EP2185674B2 - Détergents - Google Patents

Détergents Download PDF

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Publication number
EP2185674B2
EP2185674B2 EP08803450.9A EP08803450A EP2185674B2 EP 2185674 B2 EP2185674 B2 EP 2185674B2 EP 08803450 A EP08803450 A EP 08803450A EP 2185674 B2 EP2185674 B2 EP 2185674B2
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EP
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Prior art keywords
automatic dishwashing
weight
dishwashing detergent
carbon atoms
mixtures
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EP08803450.9A
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German (de)
English (en)
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EP2185674B1 (fr
EP2185674A1 (fr
Inventor
Johannes Zipfel
Nadine Warkotsch
Arnd Kessler
Christian Nitsch
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • 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
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
    • 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
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C11D1/831—Mixtures of non-ionic with anionic compounds of sulfonates with ethers of polyoxyalkylenes without phosphates
    • 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

Definitions

  • the present patent application describes cleaning agents, in particular cleaning agents for machine cleaning of dishes.
  • This application relates in particular to automatic dishwashing agents which contain a combination of specific nonionic surfactants and anionic polymers.
  • Dishwashing detergents are available to consumers in a variety of forms. In addition to traditional liquid hand dishwashing detergents, with the spread of household dishwashers, automatic dishwashing detergents in particular are of great importance. These automatic dishwashing detergents are typically offered to the consumer in solid form, for example as a powder or as tablets, but increasingly also in liquid form.
  • the drying performance is another essential characteristic of automatic dishwashing detergents. Since the drying of the dishes is essentially brought about by the own heat of the dishes after the machine cleaning process has ended, high-temperature cleaning processes are generally distinguished by improved drying compared to low-temperature cleaning processes. However, high-temperature cleaning processes are necessarily characterized by increased energy consumption and consequently increased costs for people and the environment.
  • DE 101 331 37 discloses liquid, aqueous machine dishwashing detergents which may contain end-capped poly (oxyalkylated) note lines.
  • the object of this application was to provide an automatic dishwashing agent which has good cleaning and rinsing performance and improved drying of the cleaned dishes even in low-temperature cleaning cycles or in cleaning cycles with low water consumption.
  • Automatic dishwashing agents according to the invention contain one or more builders as the first essential component.
  • the weight proportion of the builders in the total weight of automatic dishwashing agents according to the invention is preferably 15 to 50% by weight and in particular 20 to 40% by weight.
  • the builders include, in particular, carbonates, phosphates, organic cobuilders and silicates.
  • alkali metal carbonate (s) particularly preferably sodium carbonate
  • Organic cobuilders that may be mentioned are, in particular, polycarboxylates / polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals, dextrins and organic cobuilders. These substance classes are described below.
  • Organic builder substances which can be used are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or its sodium salts, polycarboxylic acids being understood as 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), provided that such use is not objectionable for ecological reasons, as well as mixtures of these.
  • the free acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH value in detergents or cleaning agents.
  • Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these should be mentioned in particular.
  • Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of 2000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates from this group, which have molecular weights from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, can be preferred.
  • Automatic dishwashing agents can use crystalline layered silicates of the general formula NaMSi x O 2x + 1 ⁇ y H 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, as a builder particularly preferred values for x are 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20.
  • the phosphates In addition to the citrates, the phosphates have proven to be the most effective builders in terms of cleaning performance. Of the large number of commercially available phosphates, the alkali metal phosphates, with particular preference being given to pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), are of the greatest importance in the detergent and cleaning agent industry.
  • Alkali metal phosphate is the summary name for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which metaphosphoric acids (HPO 3 ) n and orthophosphoric acid H 3 PO 4 can be distinguished in addition to higher molecular representatives.
  • the phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts or lime incrustations in fabrics and also contribute to cleaning performance.
  • phosphates are 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).
  • Sodium potassium tripolyphosphates are also preferably used according to the invention.
  • phosphates are used as washing or cleaning-active substances in detergents or cleaning agents
  • preferred agents contain these phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or Potassium tripolyphosphate), in amounts from 2 to 50% by weight, preferably from 2 to 30% by weight and in particular from 3 to 25% by weight, particularly preferably from 3 to 15% by weight, in each case based on the Weight of the detergent or cleaning agent.
  • amorphous sodium silicates with a Na 2 O: SiO 2 module of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and in particular 1: 2 to 1: 2.6, which are preferably delayed in dissolution and have secondary washing properties.
  • the content of silicates is below 10% by weight, preferably below 5% by weight and in particular below 2% by weight.
  • Automatic dishwashing agents according to the invention which are particularly preferred are silicate-free.
  • the automatic dishwashing agents according to the invention can of course contain the aforementioned builders both in the form of individual substances and in the form of substance mixtures composed of two, three, four or more builders.
  • dishwashing agents are characterized in that the dishwashing agent contains at least two builders from the group of phosphates, carbonates and citrates, the weight fraction of these builders, based on its total weight of the automatic dishwashing agent, preferably 2 to 50% by weight, preferably 5 to 40% by weight and in particular 10 to 30% by weight.
  • the combination of two or more builders from the group mentioned above has proven to be advantageous for the cleaning and rinsing performance of automatic dishwashing agents according to the invention.
  • Some exemplary formulations for preferred automatic dishwashing agents according to the invention can be found in the following tables: (not according to the invention): ingredient Formula 1 [% by weight] Formulation 2 [% by weight] Formulation 3 [% by weight] Formulation 4 [% by weight] Tripolyphosphate 5 to 50 5 to 35 - - Citrate - *** - 5 to 30 5 to 20 Carbonate 2 to 45 2 to 35 2 to 45 2 to 35 Nonionic surfactant * 0.1 to 15 0.2 to 10 0.5 to 8 1 to 6 Anionic copolymer ** 0.1 to 20 0.1 to 20 0.1 to 20 0.1 to 20 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
  • Dishwashing detergents according to the invention contain nonionic surfactants 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) as a second essential component ) R 2 .
  • the addition of surfactants has proven to be particularly advantageous with regard to the rinsing performance and drying.
  • the automatic dishwashing agent 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 from 0.1 to 15 % By weight, preferably 0.2 to 10% by weight, particularly preferably 0.5 to 8% by weight and in particular from 1.0 to 6% by weight.
  • R 1 denotes a linear or branched aliphatic hydrocarbon radical with 4 up 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
  • y stands for a value between 15 and 120, preferably 20 to 100, in particular 20 to 80.
  • 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 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 represents values between 0.5 and 4, preferably 0.5 to 1.5, and y represents a value of at least 15 stands.
  • 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 are also preferred, in which R 1 is a linear or branched aliphatic Hydrocarbon radical with 4 to 22 carbon atoms or mixtures thereof, R 2 denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x stands for a value between 1 and 40 and y stands for a value between 15 and 40, the alkylene units [CH 2 CH (CH 3 ) O] and [CH 2 CH 2 O] are randomized, ie in the form of a statistical, random distribution.
  • the rinsing performance and drying can be significantly improved compared to conventional polalkoxylated fatty alcohols without a free hydroxyl group.
  • the specified carbon chain lengths and degrees of ethoxylation or degrees of alkoxylation of the aforementioned nonionic surfactants represent statistical mean values which, for a specific product, can be an integer or a fraction. Due to the manufacturing process, commercial products of the formulas mentioned mostly do not consist of an individual representative, but rather of mixtures, which can result in mean values and fractional numbers for both the carbon chain lengths and the degrees of ethoxylation or alkoxylation.
  • 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 above general formulas, but rather those mixtures which contain two, three, four or more nonionic surfactants which are described by different ones of the above or other general formulas can be.
  • Nonionic surfactants b) which have a melting point above room temperature are particularly preferred.
  • a third characteristic component of automatic dishwashing detergents according to the invention are the copolymers c) containing sulfonic acid groups, which, in addition to monomer (s) containing sulfonic acid groups, comprise at least one unsaturated carboxylic acid.
  • the copolymers c) can have two, three, four or more different monomer units.
  • Preferred automatic dishwashing detergents contain the polymer c) in amounts of 0.2 to 18% by weight, preferably 0.5 to 15% by weight and in particular 1.0 to 12% by weight, based in each case on the total weight of the machine Dishwashing detergent.
  • the unsaturated carboxylic acid (s) used is / are particularly preferably 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.
  • the unsaturated dicarboxylic acids can of course also be used.
  • 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-hydroxy-propanesulphonic acid, allylsulphonic acid, methallylsulphonic acid, allyloxybenzenesulphonic acid, methallyloxybenzenesulphonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulphonic acid, 2-methyl-2-propen1-sulphonic acid, 3-sulphate, 3-sulphonyl methacrylate, vinylsulpho-propyl, 3-sulphate, sulfo methacrylate , Sulfomethacrylamide, sulfomethyl methacrylamide and mixtures of the acids mentioned or their water-soluble salts.
  • the sulfonic acid groups can be completely or partially in neutralized form, ie the acidic hydrogen atom 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 copolymers containing sulfonic acid groups 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 application.
  • Preferred automatic dishwashing detergents are characterized in that the copolymers have molar masses 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 .
  • 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, 2,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethylhexene-1, 3,5-dimethylhexene-1, 4 , 4-dimethylhexane-1, ethylcyclohexyn, 1-octene, ⁇ -olefones with 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C22-
  • a weight ratio of components c) and b) of less than 2.8: 1 has proven to be advantageous, particularly in the case of low-temperature cleaning processes.
  • the weight ratio of components c) and b) denotes the ratio of the weight fractions c) and b) to one another in relation to the total weight of the automatic dishwasher detergent.
  • the proportion by weight of the surfactant b) should accordingly be at least one third of the proportion by weight of the anionic polymer c).
  • the weight proportion of the surfactant is therefore at least 3% by weight of the total weight of the automatic dishwashing agent.
  • Automatic dishwashing detergent according to one of the preceding claims, characterized in that the weight ratio of components c) and b) is less than 2.8: 1, preferably less than 2.5: 1, particularly preferably less than 2.2: 1 and in particular between 2.2: 1 and 1:10 are preferred according to the invention.
  • Ethylenediamine tetramethylene phosphonate (EDTMP), diethylenetriamine pentamethylene phosphonate (DTPMP) and their higher homologues are preferred as aminoalkanephosphonates. They are preferably in the form of the neutrally reacting sodium salts, e.g. B. as the hexasodium salt of EDTMP or as the hepta- and octasodium salt of DTPMP. From the group of phosphonates, HEDP is preferably used.
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • DTPMP diethylenetriaminepenta
  • phosphonates are particularly preferred.
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • the dishwashing detergents according to the invention can also contain enzymes to increase cleaning performance. These include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are in principle of natural origin; Based on the natural molecules, improved variants are available for use in detergents or cleaning agents, which are accordingly preferred. Washing or cleaning agents preferably contain enzymes in total amounts of 1 ⁇ 10 -6 to 5% by weight, based on active protein. The protein concentration can be determined using known methods, for example the BCA method or the biuret method.
  • subtilisin type those of the subtilisin type are preferred. Examples of this are the subtilisins BPN 'and Carlsberg as well as their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the subtilases, but no longer the subtilisins in the narrower sense of the term, thermitase, Proteinase K and the proteases TW3 and TW7.
  • lipases or cutinases can also be used, in particular because of their triglyceride-cleaving activities, but also in order to generate peracids in situ from suitable precursors.
  • suitable precursors include, for example, the lipases originally obtained from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, especially those with the amino acid exchange D96L.
  • the cutinases which were originally isolated from Fusarium solani pisi and Humicola insolens can be used.
  • Lipases or cutinases whose starting enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii can also be used.
  • 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 to increase the bleaching effect.
  • organic, particularly preferably aromatic, compounds that interact with the enzymes are added in order to increase the activity of the oxidoreductases in question (enhancers) or to ensure the flow of electrons (mediators) in the event of greatly differing redox potentials between the oxidizing enzymes and the soiling.
  • a protein and / or enzyme can be protected against damage such as inactivation, denaturation or disintegration, for example due to physical influences, oxidation or proteolytic cleavage, particularly during storage.
  • damage such as inactivation, denaturation or disintegration, for example due to physical influences, oxidation or proteolytic cleavage, particularly during storage.
  • inhibition of proteolysis is particularly preferred, in particular if the agents also contain proteases. Washing or cleaning agents can contain stabilizers for this purpose; the provision of such means represents a preferred embodiment of the present invention.
  • the automatic dishwashing agent based in each case on its total weight, is 0.1 to 12% by weight, preferably 0.2 to 10% by weight and in particular 0.5 to 8% by weight Contains enzyme preparations.
  • Proteases and amylases which are active in washing or cleaning are generally not provided in the form of the pure protein, but rather in the form of stabilized preparations that can be stored and transported.
  • These ready-made preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, in particular in the case of liquid or gel-like agents, solutions of the enzymes, advantageously As concentrated as possible, low in water and / or mixed with stabilizers or other auxiliaries.
  • the enzymes can be encapsulated both for the solid and for the liquid dosage form, for example by spray drying or extrusion of the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are enclosed as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a protective layer impermeable to water, air and / or chemicals.
  • Additional active ingredients for example stabilizers, emulsifiers, pigments, bleaches or dyes, can also be applied in superimposed layers.
  • Such capsules are applied by methods known per se, for example by shaking or roller granulation or in fluid bed processes. Such granules are advantageously low in dust, for example due to the application of polymeric film formers, and due to the coating are stable in storage.
  • 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% by weight of the enzyme protein.
  • Glass corrosion inhibitors are further preferred ingredients of dishwasher detergents according to the invention. Glass corrosion inhibitors prevent the appearance of cloudiness, streaks and scratches, but also the iridescence of the glass surface of machine-cleaned glasses. Preferred glass corrosion inhibitors come from the group of the magnesium and zinc salts and the magnesium and zinc complexes.
  • the spectrum of zinc salts preferred according to the invention ranges from salts that are sparingly or insoluble in water, i.e. a solubility below 100 mg / l, preferably below 10 mg / l, in particular below 0.01 mg / l, up to those salts which have a solubility in water above 100 mg / l, preferably above 500 mg / l, particularly preferably above 1 g / l and in particular above 5 g / l (all solubilities at 20 ° C Water temperature).
  • the first group of zinc salts includes, for example, zinc citrate, zinc oleate and zinc stearate
  • the group of soluble zinc salts includes, for example, zinc formate, zinc acetate, zinc lactate and zinc gluconate.
  • At least one zinc salt of an inorganic or organic carboxylic acid is used with particular preference as the glass corrosion inhibitor.
  • Zinc ricinoleate, zinc abietate and zinc oxalate are also preferred.
  • the content of zinc salt in detergents or cleaning agents is preferably between 0.1 to 5% by weight, more preferably between 0.2 to 4% by weight and in particular between 0.4 to 3% by weight , or the content of zinc in oxidized form (calculated as Zn 2+ ) between 0.01 to 1 wt .-%, preferably between 0.02 to 0.5 wt .-% and in particular between 0.04 to 0, 5% by weight, based in each case on the total weight of the agent containing the glass corrosion inhibitor.
  • Automatic dishwashing agents according to the invention can contain an oxygen bleaching agent as a further essential component.
  • Sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance among the compounds which serve as bleaching agents and produce H 2 O 2 in water.
  • Further bleaching agents which can be used are, for example, peroxypyrophosphates, citrate perhydrates and peracid salts or peracids which provide H 2 O 2 , such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloimino peracid 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.
  • Further typical organic bleaching agents are the peroxy acids, the alkyl peroxy acids and the aryl peroxy acids being mentioned as examples.
  • Preferred automatic dishwashing agents are characterized in that the dishwashing agent, based in each case on the total weight of the dishwashing agent, contains 1.0 to 20% by weight, preferably 4.0 to 18% by weight and in particular 8 to 15% by weight of an oxygen bleaching agent , preferably 1.0 to 20% by weight, preferably 4.0 to 18% by weight and in particular 8 to 15% by weight sodium percarbonate.
  • the automatic dishwashing agents according to the invention can additionally contain bleach activators.
  • Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid. Substances which carry O- and / or N-acyl groups with the number of carbon atoms mentioned and / or optionally substituted benzoyl groups are suitable. Multiple acylated alkylenediamines are preferred, tetraacetylethylenediamine (TAED) having proven particularly suitable.
  • TAED tetraacetylethylenediamine
  • bleach activators in particular TAED, are preferably used in amounts of up to 10% by weight, in particular 0.1% by weight to 8% by weight, particularly 2 to 8% by weight and particularly preferably 2 to 6% by weight , each based on the total weight of the bleach activator-containing agents.
  • bleach catalysts can also be used.
  • These substances are bleach-intensifying transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salen 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.
  • Manganese complexes in the II, III, IV or IV oxidation state which preferably contain one or more macrocyclic ligand (s) with the donor functions N, NR, PR, O and / or S, are used with particular preference.
  • Ligands are preferably used which have nitrogen donor functions.
  • bleach catalyst (s) in the agents according to the invention which have 1,4,7-trimethyl-1,4,7-triazacyclononane (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-triazacyclononane
  • TACN 1,4,7-triazacyclononane
  • TACD 1,5,9-trimethyl-1,5,9-triazacyclododecane
  • Automatic dishwashing detergents characterized in that they also selected a bleach catalyst from the group of the bleach-intensifying transition metal salts and transition metal complexes, preferably from the group of the 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 the abovementioned bleach catalysts in particular can significantly improve the cleaning result.
  • a bleach catalyst from the group of the bleach-intensifying transition metal salts and transition metal complexes, preferably from the group of the 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 the abovementioned bleach
  • the automatic dishwashing detergents used according to the invention can be packaged in solid or liquid form, but also, for example, as a combination of solid and liquid supply forms.
  • Powders, granules, extrudates or compacts, in particular tablets, are particularly suitable as solid supply forms.
  • the liquid supply forms preferably based on water and / or organic solvents, can be thickened, in the form of gels.
  • Aqueous automatic dishwashing agents are preferred according to the invention.
  • the water content of these aqueous automatic dishwashing agents is preferably between 10 and 80% by weight, preferably between 20 and 70% by weight and in particular between 30 and 60% by weight.
  • preferred automatic dishwashing agents are characterized in that the automatic dishwashing agent has a pH value (20 ° C) between 8 and 12, preferably between 9 and 11.5, preferably between 9.5 and 11.5.
  • Machine dishwashing detergents which are in the form of a liquid, aqueous, low-alkaline preparation with a pH (20 ° C.) between 8 and 12, preferably between 9 and 11.5, preferably between 9.5 and 11.5, are particularly preferred.
  • the cleaning performance of automatic dishwashing detergents according to the invention can be improved by adding organic solvents.
  • the present application therefore preferably relates to automatic dishwashing agents which, in addition to the other ingredients listed, also contain at least one organic solvent.
  • Preferred liquid automatic dishwashing agents are characterized in that the dishwashing agent, based on its total weight, contains organic solvent in amounts of 0.2 to 15% by weight, preferably 0.5 to 12% by weight, particularly preferably 1.0 to 10% by weight Contains wt .-%.
  • organic solvents originate, for example, from the groups of monoalcohols, diols, triols or polyols, ethers, esters and / or amides.
  • Organic solvents which are water-soluble are particularly preferred, "water-soluble" solvents in the context of the present application being solvents which are completely miscible with water at room temperature, i.e. without a miscibility gap.
  • Organic solvents which can be used in the agents according to the invention preferably come from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided that they are miscible with water in the specified concentration range.
  • the solvents are preferably selected from ethanol, n- or i-propanol, butanols, glycol, propane or butanediol, especially 1,2 propanediol, glycerol, diglycol, propyl or butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol methyl or ethyl ether, methoxy, ethoxy or butoxy t
  • organic solvents from the group of organic amines and / or alkanolamines have proven to be particularly effective with regard to cleaning performance and here again with regard to cleaning performance on bleachable stains, in particular tea stains.
  • the primary and secondary alkylamines, the alkyleneamines and mixtures of these organic amines are particularly preferred as organic amines.
  • the group of preferred primary alkylamines includes monomethylamine, monoethylamine, monopropylamine, monobutylamine, monopentylamine and cyclohexylamine.
  • the group of preferred secondary alkylamines includes, in particular, dimethylamine.
  • thickeners are preferably added to these agents.
  • a large group of particularly preferred thickeners are the fully synthetic polymers such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes. Thickening agents from these classes of compounds are widely available commercially and are sold for example under the trade name Acusol ® -810, Acusol ® -820 (methacrylic acid (stearyl alcohol 20 EO) ester-acrylic acid copolymer, 30% in water, Rohm & Haas), Dapral ® -GT-282-S (alkyl polyglycol ether, Akzo), Deuterol ® -Polymer-11 (dicarboxylic acid copolymer, Schöner GmbH), Deuteron ® -XG (anionic heteropolysaccharide based on ⁇ -D-glucose, D-manose, D- Glucuronic acid, Schöner GmbH), Deuteron ® -XN (non-ionic
  • thickeners examples include agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, carob gum, starch, dextrins, gelatin, casein, carboxymethyl cellulose, gum ethers, polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids , Polyethers, polyimines, polyamides, polysilicic acids, clay minerals such as montmorillonites, zeolites and silicas.
  • the automatic dishwashing agents according to the invention contain the thickener in amounts between 0.1 and 8% by weight, preferably between 0.2 and 6% by weight and particularly preferably between 0.4 and 4% by weight. -% based on the total weight of the automatic dishwasher detergent.
  • the pourability and settling stability of the liquid automatic dishwashing agents preferred according to the invention can, in addition to the thickeners, also be influenced by the ratio of the potassium and sodium ions in these agents.
  • Liquid agents preferred according to the invention are made up and packaged using the water-soluble or water-insoluble packaging agents known to those skilled in the art.
  • the packaging means can be single, double or multi-chamber containers.
  • Water-insoluble two- or multi-chamber containers are particularly preferred.
  • Such two- or multi-chamber containers typically have a total volume between 100 and 5000 ml, preferably between 200 and 2000 ml.
  • the volume of the individual chambers is preferably between 50 and 2000 ml, preferably between 100 and 1000 ml.
  • Preferred two- or multi-chamber containers have the shape of a bottle.
  • the automatic dishwashing agents according to the invention are preferably present in these packaging agents in the form of separate partial recipes. These sub-formulations do not form a common phase boundary, but rather are located in separate areas of the packaging means and have compositions that differ from one another.
  • the two- or multi-chamber container preferably has at least one spout, which can be designed, for example, in the form of a common spout for all the agents contained in the bottle.
  • the weight information given above for the active washing and cleaning ingredients and the information on the pH value naturally relate to the automatic dishwashing detergent obtained by combining all sub-formulations.
  • individual partial recipes contained in the chambers can therefore differ from the features characterizing the inventive automatic dishwasher detergent, provided that only the combination of all partial recipes of an inventive automatic dishwasher detergent with the above-mentioned characteristic and possibly preferred Has features.
  • individual sub-recipes can be free of phosphonate or anionic copolymers, provided that the combination of all sub-recipes results in an automatic dishwashing agent which contains nonionic surfactant b) and anionic copolymer, comprising i) unsaturated carboxylic acid (s) and ii) sulfonic acid group-containing monomer (s) ( e) contains.
  • the information given above on the pH of the lower alkaline dishwashing detergents preferred according to the invention also relate to the pH of the overall composition and not to the pH of any partial recipes.
  • Individual sub-recipes can therefore have pH values (20 ° C) below 8 or above 12, provided that the combination of the sub-recipes results in an automatic dishwashing agent with a pH (20 ° C) between 8 and 12.
  • the automatic dishwashing detergents according to the invention show their advantageous cleaning properties in particular also low-temperature cleaning processes.
  • Preferred dishwashing processes using agents according to the invention are therefore characterized in that these processes are carried out at temperatures up to a maximum of 55 ° C, preferably up to a maximum of 50 ° C.

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Claims (14)

  1. Détergent pour lave-vaisselle automatique contenant :
    a) 10 à 60 % en poids d'un adjuvant
    b) un tensioactif non ionique de formule générale
    R1O[CH2CH(CH3)O]x[CH2CH2O]y[CH2CH(CH3)O]zCH2CH(OH)R2, dans laquelle R1 représente un radical hydrocarboné aliphatique linéaire ou ramifié comportant 4 à 22 atomes de carbone ou leurs mélanges, R2 représente un radical hydrocarboné linéaire ou ramifié comportant 2 à 26 atomes de carbone ou leurs mélanges, et x et z représentent des valeurs comprises entre 0 et 40 et y représente une valeur d'au moins 15
    c) un copolymère anionique comprenant
    i) des acides carboxyliques insaturés
    ii) des monomères contenant des groupes d'acide sulfonique,
    caractérisé en ce que le rapport pondéral des constituants c) et b) est inférieur à 3:1, le détergent pour lave-vaisselle contenant, par rapport au poids total du détergent pour lave-vaisselle automatique, du phosphonate en des quantités de 2.0 à 5 % en poids.
  2. Détergent pour lave-vaisselle automatique selon la revendication 1, caractérisé en ce que le rapport pondéral des constituants c) et b) est inférieur à 2,8:1, de préférence inférieur à 2,5:1, de manière particulièrement préférée inférieur à 2,2:1, en particulier compris entre 2,2:1 et 1:10 et de manière tout particulièrement préférée compris entre 2,2:1 et 1:5.
  3. Détergent pour lave-vaisselle automatique selon l'une des revendications précédentes, caractérisé en ce que le détergent pour lave-vaisselle automatique contient, en tant que tensioactif non ionique b), un tensioactif de formule générale
    R1O[CH2CH2O]yCH2CH(OH)R2,
    dans laquelle R1 représente un radical hydrocarboné aliphatique linéaire ou ramifié comportant 4 à 22 atomes de carbone ou leurs mélanges, R2 désigne un radical hydrocarboné linéaire ou ramifié comportant 2 à 26 atomes de carbone ou leurs mélanges, et y représente une valeur comprise entre 15 et 120.
  4. Détergent pour lave-vaisselle automatique selon l'une des revendications précédentes, caractérisé en ce que le détergent pour lave-vaisselle automatique contient, en tant que tensioactif non ionique b), un tensioactif de formule générale R1O[CH2CH(CH3)O]x[CH2CH2O]yCH2CH(OH)R2,
    dans laquelle R1 représente un radical hydrocarboné aliphatique linéaire ou ramifié comportant 4 à 22 atomes de carbone ou leurs mélanges, R2 désigne un radical hydrocarboné linéaire ou ramifié comportant 2 à 26 atomes de carbone ou leurs mélanges, et x représente des valeurs comprises entre 0,5 et 4 et y représente une valeur d'au moins 15.
  5. Détergent pour lave-vaisselle automatique selon l'une des revendications précédentes, caractérisé en ce que le détergent pour lave-vaisselle automatique contient, en tant que tensioactif non ionique b), un tensioactif de formule générale R1O[CH2CH(CH3)O]x[CH2CH2O]yCH2CH(OH)R2,
    dans laquelle R1 représente un radical hydrocarboné aliphatique linéaire ou ramifié comportant 4 à 22 atomes de carbone ou leurs mélanges, R2 désigne un radical hydrocarboné linéaire ou ramifié comportant 2 à 26 atomes de carbone ou leurs mélanges et x représente une valeur comprise entre 1 et 40 et y représente une valeur comprise entre 15 et 40, les motifs alkylène [CH2CH(CH3)O] et [CH2CH2O] étant présents de façon randomisée, c'est-à-dire sous la forme d'une distribution statistique aléatoire.
  6. Détergent pour lave-vaisselle automatique selon l'une des revendications précédentes, caractérisé en ce que le détergent pour lave-vaisselle contient, par rapport à son poids total, un tensioactif non ionique en des quantités de 0,1 à 15 % en poids, de préférence de 0,2 à 10 % en poids, de manière particulièrement préférée de 0,5 à 8 % en poids et en particulier de 1,0 à 6 % en poids.
  7. Détergent pour lave-vaisselle automatique selon l'une des revendications précédentes, caractérisé en ce que le détergent pour lave-vaisselle automatique contient, en tant que polymère anionique c), un copolymère comprenant
    i) des acides carboxyliques insaturés
    ii) des monomères contenant des groupes d'acide sulfonique
    iii) d'autres monomères non ionogènes.
  8. Détergent pour lave-vaisselle automatique selon l'une des revendications précédentes, caractérisé en ce que le détergent pour lave-vaisselle automatique contient, par rapport à son poids total, de 0,2 à 18 % en poids, de préférence de 0,5 à 15 % en poids et en particulier de 1,0 à 12 % en poids du polymère anionique c).
  9. Détergent pour lave-vaisselle automatique selon l'une des revendications précédentes, caractérisé en ce qu'il contient, par rapport à son poids total, une enzyme en des quantités de 0,1 à 12 % en poids, de préférence de 0,2 à 10 % en poids et en particulier de 0,5 à 8 % en poids.
  10. Détergent pour lave-vaisselle automatique selon l'une des revendications précédentes, caractérisé en ce qu'il se présente sous la forme d'une préparation liquide, aqueuse, faiblement alcaline, avec un pH (à 20 °C) d'une valeur comprise entre 8 et 12.
  11. Procédé de nettoyage de vaisselle dans un lave-vaisselle au moyen d'un détergent pour lave-vaisselle automatique selon l'une des revendications 1 à 10.
  12. Procédé selon la revendication 11, caractérisé en ce qu'aucun adoucisseur d'eau supplémentaire ni agent de rinçage supplémentaire ne sont ajoutés dans l'espace intérieur du lave-vaisselle pendant le procédé de nettoyage.
  13. Procédé selon l'une des revendications précédentes, caractérisé en ce que ce procédé est mis en oeuvre à des températures allant jusqu'à 55 °C au maximum, de préférence jusqu'à 50 °C au maximum.
  14. Utilisation d'un détergent pour lave-vaisselle automatique selon l'une des revendications 1 à 10 pour améliorer le séchage lors du lavage automatique de vaisselle.
EP08803450.9A 2007-09-10 2008-09-01 Détergents Active EP2185674B2 (fr)

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KR101548387B1 (ko) 2015-08-28
EP2185674B1 (fr) 2012-11-21
US20100160204A1 (en) 2010-06-24
WO2009033972A1 (fr) 2009-03-19
ES2395886T5 (es) 2021-10-11
EP2185674A1 (fr) 2010-05-19
ES2395886T3 (es) 2013-02-15
PL2185674T5 (pl) 2021-04-06
DE102007042860A1 (de) 2009-03-12
KR20100061670A (ko) 2010-06-08
PL2185674T3 (pl) 2013-04-30

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