EP2225357B1 - Composition détergente - Google Patents

Composition détergente Download PDF

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Publication number
EP2225357B1
EP2225357B1 EP08858511.2A EP08858511A EP2225357B1 EP 2225357 B1 EP2225357 B1 EP 2225357B1 EP 08858511 A EP08858511 A EP 08858511A EP 2225357 B1 EP2225357 B1 EP 2225357B1
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EP
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Prior art keywords
weight
washing
phase
cleaning agent
bleach
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EP08858511.2A
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German (de)
English (en)
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EP2225357A1 (fr
Inventor
Johannes Zipfel
Thomas Holderbaum
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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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0078—Multilayered tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • C11D17/045—Multi-compartment
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3932—Inorganic compounds or complexes

Definitions

  • the present patent application describes detergents or cleaning agents, in particular detergents for the machine cleaning of dishes.
  • This application relates in particular to two-phase or multiphase machine dishwashing detergents which contain bleach catalysts.
  • Machine-washed dishes are often subject to more stringent requirements today than manually-washed dishes.
  • a tableware that has been completely cleaned at first glance of food waste is then rated as not having any flaw if, after machine dishwashing, it still has discolorations which are based, for example, on the attachment of vegetable dyes to the dish surface.
  • automatic dishwashing detergents In order to obtain spotless dishes, bleaching agents are used in automatic dishwashing detergents. In order to activate these bleaching agents and to achieve an improved bleaching effect during cleaning at temperatures of 60 ° C. and below, automatic dishwashing detergents generally also contain bleach activators or bleach catalysts, with the bleach catalysts in particular having proven to be particularly effective.
  • EP 481 793 A1 Unilever detergent tablets are disclosed which contain sodium percarbonate, which according to the teaching of this application, preferably from other components detrimental to its stability, for example, in a separate layer, assembled.
  • EP 1162257 A describes multi-phase detergent tablets wherein one phase contains percarbonate, TAED and bleach catalyst.
  • the International Patent Publication WO 02/08380 describes multi-chamber bags for detergents containing in one chamber bleach catalyst, NOBS (activator) and PAP (peracid) and in another percarbonate or percarbonate and TAED.
  • EP 0851025 A describes multi-phase detergent tablets, one phase containing bleach, bleach activator, and bleach catalyst.
  • EP 0979864 A describes multi-phase detergent tablets, one phase containing bleach, bleach activator, and bleach catalyst.
  • the International Patent Publication WO 2005/105303 describes single-phase dishwashing tablets containing percarbonate, TAED and Mn catalyst with improved tea cleaning.
  • EP 1721962 A describes single-phase machine dishwashing tablets containing percarbonate, TAED and Mn catalyst.
  • Bleach catalysts are used in automatic dishwasher detergents, preferably in the form of prefabricated granules. This is how the European patents describe EP 458 397 B1 (Unilever) EP 458 398 B1 (Unilever) and EP 530 870 B1 (Unilever) bleach catalysts based on various manganese-containing transition metal complexes.
  • bleach catalysts may not yet be considered satisfactory to one skilled in the art.
  • phosphate-free, automatic dishwashing detergents often unexpectedly poor bleaching effects observed.
  • the storage stability of bleach catalyst-containing detergents often leaves something to be desired.
  • Characteristic of the two- or multi-phase detergents or cleaning agents according to the invention is the fact that the bleaching agent a) with one of the components b) or c) is present together in one phase of the washing or cleaning agent, and the other component in a different phase is present.
  • the two- or multi-phase detergents or cleaners are therefore characterized in that the total quantity of bleaching agent a) present in the two-phase or multi-phase detergent or cleaning agent together with the total amount of one of components b) or c) is present in one phase, while the other of components b) and c ) is in a different phase.
  • the two- or more-phase detergents or cleaners of the invention are therefore characterized in that the total amount of bleach a) with the total amount of one of components b) or c) is present in one phase in one phase, while the second component b ) or c) is present in a separate phase in a separate phase.
  • Multi-phase detergents or cleaners according to the invention contain as the first essential constituent an oxygen bleach.
  • an oxygen bleach is of particular importance.
  • Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -forming peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid 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 two- or more-phase detergents or cleaners are characterized in that the bleach a) is sodium percarbonate, more preferably a coated sodium percarbonate.
  • the proportion by weight of the bleaching agent a), based on the total weight of the washing or cleaning agent, is between 2 and 30% by weight, preferably between 4 and 20% by weight and in particular between 6 and 15% by weight.
  • two- or more-phase detergents or cleaners according to the invention contain bleach activators.
  • bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
  • TAED tetraacetylethylenediamine
  • Two-phase or multi-phase detergents or cleaners characterized in that the bleach activator b) is a bleach activator from the group of the acetylated amines, preferably tetraacetylenediamine (TAED), are preferred according to the invention.
  • the bleach activator b) is a bleach activator from the group of the acetylated amines, preferably tetraacetylenediamine (TAED), are preferred according to the invention.
  • bleach activators in particular TAED, are used in amounts of from 0.1% by weight to 10% by weight, especially from 0.5 to 8% by weight and particularly preferably from 1.0 to 6% by weight.
  • Two- or multi-phase detergents or cleaners characterized in that the proportion by weight of the bleach activator b), based on the total weight of the washing or cleaning agent, between 0.5 and 8 wt .-% and in particular between 1.0 and 6 wt. %, are preferred according to the invention.
  • the bleach activator b) used according to the invention is preferably used in particulate form, these particles preferably having a content of bleach activator above 80% by weight, based on their total weight. For the bleaching action described above, it has proven to be advantageous to realize the highest possible Blleichinatorgehalt in the granules.
  • Preferred two-phase or multi-phase detergents or cleaners according to the invention are characterized in that the bleach activator b) is in particulate form which, based on its total weight, has a content of bleach activator above 85% by weight, preferably above 90% by weight, particularly preferably above 95 wt .-% and in particular above 97 wt .-%.
  • the group of polymeric granulation aids includes the natural, but especially the synthetic organic polymers, for example the polymeric polycarboxylates or the polymeric polysulfonates.
  • the group of stabilizers includes in particular the phosphonates described below.
  • Preferred two- or multi-phase detergents or cleaning agents according to the invention are characterized in that the bleach activator b) is in particulate form, which, based on their total weight, less than 20 wt .-%, preferably less than 15 wt .-%, especially preferably contains less than 10 wt .-% and in particular less than 5 wt .-% of a polymeric granulation aid.
  • Preferred two- or multi-phase detergents or cleaners according to the invention are furthermore characterized in that the bleach activator b) is in particulate form, which, based on its total weight, is less than 20% by weight, preferably less than 15% by weight preferably contains less than 10 wt .-% and in particular less than 5 wt .-% stabilizing additives.
  • the detergents or cleaners according to the invention contain as third essential constituent at least one bleach catalyst c).
  • bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.
  • 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 which have 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
  • Two-phase or multi-phase detergents or cleaners characterized in that the bleach catalyst c) is a complex of manganese, 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-triaza-cyclononane (Me 4 -TACN) are preferred according to the invention.
  • the abovementioned bleach-enhancing transition metal complexes are used in conventional amounts, preferably in an amount of from 0.0025% by weight to 1% by weight and more preferably from 0.01% by weight to 0.30 % By weight, based in each case on the total weight of the bleach catalyst-containing agents. In special cases, however, more bleach catalyst can be used.
  • the two-phase or multi-phase detergents or cleaners of the invention are characterized in that the weight fraction of the bleach catalyst c), based on the total weight of the detergent or cleaner, is between 0.001 and 3.0% by weight, preferably between 0.01 and 2 , 0 wt .-% and in particular between 0.01 to 1.0 wt .-% is.
  • Some exemplary formulations for preferred two- or more-phase detergents or cleaners can be found in the following tables: ingredient Recipe 1 [% by weight] Recipe 2 [% by weight] Recipe 3 [% by weight] Recipe 4 [% by weight] Oxygen bleaches 2 to 30 4 to 20 4 to 20 6 to 15 bleach 0.1 to 10 0.5 to 8 0.5 to 8 1 to 6 bleach catalyst 0.001 to 3 0.001 to 3 0.01 to 2 0.01 to 1.0 ingredient Recipe 5 [% by weight] Recipe 6 [% by weight] Recipe 7 [% by weight] Recipe 8 [% by weight] sodium 2 to 30 4 to 20 4 to 20 6 to 15 bleach 0.1 to 10 0.5 to 8 0.5 to 8 1 to 6 bleach catalyst 0.001 to 3 0.001 to 3 0.01 to 2 0.01 to 1.0 ingredient Recipe 9 [% by weight] Recipe 10 [% by weight] Recipe 11 [% by weight] Recipe 12 [% by weight] sodium 2 to 30 4 to 20 4 to 20 6 to 15 TAED 0.1 to 10 0.5 to 8 0.5 to 8 1 to 6 bleach catalyst 0.001
  • two- or multi-phase detergents or cleaners according to the invention are characterized in that the bleaching agent a) is present together with one of the components b) or c) together in one phase of the washing or cleaning agent.
  • a first preferred embodiment of washing or cleaning agents according to the invention is characterized in that the bleaching agent a) is present together with the bleach activator b) in one phase of the washing or cleaning agent.
  • a second preferred embodiment of washing or cleaning agents according to the invention is characterized in that the bleaching agent a) is present together with the bleach catalyst c) in one phase of the washing or cleaning agent.
  • compositions according to the invention may contain further washing- or cleaning-active substances, preferably from the group of builders, surfactants, polymers, enzymes, glass corrosion inhibitors, corrosion inhibitors, disintegration aids, fragrances and perfume carriers. These preferred ingredients will be described in more detail below.
  • the builders include, in particular, the zeolites, silicates, carbonates, organic cobuilders and, where there are no ecological prejudices against their use, also the phosphates.
  • Detergents or cleaning agents preferably contain a weight fraction of the crystalline layered silicate of the formula NaMSi x O 2x + 1 .yH 2 O of from 0.1 to 20% by weight, preferably from 0.2 to 15% by weight and in particular of 0.4 to 10 wt .-%, each based on the total weight of these agents.
  • 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.
  • Preferred washing or cleaning agents are free of water-insoluble aluminum silicates, such as the natural or synthetic zeolites used for water softening.
  • 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.
  • phosphates are used as detergents or cleaning agents in the context of the present application
  • preferred agents comprise these phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or pentasodium) Potassium tripolyphosphate), in amounts of 5 to 80 wt .-%, preferably from 15 to 75 wt .-% and in particular from 20 to 70 wt .-%, each based on the weight of the detergent or cleaning agent.
  • alkali metal phosphate preferably pentasodium or pentapotassium triphosphate (sodium or pentasodium) Potassium tripolyphosphate
  • 5 to 80 wt .-% preferably from 15 to 75 wt .-% and in particular from 20 to 70 wt .-%, each based on the weight of the detergent or cleaning agent.
  • the washing or cleaning compositions according to the invention comprise at least one acid group-containing polymer which acts as a softener.
  • the acid group-containing polymer comprises at least one acid group-containing monomer and optionally further nonionic (s), preferably hydrophobic monomer (s).
  • the proportion by weight of this polymer or these polymers in the total weight of the automatic dishwashing agent is preferably 0.1 to 30 wt .-%, preferably 0.5 to 25 wt .-% and in particular 1.0 to 20 wt .-%.
  • the acid group-containing monomer i) has a carboxylic acid group and / or a sulfonic acid group.
  • Particularly preferred 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 copolymers further comprise at least one additional ionic monomer in addition to at least one carboxylic acid group-containing monomer.
  • 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-propenylsulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate , Sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of said acids or their water-soluble salt
  • the sulfonic acid groups may be wholly or partly in neutralized form, ie that the acidic acid of the sulfonic acid group in some or all sulfonic acid groups may be exchanged for metal ions, preferably alkali metal ions and especially sodium ions.
  • 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 i) and from 10 to 50% by weight of monomer from group ii), 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 further comprise at least one additional ionic monomer in addition to at least one sulfonic acid group-containing monomer.
  • Particularly preferred unsaturated hydrocarbon radicals 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-octadec
  • alkali carriers are, for example, alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal sesquicarbonates, the cited alkali metal silicates, alkali metal silicates and mixtures of the abovementioned substances, preference being given to using alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate for the purposes of this invention.
  • alkali metal carbonates in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate for the purposes of this invention.
  • a builder system comprising a mixture of tripolyphosphate and sodium carbonate.
  • a builder system comprising a mixture of tripolyphosphate and sodium carbonate and sodium disilicate.
  • the alkali metal hydroxides are preferably only in small amounts, preferably in amounts below 10 wt .-%, preferably below 6 wt .-%, more preferably below 4 wt .-% and in particular below 2 wt .-%, each based on the total weight of the detergent or cleaning agent used.
  • Particularly preferred are agents which, based on their total weight, contain less than 0.5% by weight and in particular no alkali metal hydroxides.
  • compositions which, based on the weight of the washing or cleaning agent, contain less than 20% by weight, preferably less than 17% by weight, preferably less than 13% by weight and in particular less than 9% by weight of carbonate ( e) and / or bicarbonate (s), preferably alkali metal carbonate (s), particularly preferably sodium carbonate.
  • 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.
  • 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, due to its structural relationship with gives the investigated polymers realistic molecular weight values. 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.
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution.
  • the content of detergents or cleaning agents in (co) polymeric polycarboxylates is preferably from 0.5 to 20% by weight and in particular from 3 to 10% by weight.
  • the polymers may also contain allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.
  • biodegradable polymers of more than two different monomer units for example those which contain as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives ,
  • copolymers are those which have as their monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
  • Effective polymers as softeners are, for example, the sulfonic acid-containing polymers which are used with particular preference.
  • Corresponding polymers have already been described above as constituents of bleach activator granules according to the invention, for which reason reference is made to the statements there to avoid repetitions at this point.
  • polymeric aminodicarboxylic acids their salts or their precursors. Particular preference is given to polyaspartic acids or their salts.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • 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. Suitable amounts are from 3 to 15 wt .-%.
  • 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
  • It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9).
  • 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.
  • automatic dishwashing detergents 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 automatic dishwashing compositions of the invention may contain two or more different phosphonates.
  • Two-phase or multi-phase washing or cleaning agent characterized in that the two- or multi-phase detergent or cleaning agent further contains at least one phosphonate, preferably 1-hydroxyethane-1,1-diphosphonic acid (HEDP), which together with the bleaching agent a) is present in a phase of the washing or cleaning agent, are preferred according to the invention.
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • the proportion by weight of the phosphonates is preferably 0.5 to 14 wt .-%, preferably 1 to 12 wt .-% and in particular 2 to 8 wt .-%.
  • Some exemplary formulations for preferred two- or more-phase phosphonate-containing detergents or cleaners can be found in the following tables, wherein the formulations 81 to 84 serve as comparative examples.
  • the inventive machine dishwashing detergents contain methylglycinediacetic acid or a salt of methylglycinediacetic acid, wherein the weight fraction of methylglycinediacetic acid or of the salt of methylglycinediacetic acid is preferably between 0.5 and 15% by weight, preferably between 0.5 and 10% by weight and in particular between 0.5 and 6 wt .-% is.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • the group of surfactants includes nonionic, anionic, cationic and amphoteric surfactants.
  • Nonionic surfactants which can be used are the nonionic surfactants known to the person skilled in the art. Suitable nonionic surfactants are, for example, alkyl glycosides of the general formula RO (G) x in which R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which is a glycose unit having 5 or 6 C atoms, preferably glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.
  • nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain.
  • washing or cleaning agents in particular automatic dishwashing detergents, contain nonionic surfactants from the group of the alkoxylated alcohols.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
  • EO ethylene oxide
  • alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 moles of EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohols with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 -alcohol with 3 EO and C 12-18 -alcohol with 5 EO.
  • the stated degrees of ethoxylation represent statistical averages, which may correspond to a particular product of an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • NRE narrow range ethoxylates
  • Nonionic surfactants can also be used fatty alcohols with more than 12 EO. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • ethoxylated nonionic surfactants consisting of C 6-20 monohydroxyalkanols or C 6-20 alkylphenols or C 16-20 fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 mol of ethylene oxide per mol Alcohol was used.
  • a particularly preferred nonionic surfactant is obtained from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C 16-20 alcohol), preferably a C 18 -alcohol and at least 12 mol, preferably at least 15 mol and especially at least 20 mol of ethylene oxide.
  • C 16-20 alcohol straight-chain fatty alcohol having 16 to 20 carbon atoms
  • C 18 -alcohol preferably a C 18 -alcohol
  • at least 12 mol preferably at least 15 mol and especially at least 20 mol of ethylene oxide.
  • the so-called “narrow range ethoxylates” are particularly preferred.
  • Nonionic surfactants which have a melting point above room temperature.
  • surfactants come from the groups of alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants).
  • Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.
  • More particularly preferred nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight. % of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.
  • nonionic surfactants have been low foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units.
  • surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows.
  • nonionic surfactants of the general formula in which R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 alkyl or alkenyl radical; each group R 2 or R 3 is independently selected from -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , CH (CH 3 ) 2 and the indices w, x, y, z independently stand for integers from 1 to 6.
  • nonionic surfactants having a C 9-15 alkyl group having 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units followed by 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units. These surfactants have the required low viscosity in aqueous solution and can be used according to the invention with particular preference.
  • R 1 -CH (OH) CH 2 O- (AO) w - (A'O) x - (A "O) y - (A"'O) z -R 2 in which R 1 and R 2 independently of one another represents a straight-chain or branched, saturated or mono- or polyunsaturated C 2-40 -alkyl or -alkenyl radical;
  • A, A ', A "and A'” independently represent a radical from the group -CH 2 CH 2 , -CH 2 CH 2 -CH 2 , -CH 2 -CH (CH 3 ), -CH 2 -CH 2 -CH 2 -CH 2 , -CH 2 -CH (CH 3 ) -CH 2 -, -CH 2 -CH (CH 2 -CH 3 ); and w, x, y and z are values between 0.5 and 90, where x, y and / or z can also be 0 are preferred according to the invention
  • 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 z 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.
  • 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 OR 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, iso-propyl, 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.
  • 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, resulting in both the C chain lengths as well as for the degrees of ethoxylation or degrees of alkoxylation may give mean values and, consequently, fractional numbers.
  • nonionic surfactants can be used not only as individual substances, but also as surfactant mixtures of two, three, four or more surfactants.
  • Mixtures of surfactants are not mixtures of nonionic surfactants which fall in their entirety under one of the abovementioned general formulas, but rather mixtures which contain two, three, four or more nonionic surfactants which can be described by different general formulas ,
  • anionic surfactants are used as constituents of automatic dishwasher detergents, their content, based on the total weight of the compositions, is preferably less than 4% by weight, preferably less than 2% by weight and very particularly preferably less than 1% by weight. Machine dishwashing detergents which do not contain anionic surfactants are particularly preferred.
  • the content of cationic and / or amphoteric surfactants is preferably less than 6% by weight, preferably less than 4% by weight, very particularly preferably less than 2% by weight and in particular less than 1% by weight.
  • Automatic dishwashing detergents containing no cationic or amphoteric surfactants are particularly preferred.
  • Some exemplary formulations for preferred two- or more-phase surfactant-containing detergents or cleaners can be found in the following Tables, with Formulations 93-96 serving as comparative examples.
  • the group of polymers includes, in particular, the washing or cleaning-active polymers, for example the rinse aid polymers and / or polymers which act as softeners.
  • the washing or cleaning-active polymers for example the rinse aid polymers and / or polymers which act as softeners.
  • cationic, anionic and amphoteric polymers can be used in detergents or cleaners in addition to nonionic polymers.
  • “Cationic polymers” in the context of the present invention are polymers which carry a positive charge in the polymer molecule. This can be realized, for example, by (alkyl) ammonium groups or other positively charged groups present in the polymer chain.
  • Particularly preferred cationic polymers come from the groups of quaternized cellulose derivatives, the polysiloxanes with quaternary groups, the cationic guar derivatives, the polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, the copolymers of vinylpyrrolidone with quaternized derivatives of dialkylamino and methacrylates, the vinylpyrrolidone-methoimidazolinium chloride copolymers, the quaternized polyvinyl alcohols or the polymers specified under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.
  • amphoteric polymers further comprise, in addition to a positively charged group in the polymer chain, also negatively charged groups or monomer units. These groups may be, for example, carboxylic acids, sulfonic acids or phosphonic acids.
  • particularly preferred cationic or amphoteric polymers contain as monomer unit a compound of the general formula in which R 1 and R 4 are each independently H or a linear or branched hydrocarbon radical having 1 to 6 carbon atoms; R 2 and R 3 are independently an alkyl, hydroxyalkyl, or aminoalkyl group in which the alkyl group is linear or branched and has from 1 to 6 carbon atoms, preferably a methyl group; x and y independently represent integers between 1 and 3.
  • X - represents a counterion, preferably a counterion from the group chloride, bromide, iodide, sulfate, hydrogen sulfate, methosulfate, lauryl sulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate), cumene sulfonate, xylenesulfonate, phosphate, citrate, formate, acetate or mixtures thereof.
  • Preferred radicals R 1 and R 4 in the above formula are selected from -CH 3 , -CH 2 -CH 3 , -CH 2 -CH 2 -CH 3 , -CH (CH 3 ) -CH 3 , -CH 2 -OH , -CH 2 -CH 2 -OH, -CH (OH) -CH 3 , -CH 2 -CH 2 -CH 2 -OH, -CH 2 -CH (OH) -CH 3 , - CH (OH) -CH 2 -CH 3 , and - (CH 2 CH 2 -O) n H.
  • amphoteric polymers have not only cationic groups but also anionic groups or monomer units.
  • anionic monomer units are derived, for example, from the group of linear or branched, saturated or unsaturated carboxylates, linear or branched, saturated or unsaturated phosphonates, linear or branched, saturated or unsaturated sulfates or linear or branched, saturated or unsaturated sulfonates.
  • Preferred monomer units are acrylic acid, (meth) acrylic acid, (dimethyl) acrylic acid, (ethyl) acrylic acid, cyanoacrylic acid, vinylessingic acid, allylacetic acid, crotonic acid, maleic acid, fumaric acid, cinnamic acid and its derivatives, allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid or the allylphosphonic acids.
  • Preferred employable amphoteric polymers are from the group of the alkylacrylamide / acrylic acid copolymers, the alkylacrylamide / methacrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid copolymers, the alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methacrylic acid / Alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / alkymethacrylate / alkylaminoethylmethacrylate / alkylmethacrylate copolymers and the copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally other ionic or nonionic monomers
  • Preferred zwitterionic polymers are from the group of acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali metal and ammonium salts, the acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali metal and ammonium salts and the methacroylethylbetaine / methacrylate copolymers.
  • amphoteric polymers which comprise, in addition to one or more anionic monomers as cationic monomers Methacrylamidoalkyl-trialkylammonium chloride and dimethyl (diallyl) -ammonium chloride.
  • amphoteric polymers are selected from the group consisting of the methacrylamidoalkyl trialkyl ammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the methacrylamidoalkyl trialkyl ammonium chloride / dimethyl (diallyl) ammonium chloride / methacrylic acid copolymers and the methacrylamidoalkyl trialkyl ammonium chloride / dimethyl (diallyl) ammonium chloride / alkyl ( meth) acrylic acid copolymers and their alkali metal and ammonium salts.
  • amphoteric polymers from the group of the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers and the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl ) ammonium chloride / alkyl (meth) acrylic acid copolymers and their alkali metal and ammonium salts.
  • Detergents or cleaning agents preferably contain the abovementioned cationic and / or amphoteric polymers in amounts of between 0.01 and 10% by weight, based in each case on the total weight of the detergent or cleaning agent.
  • detergents or cleaners enzymes can be used. These include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, 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 cleaners contain enzymes preferably in total amounts of 1 ⁇ 10 -6 to 5% by weight, based on active protein. The protein concentration can be determined by known methods, for example the BCA method or the biuret method.
  • subtilisins those of the subtilisin type are preferable.
  • examples include the subtilisins BPN 'and Carlsberg and their advanced forms, the protease PB92, the subtilisins 147 and 309, the Alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, proteinase K and the proteases TW3 and TW7, which are assigned to the subtilases, but no longer to the subtilisins in the narrower sense.
  • 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).
  • the spectrum of the invention preferred zinc salts, preferably organic acids, particularly preferably organic carboxylic acids, ranging from salts which are difficult or insoluble in water, ie a solubility below 100 mg / l, preferably below 10 mg / l, in particular below 0.01 have mg / l, to those salts which have a solubility in water above 100 mg / l, preferably above 500 mg / l, more 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 organic carboxylic acid particularly preferably a zinc salt from the group zinc stearate, zinc oleate, zinc gluconate, zinc acetate, zinc lactate and zinc citrate.
  • Zinc ricinoleate, zinc abietate and zinc oxalate are also preferred.
  • the content of zinc salt in detergents or cleaners is preferably between 0.1 and 5% by weight, preferably between 0.2 and 4% by weight and in particular between 0.4 and 3% by weight.
  • 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, 2 wt .-%, each based on the total weight of the glass corrosion inhibitor-containing agent.
  • Corrosion inhibitors serve to protect the items to be washed or the machine, with particular silver protectants being of particular importance in the field of automatic dishwashing. It is possible to use the known substances of the prior art. In general, silver protectants selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes can be used in particular. Particularly preferred to use are benzotriazole and / or alkylaminotriazole.
  • cleaner formulations often contain active chlorine-containing agents which can markedly reduce the corrosion of the silver surface.
  • active chlorine-containing agents such as oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, such as hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds are used.
  • salt and complex inorganic compounds such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used.
  • transition metal salts which are selected from the group of manganese and / or cobalt salts and / or complexes, especially preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese and manganese sulfate.
  • zinc compounds can be used to prevent corrosion on the items to be washed.
  • the metal salts and / or metal complexes mentioned are contained in cleaning agents, preferably in an amount of 0.05 to 6 wt .-%, preferably 0.2 to 2.5 wt .-%, each based on the total agent.
  • Two- or multi-phase detergent or cleaning agent characterized in that the two- or multi-phase detergent or cleaning agent further contains a silver protection agent which is present together with the bleaching agent a) in a phase of the detergent or cleaning agent, are preferred according to the invention.
  • Some exemplary formulations for preferred two- or more-phase silver-protecting agent-containing detergents or cleaners can be taken from the following tables, wherein the formulations 117-120 serve as comparative examples.
  • Silver protection agent [1] 0.05 to 6 0.05 to 6 0.2 to 2.5 0.2 to 2.5
  • perfume oils or perfumes within the scope of the present invention, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance.
  • perfume oils may also contain natural fragrance mixtures such as are available from vegetable sources, e.g. Pine, Citrus, Jasmine, Patchouly, Rose or Ylang-Ylang oil.
  • Preferred dyes the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the agents and to light and no pronounced substantivity to the substrates to be treated with the dye-containing agents such as textiles, glass, ceramics or plastic dishes do not stain them.
  • disintegration aids so-called tablet disintegrants
  • tablet disintegrants or disintegrants are meant excipients which ensure the rapid disintegration of tablets in water or other media and for the rapid release of the active ingredients.
  • 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 disintegration aids preferably a disintegration aid based on cellulose, preferably in granular, cogranulated or compacted form, are present 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 of 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.
  • the gas-evolving effervescent system may consist of a single substance that releases a gas upon contact with water. Among these compounds, mention should be made in particular of magnesium peroxide, which liberates oxygen on contact with water.
  • the gas-releasing effervescent system in turn consists of at least two components which react with each other to form gas. While a variety of systems are conceivable and executable here, which release, for example, nitrogen, oxygen or hydrogen, the bubble system used in detergents and cleaners can be selected both on the basis of economic and environmental considerations.
  • Preferred effervescent systems consist of 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.
  • Acidificationsmittel which release carbon dioxide from the alkali metal salts in aqueous solution, for example, boric acid and alkali metal hydrogen sulfates, alkali metal dihydrogen phosphates and other inorganic salts can be used.
  • organic acidifying agents preference is given to using organic acidifying agents, the citric acid being a particularly preferred acidifying agent. Acidifying agents in the effervescent system from the group of organic di-, tri- and oligocarboxylic acids or mixtures are preferred.
  • the detergents or cleaners according to the invention are in the form of two- or multiphase offer forms, preferably in the form of two-, three- or four-phase offer forms.
  • forms of offer themselves are preferably made up in the form of a dosing unit.
  • the term "detergent or makesffendosierü” referred to in the present application in particular such forms of supply, which contain sufficient to carry out individual cleaning cycles amount of washing and cleaning-active substances.
  • Such forms of supply preferably have, for example, a weight between 8 and 35 g, preferably between 10 and 30 g and in particular between 12 and 25 g.
  • the volume of the shaped bodies is usually in the range between 5 and 40 ml, preferably between 8 and 30 ml and in particular between 12 and 20 ml.
  • washing or cleaning agent dosing units have dimensions in the range 5 cm ⁇ 3 cm ⁇ 3 cm, preferably in the range 4.5 cm ⁇ 2.5 cm ⁇ 2.5 cm, particularly preferably in the range 4 cm ⁇ 2 cm, 2 cm ,
  • phase of these two- or multi-phase detergent or makesmitteldosierüen macroscopically visible areas of these dosing units are referred to in the context of this application.
  • tableted detergent or detergent dosing units these are, for example, layers or cores.
  • metering units in the form of injection-molded bodies or foil bags the washing or cleaning-active preparations present in the receiving chambers of these metering units are referred to as "phases".
  • the two- or multi-phase detergents or cleaners according to the invention can have solid or liquid phases or combinations of solid and liquid phases.
  • two-phase or multi-phase detergent or dosing units are, as stated above, two-layered or multi-layered tablets or injection-molded articles with two or more separate receiving chambers.
  • the two- or multi-phase detergents or cleaners according to the invention are in the form of a two-phase or multi-phase, preferably one two-layered or multi-layered tablet.
  • the individual phases of the two- or multi-phase base tablet or core tablet are preferably arranged in layers.
  • the proportion by weight of the smallest phase, based on the total tablet, is preferably at least 5% by weight, preferably at least 10% by weight and in particular at least 20% by weight.
  • the proportion by weight of the phase with the highest proportion by weight of the tablet in the case of biphasic tablets is preferably not more than 90% by weight, preferably not more than 80% by weight and in particular between 55 and 70% by weight.
  • the proportion by weight of the phase with the highest proportion by weight of the tablet is preferably not more than 80% by weight, preferably not more than 70% by weight and in particular between 35 and 60% by weight.
  • the manufacture of the dishwasher tablets preferably takes place in a manner known to the person skilled in the art by compressing particulate premixes.
  • the particulate premix has an average particle size between 0.4 and 3.0 mm, preferably between 0.6 and 2.5 mm and in particular between 0.8 and 2.0 mm.
  • Preferred processes in the context of the present invention are characterized in that the pressing takes place at pressing pressures of 0.01 to 50 kNcm -2 , preferably of 0.1 to 40 kNcm -2 and in particular of 1 to 25 kNcm -2 .
  • the density of dishwasher tablets preferred according to the invention is between 1.1 and 1.8 g / cm 3 , preferably between 1.2 and 1.7 cm 3 and in particular between 1.3 and 1.6 g / cm 3 .
  • Concentric presses can be provided to increase the throughput with two filling shoes, which only a semicircle must be run through to produce a tablet.
  • the tablets in the context of the present invention can also be multi-phase, in particular multi-layered.
  • the moldings can be made in a predetermined spatial form and predetermined size.
  • a form of space practically all useful manageable configurations come into consideration, for example, the training as a blackboard, the bar or bar shape, cubes, cuboids and corresponding space elements with flat side surfaces and in particular cylindrical configurations with circular or oval cross-section.
  • This last embodiment covers the presentation form of the tablet up to compact cylinder pieces with a ratio of height to diameter above 1.
  • Particularly preferred two- or multi-phase detergents or cleaners according to the invention have the form of a well tablet with a core inserted into the well, preferably compressed.
  • the detergent tablets After pressing, the detergent tablets have a high stability.
  • ⁇ is the diametrical fracture stress (DFS) in Pa
  • P is the force in N which results in the pressure applied to the molded article causing the breakage of the molded article
  • D is the molded article diameter in meters and t the height of the moldings.
  • the two- or multi-phase detergents or cleaners according to the invention are in the form of injection-molded metering units with two or more separate receiving chambers.
  • Injection molding refers to the forming of a molding material such that the mass contained in a mass cylinder for more than one injection molding plastically softens under heat and flows under pressure through a nozzle into the cavity of a previously closed tool.
  • the method is mainly applied to non-hardenable molding compounds which solidify in the tool by cooling.
  • Injection molding is a very economical modern process for producing non-cutting shaped articles and is particularly suitable for automated mass production.
  • thermoplastic molding compounds are heated to liquefaction (up to 180 ° C) and injected under high pressure (up to 140 MPa) in closed, two-piece, that is from Gesenk (earlier Die) and core (formerly male) existing, preferably water-cooled molds, where they cool and solidify.
  • Suitable molding compositions are water-soluble polymers such as, for example, cellulose ethers, pectins, polyethylene glycols, polyvinyl alcohols, polyvinylpyrrolidones, alginates, gelatin or starch.
  • the automatic dishwasher 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.
  • compositions according to the invention are distinguished from conventional automatic dishwasher detergents by an improved cleaning performance on bleachable soiling.
  • An object of the present application is therefore also the use of a machine dishwashing detergent according to the invention for improving the bleaching performance in automatic dishwashing, in particular for removing tea stains.
  • the values given are the mean values of purification tests which were carried out immediately after preparation of the dishwasher tablets and after storage for 4 weeks.

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Claims (13)

  1. Agent de lavage ou de nettoyage contenant deux phases ou plus, comprenant :
    a) un agent de blanchiment ;
    b) un activateur du blanchiment ;
    c) un catalyseur du blanchiment choisi parmi le groupe des sels de métaux de transition et des complexes de métaux de transition renforçant le blanchiment;
    dans lequel l'agent de blanchiment a) est présent de manière conjointe avec au moins un des constituants b) ou c) dans une phase de l'agent de lavage ou de nettoyage, l'agent de lavage ou de nettoyage est présent sous la forme d'un comprimé contenant deux phases ou plus ou sous la forme d'une unité de dosage moulée par injection comprenant deux chambres de réception séparées l'une de l'autre et, en ce qui concerne l'agent de blanchiment, il s'agit d'un agent de blanchiment oxygéné ;
    caractérisé en ce que parmi les trois composants, à savoir l'agent de blanchiment oxygéné, l'activateur du blanchiment et le catalyseur du blanchiment, l'agent de blanchiment oxygéné se trouve respectivement avec un des deux autres composants dans une première phase et le troisième composant respectif se trouve dans une deuxième phase, l'agent de blanchiment oxygéné étant présent en une quantité de 2 à 30 % en poids, l'activateur du blanchiment en une quantité de 0,1 à 10 % en poids et le catalyseur du blanchiment en une quantité de 0,001 à 3 % en poids, chaque fois rapportés au poids total de l'agent de lavage ou de nettoyage.
  2. Agent de lavage ou de nettoyage contenant deux phases ou plus selon la revendication 1, caractérisé en ce que, en ce qui concerne l'agent de blanchiment oxygéné, il s'agit de percarbonate de sodium, de préférence de percarbonate de sodium enduit.
  3. Agent de lavage ou de nettoyage contenant deux phases ou plus selon l'une quelconque des revendications précédentes, caractérisé en ce que la fraction pondérale de l'agent de blanchiment a), rapportée au poids total de l'agent de lavage ou de nettoyage, se situe entre 4 et 20 % en poids et en particulier entre 6 et 15 % en poids.
  4. Agent de lavage ou de nettoyage contenant deux phases ou plus selon l'une quelconque des revendications précédentes, caractérisé en ce que, en ce qui concerne l'activateur du blanchiment b), il s'agit d'un activateur du blanchiment choisi parmi le groupe des amines acétylées, de préférence de la tétraacéthylènediamine (TAED).
  5. Agent de lavage ou de nettoyage contenant deux phases ou plus selon l'une quelconque des revendications précédentes, caractérisé en ce que la fraction pondérale de l'activateur du blanchiment b), rapportée au poids total de l'agent de lavage ou de nettoyage, se situe entre 0,5 et 8 % en poids et en particulier entre 1,0 et 6 % en poids.
  6. Agent de lavage ou de nettoyage contenant deux phases ou plus selon l'une quelconque des revendications précédentes, caractérisé en ce que, en ce qui concerne le catalyseur du blanchiment c), il s'agit d'un complexe du manganèse, de préférence choisi parmi le groupe des complexes du manganèse avec le 1,4,7-triméthyl-1,4,7-triazacyclononane (Me3-TACN) ou avec le 1,2,4,7-tétraméthyl-1,4,7-triazacyclononane (Me4-TACN).
  7. Agent de lavage ou de nettoyage contenant deux phases ou plus selon l'une quelconque des revendications précédentes, caractérisé en ce que la fraction pondérale du catalyseur du blanchiment c), rapportée au poids total de l'agent de lavage ou de nettoyage, se situe entre 0,01 et 2,0 % en poids et en particulier entre 0,01 et 1,0 % en poids.
  8. Agent de lavage ou de nettoyage contenant deux phases ou plus selon l'une quelconque des revendications précédentes, caractérisé en ce que l'agent de blanchiment a) est présent de manière conjointe avec l'activateur du blanchiment b) dans une phase de l'agent de lavage ou de nettoyage.
  9. Agent de lavage ou de nettoyage contenant deux phases ou plus selon l'une quelconque des revendications précédentes, caractérisé en ce que l'agent de blanchiment a) est présent de manière conjointe avec le catalyseur du blanchiment c) dans une phase de l'agent de lavage ou de nettoyage.
  10. Agent de lavage ou de nettoyage contenant deux phases ou plus selon l'une quelconque des revendications précédentes, caractérisé en ce que l'agent de lavage ou de nettoyage contenant deux phases ou plus contient en outre au moins un phosphonate, de préférence l'acide 1-hydroxyéthane-1,1 diphosphonique (HEDP), qui est présent de manière conjointe avec l'agent de blanchiment a) dans une phase de l'agent de lavage ou de nettoyage.
  11. Agent de lavage ou de nettoyage contenant deux phases ou plus selon l'une quelconque des revendications précédentes, caractérisé en ce que l'agent de lavage ou de nettoyage est présent sous la forme d'un comprimé contenant deux couches ou plus.
  12. Procédé pour le nettoyage de la vaisselle dans un lave-vaisselle, dans lequel on met en oeuvre un détergent pour le lavage mécanique de la vaisselle selon l'une quelconque des revendications 1 à 11.
  13. Procédé selon la revendication 12, caractérisé en ce qu'on n'ajoute, au cours du processus de nettoyage, aucun adoucisseur d'eau supplémentaire et aucun un agent de rinçage supplémentaire à l'intérieur du lave-vaisselle.
EP08858511.2A 2007-12-11 2008-11-05 Composition détergente Revoked EP2225357B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL08858511T PL2225357T3 (pl) 2007-12-11 2008-11-05 Środki czyszczące

Applications Claiming Priority (2)

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DE102007059968A DE102007059968A1 (de) 2007-12-11 2007-12-11 Reinigungsmittel
PCT/EP2008/064970 WO2009074404A1 (fr) 2007-12-11 2008-11-05 Détergents

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EP2225357A1 EP2225357A1 (fr) 2010-09-08
EP2225357B1 true EP2225357B1 (fr) 2013-12-25

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EP08858511.2A Revoked EP2225357B1 (fr) 2007-12-11 2008-11-05 Composition détergente

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US (1) US20100249007A1 (fr)
EP (1) EP2225357B1 (fr)
KR (1) KR101577470B1 (fr)
DE (1) DE102007059968A1 (fr)
ES (1) ES2442942T3 (fr)
PL (1) PL2225357T3 (fr)
WO (1) WO2009074404A1 (fr)

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EP2260093B1 (fr) * 2008-03-31 2014-12-10 The Procter and Gamble Company Composition détergente pour lave-vaisselle contenant un copolymère sulfoné
DE102008060470A1 (de) * 2008-12-05 2010-06-10 Henkel Ag & Co. Kgaa Reinigungsmittel
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US20120258156A1 (en) 2011-04-06 2012-10-11 Evan Rumberger Shaped compositions for uniform delivery of a functional agent
CA2832887A1 (fr) 2011-04-11 2012-10-18 ADA-ES, Inc. Methode par lit fluidise et systeme de capture de composant gazeux
US9278314B2 (en) 2012-04-11 2016-03-08 ADA-ES, Inc. Method and system to reclaim functional sites on a sorbent contaminated by heat stable salts
JP6140365B2 (ja) 2013-05-02 2017-05-31 エコラボ ユーエスエー インコーポレイティド 物品洗浄用途における澱粉の改善された除去のための濃縮した洗浄剤組成物
JP6254693B2 (ja) * 2013-10-24 2017-12-27 エコラボ ユーエスエー インコーポレイティド 表面から汚れを除去する組成物及び方法
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Publication number Publication date
PL2225357T3 (pl) 2014-05-30
DE102007059968A1 (de) 2009-06-18
KR20100106375A (ko) 2010-10-01
WO2009074404A1 (fr) 2009-06-18
EP2225357A1 (fr) 2010-09-08
ES2442942T3 (es) 2014-02-14
KR101577470B1 (ko) 2015-12-14
US20100249007A1 (en) 2010-09-30

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