic dishwasher detergents according to the invention differ, for example, from the machine rinse aid agents, which are always used in combination with automatic dishwashing detergents and do not develop their own cleaning action.
  • Dishwashing compositions according to the invention contain builder (s) and enzyme (s) to ensure their cleaning action.
  • machine dishwashing detergents contain one or more builders.
  • the proportion by weight of the builders in the total weight of the machine according to the invention Dishwashing agent is preferably 15 to 80 wt .-% and in particular 20 to 70 wt .-%.
  • the builders include in particular carbonates, phosphates, citrates, organic cobuilders and silicates.
  • the alkali metal phosphates with a particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest importance in the washing and cleaning agent industry.
  • Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO 3 ) n and orthophosphoric H 3 PO 4 in addition to higher molecular weight representatives.
  • the phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance.
  • Particularly preferred phosphates according to the invention are the pentasodium triphosphate, Na 5 P 3 O 10 (sodium tripolyphosphate) and the corresponding potassium salt pentapotassium triphosphate, K 5 P 3 O 10 (potassium tripolyphosphate).
  • the sodium potassium tripolyphosphates are also preferably used according to the invention.
  • phosphates are used as washing or cleaning substances in automatic dishwasher detergents in the context of the present application, these contain phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), in quantities from 5 to 60% by weight, preferably from 15 to 45% by weight, in particular from 20 to 40% by weight, in each case based on the weight of the automatic dishwashing detergent.
  • phosphate preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate)
  • organic co-builders are polycarboxylates / polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals, dextrins and organic cobuilders. 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 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 environmental reasons, and mixtures of these.
  • NTA nitrilotriacetic acid
  • 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.
  • Machine dishwasher detergents contain citrate as one of their essential builders.
  • Machine dishwashing detergents characterized in that they contain 2 to 40% by weight, preferably 5 to 30% by weight and in particular 7 to 20% by weight citrate, are preferred according to the invention.
  • the citrates are preferably used in combination with carbonates and / or bicarbonate.
  • Preferred automatic dishwasher detergents are therefore characterized by a builder combination of phosphate and carbonate / bicarbonate or of citrate and carbonate / bicarbonate carbonate (compare Tables 1a and 1b below).
  • builder combinations of phosphate, citrate and carbonate / bicarbonate can be realized.
  • the dishwashing detergent contains at least two builders from the group of the phosphates, carbonates and citrates, the weight fraction of these builders, based on its total weight of the automatic dishwashing agent, preferably from 5 to 80% by weight, preferably 15 to 75 wt .-% and in particular 30 to 70 wt .-% is.
  • the combination of two or more builders from the above-mentioned group has proved to be advantageous for the cleaning and rinsing performance of automatic dishwashing agents according to the invention.
  • polymeric polycarboxylates for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of 500 to 70,000 g / mol.
  • 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 have 50 to 90% by weight of acrylic acid and 50 to 10 wt .-% maleic acid.
  • Their relative molecular weight, based on free acids is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.
  • the content of the automatic dishwashing agents in (co) polymeric polycarboxylates is preferably from 0.5 to 20% by weight and in particular from 3 to 10% by weight.
  • Machine dishwashing detergents according to the invention may contain as builder crystalline layered silicates of the general formula NaMSi x O 2x + 1yH 2 O, wherein M represents sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, where Particularly preferred values for x are 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20. It is also possible to use amorphous sodium silicates with a Na 2 O: SiO 2 modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which preferably delayed release and have secondary washing properties.
  • amorphous sodium silicates with a Na 2 O: SiO 2 modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which preferably delayed release and have secondary washing properties.
  • the content of silicates is limited to amounts below 10% by weight, preferably below 5% by weight and in particular below 2% by weight.
  • Particularly preferred automatic dishwasher detergents according to the invention are silicate-free.
  • the agents according to the invention may contain alkali metal hydroxides.
  • These alkali carriers are preferred in the cleaning agents only in small amounts, preferably in amounts below 10 wt .-%, preferably below 6 wt .-%, preferably below 5 wt .-%, particularly preferably between 0.1 and 5 wt .-% and in particular between 0.5 and 5 wt .-%, each based on the total weight of the cleaning agent used.
  • Alternative automatic dishwashing detergents are free of alkali metal hydroxides.
  • Dishwashing agents according to the invention contain enzyme (s) as a second constituent. These include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or Oxidöreduktasen, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents or cleaning agents, which are preferably used accordingly. Detergents or cleaning agents contain enzymes preferably in total amounts of 1 ⁇ 10 -6 to 5 wt .-% based on active protein. The protein concentration can be determined by known methods, for example the BCA method or the biuret method.
  • subtilisin type those of the subtilisin type are preferable.
  • 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.
  • 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 and improved for use in detergents and cleaners further developments of the aforementioned amylases. Furthermore, for this purpose, the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).
  • lipases or cutinases are also usable according to the invention, in particular because of their triglyceride-splitting activities, but also in order to generate in situ peracids from suitable precursors.
  • lipases or cutinases include, for example, the lipases originally obtainable from Humicola lanuginosa ( Thermomyces lanuginosus ) or further developed, in particular those with the amino acid exchange D96L.
  • 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 protein and / or enzyme may be particularly protected during storage against damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage.
  • damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage.
  • inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases.
  • Detergents may contain stabilizers for this purpose; the provision of such means constitutes a preferred embodiment of the present invention. Washing or cleaning-active proteases and amylases 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, particularly preferably between 0.4 and 20% by weight and in particular between 0, 8 and 10 wt .-% of the enzyme protein.
  • a first constituent of the active ingredient combination of nonionic surfactants A and B responsible for the improved drying of automatic dishwashing agents according to the invention and the anionic polymer is the nonionic surfactant A.
  • the proportion by weight of the nonionic surfactant A in the total weight of the inventive automatic dishwashing agent in a preferred embodiment is between 0.05 and 10% by weight, preferably between 0.1 and 8% by weight, preferably between 0.5 and 5% by weight. % and in particular between 1 and 3 wt .-%.
  • Some exemplary formulations for preferred automatic dishwashing detergents according to the invention can be found in the following Table 3: ingredient Recipe 1 [% by weight] Recipe 2 [% by weight] Recipe 3 [% by weight] Recipe 4 [% by weight] tripolyphosphate 5 to 50 15 to 40 - - citrate - * - 5 to 40 15 to 30 carbonate 2 to 45 2 to 35 2 to 45 2 to 35 Enzyme ** 0.2 to 10 0.2 to 10 0.5 to 8 0.5 to 8 Nonionic surfactant A 1 0.05 to 10 0.05 to 10 0.05 to 10 0.05 to 10 Nonionic surfactant B 2 1 to 10 1 to 10 1 to 10 1 to 10 Anionic copolymer C 3 0.5 to 18 0.5 to 18 0.5 to 18 0.5 to 18 Misc Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 1 is a nonionic surfactant A of the general formula R 1 -CH (OH) CH 2 -O (CH 2 CH 2 O) x CH 2 CHR (OCH 2 CH 2 ) y O-CH
  • R 1 -CH (OH) CH 2 -O (CH 2 CH 2 O) x CH 2 CHR (OCH 2 CH 2 ) y O-CH 2 CH (OH) -R 2 in which R is a linear, saturated alkyl radical having 8 to 16 carbon atoms, preferably 10 to 14 carbon atoms, and n and m independently of one another have values of 20 to 30.
  • Corresponding compounds can be obtained, for example, by reaction of alkyldiols HO-CHR-CH 2 -OH with ethylene oxide, followed by reaction with an alkyle epoxide to close the free OH functions to form a dihydroxy ether.
  • the automatic dishwashing compositions according to the invention contain as a further essential constituent a second nonionic surfactant B.
  • the proportion by weight of the nonionic surfactant B in the total weight of the inventive automatic dishwashing agent in a preferred embodiment is between 0.1 and 30% by weight, preferably between 0.5 and 20% by weight; preferably between 1 and 10% by weight and in particular between 2 and 6% by weight.
  • Preferred nonionic surfactants B have the general formula R 1 O [CH 2 CH (CH 3 ) O] x [ CH 2 CH 2 O] y [CH 2 CH (CH 3 ) O] z CH 2 CH (OH) R 2 in which R 1 is a linear or branched aliphatic hydrocarbon radical having 4 to 22 carbon atoms or mixtures thereof, R 2 is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof, and x and z are values between 0 and 40 and y for a value of at least 15 stands.
  • R 1 is a linear or branched aliphatic hydrocarbon radical having 4 to 22 carbon atoms or mixtures thereof
  • R 2 is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof
  • x and z are values between 0 and 40 and y for a value of at least 15 stands.
  • the addition of these nonionic surfactants has proved to be advantageous, in particular with regard to the rinse power
  • the automatic dishwashing detergent contains, based on its total weight, nonionic surfactant of the general formula R 1 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y [CH 2 CH (CH 3 ) O ] z CH 2 CH (OH) R 2 in amounts of from 0.1 to 15% by weight, preferably from 0.2 to 10% by weight, particularly preferably from 0.5 to 8% by weight and in particular from 1, 0 to 6 wt .-%.
  • end-capped poly (oxyalkylated) nonionic surfactants which, according to the formula R 1 O [CH 2 CH 2 O] y, contain CH 2 CH (OH) R 2 in the R 1 group for a linear or branched aliphatic hydrocarbon radical to 22 carbon atoms or mixtures thereof, R 2 is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures
  • R 1 end-capped poly (oxyalkylated) nonionic surfactants which, according to the formula R 1 O [CH 2 CH 2 O] y, contain CH 2 CH (OH) R 2 in the R 1 group for a linear or branched aliphatic hydrocarbon radical to 22 carbon atoms or mixtures thereof
  • R 2 is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures
  • y for a value between 15 and 120 preferably 20 to 100, in particular 20 to 80 stands.
  • the group of these nonionic surfactants includes, for example, hydroxy mixed ethers of the general formula C 6-22 -CH (OH) CH 2 O- (EO) 20-120 -C 2 -26 , for example the C 8-12 fatty alcohol (EO) 22 - 2-hydroxydecyl ether and the C 4-22 fatty alcohol (EO) 40-80 -2-hydroxyalkyl ethers.
  • the nonionic surfactant B is a surfactant of the general formula R 1 CH (OH) CH 2 O- (CH 2 CH 2 O) 20-120 - R 2 is used, wherein R 1 and R 2 are independently a linear or branched aliphatic hydrocarbon radical having 2 to 20 carbon atoms particularly preferred.
  • R 1 is a linear or branched aliphatic hydrocarbon radical with 4 R 2 denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 4, preferably 0.5 to 1.5, and y for a value of at least 15 stands.
  • Also preferred according to the invention are also surfactants of the general 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 having 4 to 22 carbon atoms or mixtures thereof, R 2 denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is a value between 1 and 40 and y is a value between 15 and 40, wherein the alkylene units [CH 2 CH (CH 3 ) O] and [CH 2 CH 2 O] randomized, ie in the form of a random random distribution.
  • the rinse performance and drying can be markedly improved compared to conventional polyalkoxylated fatty alcohols without a free hydroxyl group.
  • the stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the abovementioned nonionic surfactants represent statistical mean values which, for a specific product, may be an integer or a fractional number. Due to the manufacturing process, commercial products of the formulas mentioned are usually not made of an individual representative, but of mixtures, which may result in mean values for the C chain lengths as well as for the degrees of ethoxylation or degrees of alkoxylation and subsequently broken numbers.
  • nonionic surfactants can be used not only as individual substances, but also as surfactant mixtures of two, three, four or more surfactants.
  • Surfactant mixtures are not mixtures of nonionic surfactants which in their entirety fall under one of the abovementioned general formulas, but rather those Mixtures containing two, three, four or more nonionic surfactants which may be described by different of the foregoing or other general formulas.
  • Nonionic surfactants b) which have a melting point above room temperature.
  • the automatic dishwashing compositions according to the invention contain an anionic polymer C as a further essential constituent.
  • Preferred anionic copolymers are the copolymeric polycarboxylates and the copolymeric polysulfonates.
  • the proportion by weight of the copolymeric anionic polymer C in the total weight of the inventive automatic dishwashing agent in a preferred embodiment is between 0.1 and 20% by weight, preferably between 0.5 and 18% by weight, preferably between 1.0 and 15% by weight. -% and in particular between 4 and 14 wt .-%.
  • Automatic dishwashing detergents characterized in that the copolymeric anionic polymer C is selected from the group of hydrophobically modified polycarboxylates and polysulfonates, are particularly preferred because the hydrophobic modification of the anionic copolymers improves the rinsing and drying properties of these agents while at the same time causing low deposit formation can be achieved.
  • the copolymers C may have two, three, four or more different monomer units.
  • Preferred copolymeric polysulfonates C 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 partially in neutralized form, i. the acidic acid of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions.
  • metal ions preferably alkali metal ions and in particular for sodium ions.
  • partially or fully neutralized sulfonic acid-containing copolymers is preferred according to the invention.
  • the monomer distribution of the copolymers preferably used according to the invention in the case of copolymers which contain only monomers from groups i) and ii) is preferably in each case from 5 to 95% by weight i) or ii), particularly preferably from 50 to 90% by weight monomer from group ii) and from 10 to 50% by weight of monomer from group i), in each case based on the polymer.
  • 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 C 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-dimethylhexene-1,3,5-dimethylhexene-1,4 , 4-dimethylhexane-1, ethylcyclohexyn, 1-octene, ⁇ -olefins having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C22
  • compositions according to the invention may contain further washing or cleaning-active substances, preferably from the group of bleaches, bleach activators and bleach catalysts, glass corrosion inhibitors, corrosion inhibitors, fragrances and perfume carriers. These preferred ingredients will be described in more detail below.
  • Machine dishwashing detergents according to the invention may contain a bleaching agent as further constituent, with oxygen bleaches being preferred.
  • a bleaching agent as further constituent, with oxygen bleaches being preferred.
  • the compounds which serve as bleaches and deliver H 2 O 2 in water are sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate of particular importance.
  • Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloimino peracid or diperdodecanedioic acid.
  • bleaching agents from the group of organic bleaching agents can also be used.
  • Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide.
  • Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids.
  • Preferred automatic dishwashing agents according to the invention are characterized in that they contain an oxygen bleaching agent, preferably sodium percarbonate, more preferably a coated sodium percarbonate.
  • the proportion by weight of the bleaching agent, based on the total weight of the washing or cleaning agent, in preferred embodiments is between 2 and 30% by weight, preferably between 4 and 20% by weight and in particular between 6 and 15% by weight.
  • the automatic dishwasher detergents according to the invention may contain bleach activators.
  • bleach activators These compounds give under perhydrolysis aliphatic peroxycarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the stated carbon atom number and / or optionally substituted benzoyl groups.
  • TAED tetraacetylethylenediamine
  • Automatic dishwashing detergent characterized in that it contains as bleach activator a bleach activator from the group of the acetylated amines, which is preferably tetraacetylenediamine (TAED), are preferred according to the invention.
  • TAED tetraacetylenediamine
  • the automatic dishwasher detergents according to the invention preferably contain at least one bleach catalyst.
  • bleach-enhancing transition metal salts or transition metal complexes such as, for example, 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 and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.
  • complexes of manganese in the oxidation state II, III, IV or IV which preferably contain one or more macrocyclic ligands with the donor functions N, NR, PR, O and / or S.
  • ligands are used; having the nitrogen donor functions.
  • bleach catalyst (s) in the compositions of the invention, which as macromolecular ligands 1,4,7-trimethyl-1,4,7-triazacyclononan (Me-TACN), 1,4,7-triazacyclononane (TACN ), 1,5,9-trimethyl-1,5,9-triazacyclododecane (Me-TACD), 2-methyl-1,4,7-trimethyl-1,4,7-triazacyclononane (Me / Me-TACN) and or 2-methyl-1,4,7-triazacyclononane (Me / TACN).
  • Me-TACN 1,4,7-trimethyl-1,4,7-triazacyclononan
  • TACN 1,4,7-triazacyclononane
  • TACD 1,5,9-trimethyl-1,5,9-triazacyclododecane
  • Me-TACD 2-methyl-1,4,7-trimethyl-1,4,7-triazacyclononane
  • 2-methyl-1,4,7-triazacyclononane
  • Machine dishwashing detergent characterized in that it further comprises a bleach catalyst selected from the group of bleach-enhancing transition metal salts and transition metal complexes, preferably from the group of complexes of manganese with 1,4,7-trimethyl-1,4,7-triazacyclononane (Me 3 -TACN ) or 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (Me 4 -TACN), are preferred according to the invention, since in particular the cleaning result can be significantly improved by the aforementioned bleach catalysts.
  • a bleach catalyst selected from the group of bleach-enhancing transition metal salts and transition metal complexes, preferably from the group of complexes of manganese with 1,4,7-trimethyl-1,4,7-triazacyclononane (Me 3 -TACN ) or 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (Me 4 -TACN), are preferred according to the invention, since in particular the cleaning result can be significantly improved by the aforementioned
  • the abovementioned bleach-enhancing transition metal complexes are used in customary amounts, preferably in an amount of up to 5% by weight, in particular of 0.0025% by weight to 1% by weight and more preferably of 0, 01 wt .-% to 0.30 wt .-%, each based on the total weight of the bleach catalyst-containing agents used. In special cases, however, more bleach catalyst can be used.
  • the automatic dishwasher detergents according to the invention can be present in the ready-to-use forms known to the person skilled in the art, ie for example in solid or liquid form, but also as a combination of solid and liquid supply forms.
  • powders, granules, extrudates or compactates, in particular tablets are suitable as firm supply sources.
  • the liquid supply forms based on water and / or organic solvents may be thickened, in the form of gels.
  • Inventive agents can be formulated as single-phase or multi-phase products.
  • automatic dishwashing detergents with one, two, three or four phases are preferred.
  • Machine dishwashing detergents characterized in that they are in the form of a prefabricated dosing unit with two or more phases, are particularly preferred.
  • the individual phases of multiphase agents may have the same or different states of matter.
  • Machine dishwashing detergents which have at least two different solid phases and / or at least two liquid phases and / or at least one solid and at least one liquid phase are preferred.
  • Particularly preferred are in particular two- or multi-phase tablets, for example two-layer tablets, in particular two-layer tablets with a trough and a mold body located in the trough.
  • Automatic dishwasher detergents according to the invention are preferably prefabricated to form metering units. These metering units preferably comprise the necessary for a cleaning cycle amount of washing or cleaning-active substances. Preferred metering units have a weight between 12 and 30 g, preferably between 14 and 26 g and in particular between 15 and 22 g.
  • the volume of the aforementioned metering units and their spatial form are selected with particular preference so that a metering of the prefabricated units is ensured via the metering chamber of a dishwasher.
  • the volume of the dosing unit is therefore preferably between 10 and 35 ml, preferably between 12 and 30 ml and in particular between 15 and 25 ml.
  • the automatic dishwasher detergents according to the invention in particular the prefabricated metering units, have a water-soluble coating, with particular preference.
  • disintegration aids so-called tablet disintegrants
  • Disintegration aids are preferably used in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, based in each case on the total weight of the disintegration assistant-containing agent.
  • Preferred disintegrating agents are cellulosic disintegrating agents, so that preferred washing or cleaning agents comprise such cellulose-based disintegrants in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight. % contain.
  • the cellulose used as a disintegration aid is preferably not used in finely divided form, but converted into a coarser form, for example granulated or compacted, before it is added to the premixes to be tabletted.
  • the particle sizes of such disintegrating agents are usually above 200 .mu.m, preferably at least 90 wt .-% between 300 and 1600 .mu.m and in particular at least 90 wt .-% between 400 and 1200 microns.
  • Preferred disintegration aids preferably a disintegration aid based on cellulose, preferably in granular, cogranulated or compacted form, are in the disintegrating agent-containing agents in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6 wt .-%, each based on the total weight of the disintegrating agent-containing agent.
  • gas-evolving effervescent systems can furthermore be used as tablet disintegration auxiliaries.
  • preferred effervescent systems consist of at least two components which react with one another to form gas, for example alkali metal carbonate and / or bicarbonate and an acidifying agent which is suitable for liberating carbon dioxide from the alkali metal salts in aqueous solution.
  • An acidifying agent which releases carbon dioxide from the alkali salts in aqueous solution is, for example, citric acid.
  • the dishwasher detergents according to the invention exhibit their advantageous cleaning and drying properties, in particular also in low-temperature cleaning processes.
  • Preferred dishwashing processes using agents according to the invention are therefore characterized in that the dishwashing processes are carried out at a liquor temperature below 60 ° C., preferably below 50 ° C.
  • agents according to the invention are distinguished by an improved drying performance compared to conventional automatic dishwasher detergents.
  • Another object of the present application is therefore the use of a machine dishwashing detergent according to the invention for improving the drying in automatic dishwashing.
  • a machine load of crockery comprising porcelain, glass, plastic and stainless steel, after adding a defined amount of dirt in a dishwasher (Bosch SGS 57M82; 50 ° normal without intensive drying) with 20 g of the automatic dishwashing detergent listed in the table below with a water hardness of 21 Rinsed ° dH.
  • the dosage of the dishwashing agent was carried out in the main rinse of the dishwashing process.
  • the drying index was determined 30 minutes after the end of the dishwashing process with the door of the dishwasher closed during these 30 minutes.
  • the maximum value for best drying is 0, for worst drying 6.0.
  • the deposit formation was determined together with the drying index.
EP09764241.7A 2008-12-05 2009-12-01 Maschinelles geschirrspülmittel Active EP2358853B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL09764241T PL2358853T3 (pl) 2008-12-05 2009-12-01 Środek do maszynowego zmywania naczyń

Applications Claiming Priority (2)

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DE102008060471A DE102008060471A1 (de) 2008-12-05 2008-12-05 Maschinelles Geschirrspülmittel
PCT/EP2009/066102 WO2010063690A1 (de) 2008-12-05 2009-12-01 Maschinelles geschirrspülmittel

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EP2358853A1 EP2358853A1 (de) 2011-08-24
EP2358853B1 true EP2358853B1 (de) 2017-02-08

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US (1) US8349784B2 (es)
EP (1) EP2358853B1 (es)
DE (1) DE102008060471A1 (es)
ES (1) ES2622984T3 (es)
PL (1) PL2358853T3 (es)
WO (1) WO2010063690A1 (es)

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AU2011326374B2 (en) 2010-11-11 2017-02-16 Rivertop Renewables, Inc. Corrosion inhibiting composition
GB201104244D0 (en) * 2011-03-14 2011-04-27 Reckitt Benckiser Nv Detergent composition with improved drying performance
EP2952569B1 (en) * 2011-04-21 2017-01-25 Rivertop Renewables, Inc. Calcium sequestering composition
DE102011084934A1 (de) * 2011-10-21 2013-04-25 Henkel Ag & Co. Kgaa Klarspül- und Geschirrspülmittel
DE102011086639A1 (de) 2011-11-18 2013-05-23 Henkel Ag & Co. Kgaa Nichtionische Tenside als Soil-Release-Wirkstoffe
DE102012222266A1 (de) 2012-12-05 2014-06-05 Henkel Ag & Co. Kgaa Verfahren zur Herstellung wasserarmer bis wasserfreier flüssiger Wasch- oder Reinigungsmittel
DE102012223339A1 (de) 2012-12-17 2014-06-18 Henkel Ag & Co. Kgaa Tensidkombination zur verbesserten Trocknung
US9346736B2 (en) 2013-03-13 2016-05-24 Rivertop Renewables, Inc. Oxidation process
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WO2016057497A1 (en) * 2014-10-08 2016-04-14 Rivertop Renewables, Inc. Detergent builder and dispersant synergy in calcium carbonate scale prevention
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Publication number Publication date
EP2358853A1 (de) 2011-08-24
DE102008060471A1 (de) 2010-06-10
ES2622984T3 (es) 2017-07-10
WO2010063690A1 (de) 2010-06-10
US20110232692A1 (en) 2011-09-29
PL2358853T3 (pl) 2017-08-31
US8349784B2 (en) 2013-01-08

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