EP3325596B1 - Lessive lave-vaisselle contenant des agents de blanchiment et des polymères - Google Patents

Lessive lave-vaisselle contenant des agents de blanchiment et des polymères Download PDF

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Publication number
EP3325596B1
EP3325596B1 EP16741023.2A EP16741023A EP3325596B1 EP 3325596 B1 EP3325596 B1 EP 3325596B1 EP 16741023 A EP16741023 A EP 16741023A EP 3325596 B1 EP3325596 B1 EP 3325596B1
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EP
European Patent Office
Prior art keywords
acid
dishwasher detergent
group
automatic dishwasher
weight
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EP16741023.2A
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German (de)
English (en)
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EP3325596A1 (fr
Inventor
Inga Kerstin Vockenroth
Johannes Zipfel
Volker Blank
Thomas Weber
Noelle Wrubbel
Klaus Dorra
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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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/378—(Co)polymerised monomers containing sulfur, e.g. sulfonate
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • 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
    • 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
    • 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

Definitions

  • the present invention relates to a machine dishwashing detergent which shows improved cleaning performance, particularly on bleach-sensitive stains, to the use of this dishwashing agent and to a method for machine dishwashing using this dishwashing agent.
  • German patent application DE 102013226430 A1 describes phosphate-containing dishwashing detergents which contain acrylate polymer and polymer containing sulfonic acid groups.
  • the DE 102013225591 A1 discloses automatic dishwashing detergents which contain acrylate polymer and sulfonic acid group-containing polymer in combination with specific N-based complexing agents.
  • the DE102008060470 A1 discloses automatic dishwashing detergents in which two different copolymers, comprising sulfonic acid-containing groups, are used in combination with a nonionic surfactant.
  • the object of the present invention was therefore to provide a, preferably phosphate-free, automatic dishwashing detergent which has an increased cleaning performance.
  • a first object of the present invention is therefore a machine dishwashing detergent which contains less than 1% by weight of phosphate, containing at least one bleaching agent, at least one bleaching catalyst, at least one homopolymer of an ⁇ , ⁇ -ethylenically unsaturated carboxylic acid and at least one copolymer containing at least one Monomer containing sulfonic acid groups and at least one monomer from the group of ⁇ , ⁇ ethylenically unsaturated carboxylic acids, the at least one homopolymer and the at least one copolymer each in an amount of 0.5 to 5% by weight. based on the total weight of the dishwasher detergent is included.
  • the present invention also relates to the use of an automatic dishwashing agent according to the invention in an automatic dishwashing process, in particular the use to improve the cleaning performance of bleach-sensitive stains on dishes when cleaning them in an automatic dishwasher.
  • the present invention is also directed to an automatic dishwashing method in which an automatic dishwashing agent according to the invention is used in particular for the purpose of improving the cleaning performance of bleach-sensitive soiling.
  • At least one as used herein means 1 or more, i.e. 1, 2, 3, 4, 5, 6, 7, 8, 9 or more.
  • the information refers to the type of ingredient and not to the absolute number of molecules.
  • At least one bleach catalyst thus means, for example, at least one type of bleach catalyst, i.e. that one type of bleaching catalyst or a mixture of several different bleaching catalysts can be meant.
  • the information relates to all compounds of the specified type which are contained in the composition / mixture, i.e. that the composition contains no further compounds of this type beyond the stated amount of the corresponding compounds.
  • the number average molecular weight can be determined, for example, by means of gel permeation chromatography (GPC) according to DIN 55672-1: 2007-08 with THF as the eluent.
  • the mass average molecular weight M w can also be determined by means of GPC, as described for M n .
  • a phase in the sense of the present invention is a spatial area in which physical parameters and the chemical composition are homogeneous.
  • a phase differs from another phase by different features, for example ingredients, physical properties, external appearance, etc.
  • Different phases can preferably be distinguished optically.
  • the at least one first phase must be clearly distinguished from the at least one second phase. If the washing or cleaning agent according to the invention has more than one first phase, these can likewise be distinguished from one another with the naked eye, because they differ from one another, for example, in their coloring. The same applies if there are two or more second phases. In this case too, the phases can be optically distinguished, for example on the basis of a color or transparency difference.
  • Phases in the sense of the present invention are thus self-contained areas that can be visually distinguished from one another by the consumer with the naked eye.
  • the individual phases can have different properties, such as, for example, the speed at which the phase dissolves in water and thus the speed and the sequence in which the constituents contained in the respective phase are released.
  • the phases are typically spatially separated from one another. In various embodiments, this can be done in such a way that, if one or both of the phases are liquid phases, the liquid phase is present in a separate, closed area, for example the chamber of a pouch, from the other phase.
  • a separate, closed area for example the chamber of a pouch
  • Such forms of confection are known in the prior art.
  • the two phases can be arranged spatially directly adjacent in such a way that the phases are formulated separately and contact one another, but cannot mix.
  • fatty acids or fatty alcohols or their derivatives are representative of branched or unbranched carboxylic acids or alcohols or their derivatives with preferably 6 to 22 carbon atoms.
  • the oxo alcohols or their derivatives obtainable, for example, according to ROELEN's oxo synthesis can also be used accordingly.
  • alkaline earth metals are mentioned in the following as counterions for monovalent anions, this means that the alkaline earth metal is of course only present in half the amount of the substance - sufficient to balance the charge - like the anion.
  • the homopolymers used according to the invention are homopolymers of ⁇ , ⁇ ethylenically unsaturated carboxylic acids.
  • Unsaturated carboxylic acids of the formula R 1 (R 2 ) C C (R 3 ) COOH, in which R 1 to R 3 independently of one another for -H, -CH 3 , are used as unsaturated carboxylic acid (s) straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted by -NH 2 , -OH or -COOH as defined above or for -COOH or -COOR 4 , where R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.
  • 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 (methyl maleic acid), methylene malonic acid, sorbic acid, cinnamic acid or mixtures thereof.
  • Acrylic acid is very particularly preferred.
  • the homopolymer is therefore a polyacrylic acid.
  • All or part of the carboxylic acid groups in the polymers may be in neutralized form, i.e. that the acidic hydrogen atom of the carboxylic acid group in some or all of the carboxylic acid groups can be replaced by metal ions, preferably alkali metal ions and in particular by sodium ions.
  • metal ions preferably alkali metal ions and in particular by sodium ions.
  • the use of partially or fully neutralized polymers is preferred according to the invention.
  • the molecular weight of the homopolymers used can be varied in order to adapt the properties of the polymers to the intended use.
  • Preferred dishwashing detergents are characterized in that the homopolymers, in particular the polyacrylic acids, have molar masses M n of 1000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates with molecular weights from 1100 to 10000 g / mol, and particularly preferably from 1200 to 5000 g / mol, can in turn be preferred from this group.
  • copolymers according to the invention can have two, three, four or more different monomer units.
  • Preferred copolymers contain, in addition to sulfonic acid group-containing Monomer (s) at least one monomer from the group of unsaturated carboxylic acids.
  • the unsaturated carboxylic acids described above are used with particular preference as unsaturated carboxylic acid (s).
  • Acrylic acid is very particularly preferred.
  • 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-propanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propen1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate , Sulfomethacrylamide, sulfomethyl methacrylamide and mixtures of the acids mentioned or their water-soluble salts.
  • the acid groups can be wholly or partly in neutralized form, i.e. that the acidic hydrogen atom of the sulfonic and / or carboxylic acid group in some or all of the acid groups can be replaced by metal ions, preferably alkali metal ions and in particular by sodium ions.
  • metal ions preferably alkali metal ions and in particular by sodium ions.
  • the monomer distribution of the preferably used copolymers is preferably 5 to 95% by weight in each case in copolymers which contain only monomers containing carboxylic acid groups and monomers containing sulfonic acid groups, particularly preferably the proportion of the monomer containing sulfonic acid groups is 50 to 90% by weight. and the proportion of the carboxylic acid group-containing monomer 10 to 50 wt .-%, the monomers are preferably selected from the aforementioned.
  • the copolymers may contain, in addition to the monomers containing carboxylic acid groups and monomers containing sulfonic acid groups described above, further monomers, in particular monomers containing unsaturated carboxylic acid ester groups.
  • Particularly preferred unsaturated carboxylic acid esters are alkyl esters of monocarboxylic acids such as acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, ⁇ -cyanoacrylic acid, crotonic acid, ⁇ -phenyl-acrylic acid, sorbic acid, cinnamic acid or mixtures thereof.
  • C 1-8 alkyl esters of acrylic acid, such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, are very particularly preferred.
  • Ethyl acrylate is very particularly preferred.
  • the molar mass of the copolymers used can also be varied in order to adapt the properties of the polymers to the desired intended use.
  • Preferred dishwashing detergents are characterized in that the copolymers have molecular weights M n of from 2000 to 200,000 g / mol, preferably from 4000 to 25,000 g / mol and in particular from 5000 to 15,000 g / mol.
  • the homopolymers and copolymers are each used in amounts of 0.5 to 5% by weight, based on the total weight of the composition. Absolute amounts are typically in the range from 0.1 to 2 g / job, preferably in the range from 0.2 to 1.0 g / job.
  • the mass ratio of the polymers to one another, ie homopolymer to copolymer is in various embodiments 5: 1 to 1: 5, preferably 2: 1 to 1: 2.
  • the polymer combinations used according to the invention which are defined as above, have the property of improving the performance of bleaching catalysts contained in the dishwashing detergent and therefore lead to improved cleaning performance on bleach-sensitive soils.
  • the improvement in the bleaching catalyst performance or the improvement in the cleaning or bleaching performance is to be understood to mean that, when using the dishwashing detergents according to the invention, the removal of soiling, in particular bleach-sensitive soiling, from dishes when cleaning them in an automatic dishwasher compared to the use of Dishwashing detergents which do not contain the complexing agents according to the invention are markedly improved.
  • the dishwashing detergents can also contain other polymers.
  • the group of suitable polymers includes, in particular, the cleaning-active amphoteric, zwitterionic or cationic polymers, for example the rinse aid polymers and / or polymers which act as softeners.
  • Preferred amphoteric polymers that can be used come from the group of alkyl acrylamide / acrylic acid copolymers, alkyl acrylamide / methacrylic acid copolymers, alkyl acrylamide / methyl methacrylic acid copolymers, alkyl acrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, alkyl acrylamide / methacrylic acid / alkylaminoalkyl ( ) -acrylic acid copolymers, the alkyl acrylamide / methyl methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkyl acrylamide / alkymethacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers and the copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally other ionic
  • zwitterionic polymers that can be used come from the group of acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali and ammonium salts, acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali and ammonium salts and methacroylethylbetaine / methacrylate copolymers.
  • Cationic polymers which can be used come from the groups of the quaternized cellulose derivatives, the polysiloxanes with quaternary groups, the cationic guar derivatives, the polymeric dimethyldiallylammonium salts and their copolymers with acrylic acid and methacrylic acid and their esters and amides, the copolymers of vinylpyrrolidone with quaternylamino derivatives of the quaternylamino derivative and methacrylate, the vinylpyrrolidone-methoimidazolinium chloride copolymers, the quaternized polyvinyl alcohols or those under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27 indicated polymers.
  • Machine dishwashing detergents preferably contain the aforementioned cationic and / or amphoteric polymers in amounts between 0.01 and 10% by weight, in each case based on the total weight of the machine dishwashing agent.
  • preferred machine dishwashing detergents are those in which the proportion by weight of the cationic and / or amphoteric polymers is between 0.01 and 8% by weight, preferably between 0.01 and 6% by weight, preferably between 0 and 01 and 4 wt .-%, particularly preferably between 0.01 and 2 wt .-% and in particular between 0.01 and 1 wt .-%, each based on the total weight of the automatic dishwashing detergent.
  • the bleaching catalysts which can be used according to the invention include, but are not limited to, the group of bleach-enhancing transition metal salts and transition metal complexes, preferably Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can also be used as bleaching catalysts.
  • Complexes of manganese are used with particular preference in oxidation state II, III, IV or IV, which preferably contain one or more macrocyclic ligand (s) with the donor functions N, NR, PR, O and / or S.
  • Ligands which have nitrogen donor functions are preferably used.
  • bleaching catalyst (s) in the agents according to the invention which contain 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN), 1,4,7-triazacyclononane (TACN) as macromolecular ligands ), 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 contain 2-methyl-1,4,7-triazacyclononane (Me / TACN).
  • Me-TACN 1,4,7-trimethyl-1,4,7-triazacyclononane
  • TACN 1,4,7-triazacyclononane
  • Suitable manganese complexes are, for example, [Mn III 2 ( ⁇ -O) 1 ( ⁇ -OAc) 2 (TACN) 2 ] (ClO 4 ) 2 , [Mn III Mn IV ( ⁇ -O) 2 ( ⁇ -OA c ) 1 ( TACN) 2 ] (BPh 4 ) 2 , [Mn IV 4 ( ⁇ -O) 6 (TACN) 4 ] (ClO 4 ) 4 , [Mn III 2 ( ⁇ -O) 1 ( ⁇ -OAc) 2 (Me- TACN) 2 ] (ClO 4 ) 2 , [M n III M n IV ( ⁇ -O) 1 ( ⁇ -OAc) 2 (Me-TACN) 2 ] (ClO 4 ) 3 , [Mn IV 2 ( ⁇ -O ) 3 (Me-TACN) 2 ] (PF 6 ) 2 and [Mn IV 2 ( ⁇ -O) 3 (Me / Me-TACN) 2 ] (PF 6 )
  • Machine dishwashing detergent characterized in that it is a bleaching 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-TACN) or Containing 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (Me / Me-TACN) are preferred according to the invention, since the cleaning result in particular can be significantly improved by the aforementioned bleaching catalysts.
  • a bleaching 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-TACN) or Containing 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (Me / Me-TACN) are preferred according to the invention, since the cleaning result in particular can be significantly
  • the aforementioned bleach-enhancing transition metal complexes are preferably used in an amount of up to 1% by weight, in particular from 0.001% by weight to 0.1% by weight and particularly preferably from 0.01% by weight. % to 0.05% 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 bleaching agents which can be used according to the invention are substances which are active in washing or cleaning.
  • sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Further usable bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid.
  • Bleaching agents from the group of organic bleaching agents can also be used.
  • Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide.
  • Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. All other inorganic or organic peroxy bleaches known to the person skilled in the art can also be used.
  • Chlorine or bromine-releasing substances can also be used as bleaching agents.
  • Suitable materials that release chlorine or bromine include, for example, heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium.
  • DICA dichloroisocyanuric acid
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.
  • the bleach is in an amount of 1-35% by weight and more preferably 2-30% by weight, 3.5-25% by weight, 4-20% by weight and particularly preferably 5 -15% by weight in the dishwashing detergent according to the invention, in each case based on the total weight of the dishwashing detergent.
  • Preferred dishwashing detergents are further characterized in that the dishwashing detergent, based in each case on the total weight of the dishwashing detergent, contains 2 to 20 wt.%, Preferably 3 to 18 wt.% And in particular 4 to 15 wt.% Sodium percarbonate.
  • dishwashing detergents are characterized in that the bleaching catalyst is 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 (methane TACN) or 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (Me / Me-TACN), and / or the source of hydrogen peroxide is sodium percarbonate, sodium perborate tetrahydrate or sodium perborate monohydrate, or a combination thereof.
  • the bleaching catalyst is 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 (methane TACN) or 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (Me / Me-TACN), and / or the source of hydrogen peroxid
  • the bleaching catalyst is very particularly preferably a complex of the manganese with 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN), in particular [Mn IV 2 ( ⁇ -O) 3 (Me-TACN) 2 ] (PF 6 ) 2 , or 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (Me / Me-TACN) or a mixture thereof, and the hydrogen peroxide source sodium percarbonate.
  • the bleaching catalyst and the hydrogen peroxide source are preferably present in the above-mentioned amounts.
  • the automatic dishwashing detergents additionally contain at least one bleach activator.
  • Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • acylated multiply acylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT) Glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS) are particularly preferably used.
  • TAED tetraacetylethylenediamine
  • DADHT 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine
  • Glycolurils in particular
  • TAED is very particularly preferred.
  • Combinations of conventional bleach activators can also be used. These bleach activators 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, in each case based on the total weight of the agents containing bleach activator.
  • the agents according to the invention preferably contain at least one further constituent, in particular at least two further constituents, selected from the group consisting of builders, surfactants, enzymes, corrosion inhibitors and glass corrosion inhibitors, disintegration aids, fragrances and perfume carriers.
  • builder substances such as silicates, aluminum silicates (especially zeolites), salts of organic di- and polycarboxylic acids and mixtures of these substances, preferably water-soluble builder substances, can be advantageous.
  • phosphates including polyphosphates
  • the agent contains less than 1% by weight of phosphate (s).
  • the agent is particularly preferably completely phosphate-free, i.e. the agents contain less than 0.1% by weight of phosphate (s).
  • the builders include in particular carbonates, citrates, phosphonates, organic builders and silicates.
  • the weight fraction of the total builders in the total weight of agents according to the invention is preferably 15 to 80% by weight and in particular 20 to 70% by weight.
  • Organic builders which are suitable according to the invention are, for example, the polycarboxylic acids (polycarboxylates) which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which have more than one, in particular two to eight, acid functions, preferably two to six, in particular two, three, four or five acid functions carry throughout the molecule.
  • Preferred polycarboxylic acids are therefore dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids and pentacarboxylic acids, in particular di-, tri- and tetracarboxylic acids.
  • the polycarboxylic acids can also carry further functional groups, such as hydroxyl or amino groups.
  • aminocarboxylic acids in particular aminodicarboxylic acids, aminotricarboxylic acids, aminotetracarboxylic acids, such as nitrutinotitanic acid, such as, for example, nitraminotriestric acids, such as, for example, nitraminotriestric acids, such as, for example, nitraminotriestric acid, such as, for example, nitraminotriestric acid, such as, for example, nitraminotriestric acid, such as, for example, nitraminotriestric acid, such as, for example, nitraminotriestric acid, such as, for example, nitraminotriestric acid, such as, for example, nitraminotriestric acid -diacetic acid (also referred to as N, N-bis (carboxymethyl) -L-glutamic acid or GLDA), methylglycinediace
  • polymeric polycarboxylates organic polymers with a large number of (in particular greater than ten) carboxylate functions in the macromolecule
  • polyaspartates organic polymers with a large number of (in particular greater than ten) carboxylate functions in the macromolecule
  • polyacetals polyacetals and dextrins.
  • the free acids typically also have the property of an acidifying component and can therefore, if desired, also be used to set a lower pH.
  • Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.
  • dishwashing agents preferably machine dishwashing agents
  • these are preferably in a proportion of 2 to 40% by weight, in particular 5 to 30% by weight, particularly 7 to 28% by weight, particularly preferably 10 to 25% by weight, very particularly preferably 15 to Contain 20 wt .-%, each based on the total weight of the agent.
  • dishwashing agents preferably machine dishwashing agents
  • dishwashing agents are characterized in that they contain at least two builders from the group of the silicates, phosphonates, carbonates, aminocarboxylic acids and citrates, the proportion by weight of these builders, based on the total weight of the cleaning agent according to the invention, is preferably 5 to 70% by weight, preferably 15 to 60% by weight and in particular 20 to 50% 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 cleaning agents according to the invention, in particular dishwashing agents, preferably machine dishwashing agents.
  • one or more other builders may also be included.
  • Preferred cleaning agents in particular dishwashing agents, preferably machine dishwashing agents, are characterized by a combination of builders of citrate and carbonate and / or hydrogen carbonate.
  • a mixture of carbonate and citrate is used, the amount of carbonate preferably being from 5 to 40% by weight, in particular 10 to 35% by weight, very particularly preferably 15 to 30% by weight and the amount of citrate is preferably from 5 to 35% by weight, in particular 10 to 25% by weight, very particularly preferably 15 to 20% by weight, in each case based on the total amount of the cleaning agent, the total amount of these two Builders are preferably 20 to 65% by weight, in particular 25 to 60% by weight, preferably 30 to 50% by weight. In addition, one or more other builders can also be included.
  • the cleaning agents according to the invention can contain, in particular, phosphonates as a further builder.
  • a hydroxyalkane and / or aminoalkane phosphonate is preferably used as the phosphonate compound.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs.
  • Phosphonates in agents according to the invention are preferably in amounts of 0.1 to 10% by weight, in particular in amounts of 0.5 to 8% by weight, very particularly preferably 2.5 to 7.5% by weight based on the total weight of the agent.
  • citrate, (hydrogen) carbonate and phosphonate are particularly preferred. These can be used in the amounts mentioned above. In particular, in this combination, amounts of 10 to 25% by weight citrate, 10 to 30% by weight carbonate (or bicarbonate) and 2.5 to 7.5% by weight, based in each case on the total weight of the composition. Phosphonate used.
  • dishwashing agents preferably machine dishwashing agents
  • dishwashing agents contain, in addition to citrate and (hydrogen) carbonate and optionally phosphonate, at least one further phosphorus-free builder.
  • this is selected from the aminocarboxylic acids, the further phosphorus-free builder preferably being selected from methylglycinediacetic acid (MGDA), glutamic acid diacetate (GLDA), aspartic acid diacetate (ASDA), hydroxyethyliminodiacetate (HEIDA), iminodisuccinate (IDS) and ethylenediamine disuccinate, particularly preferably from EDDS MGDA or GLDA.
  • MGDA methylglycinediacetic acid
  • GLDA glutamic acid diacetate
  • ASDA aspartic acid diacetate
  • HEIDA hydroxyethyliminodiacetate
  • IDS iminodisuccinate
  • ethylenediamine disuccinate particularly preferably from EDDS MGDA or GLDA.
  • the percentage by weight of the further phosphorus-free builder, in particular the MGDA and / or GLDA, is preferably 0 to 40% by weight, in particular 5 to 30% by weight, especially 7 to 25% by weight.
  • the use of MGDA or GLDA, in particular MGDA, as granules is particularly preferred. MGDA granules which contain as little water as possible and / or have a lower hygroscopicity (water absorption at 25 ° C., normal pressure) compared to the non-granulated powder are advantageous.
  • the combination of at least three, in particular at least four builders from the group mentioned above has proven to be advantageous for the cleaning and rinsing performance of cleaning agents according to the invention, in particular dishwashing agents, preferably machine dishwashing agents. It can also contain other builders.
  • Polymeric polycarboxylates are also suitable as organic builders, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.
  • Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates which have molar masses from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, can in turn be preferred from this group.
  • the content of (homo) polymeric polycarboxylates in the cleaning agents according to the invention, in particular dishwashing agents, preferably machine dishwashing agents, is preferably 0.5 to 20% by weight, preferably 2 to 15% by weight and in particular 4 to 10% by weight.
  • Cleaning agents according to the invention can furthermore contain crystalline layered silicates of the general formula NaMSi x O 2x + 1 .yH 2 O, where M represents sodium or hydrogen, x as a builder, preferably 1.9 to 22, preferably from 1.9 to 4, with particularly preferred values for x being 2, 3 or 4 and y being a number from 0 to 33, preferably from 0 to 20.
  • Amorphous sodium silicates with a modulus Na 2 O: SiO 2 of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, can also be used are preferably delayed release and have secondary washing properties.
  • the silicate content based on the total weight of the cleaning agent, is limited to amounts below 10% by weight, preferably below 5% by weight and in particular below 2% by weight .
  • the washing or cleaning agents according to the invention can furthermore contain alkali metal hydroxides.
  • These alkali carriers are preferably only in small amounts in the washing or cleaning agents, preferably in amounts below 10% by weight, preferably below 6% by weight, preferably below 5% by weight, particularly preferably between 0.1 and 5% by weight .-% and in particular between 0.5 and 5 wt .-%, each based on the total weight of the detergent or cleaning agent.
  • Alternative cleaning agents according to the invention are free from alkali metal hydroxides.
  • the agents according to the invention can contain surfactants, the group of surfactants including nonionic, anionic, cationic and amphoteric surfactants.
  • nonionic surfactants known to the person skilled in the art can be used as nonionic surfactants.
  • Suitable nonionic surfactants are, for example, alkyl glycosides of the general formula RO (G) x , in which R corresponds to a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G is the symbol is, which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.
  • Suitable surfactants are the polyhydroxy fatty acid amides known as PHFA.
  • low-foaming nonionic surfactants are preferably used, in particular alkoxylated, especially ethoxylated, low-foaming nonionic surfactants.
  • the dishwasher detergents particularly preferably contain nonionic surfactants from the group of the alkoxylated alcohols.
  • nonionic surfactants that can be used, which can be used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are accordingly alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain.
  • Preferred surfactants come from the groups of ethoxylated primary alcohols and mixtures of these surfactants with structurally more complex surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants).
  • Such (PO / EO / PO) nonionic surfactants are characterized by good foam control.
  • Suitable nonionic surfactants are those which have alternating ethylene oxide and alkylene oxide units.
  • surfactants with EO-AO-EO-AO blocks are preferred, one to ten EO or AO groups being bonded to one another before a block follows from the other groups.
  • nonionic surfactants of the general formula preferred 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 of one another represent integers from 1 to 6.
  • nonionic surfactants which have a C 9-15 -alkyl radical 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.
  • Those end group-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 , are preferred, in addition to a radical R 1 which is saturated for linear or branched or unsaturated, aliphatic or aromatic Hydrocarbon radicals having 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, furthermore have a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R 2 having 1 to 30 carbon atoms, where x represents values between 1 and 90, preferably values between 10 and 80 and in particular for values between 20 and 60.
  • Particularly preferred are surfactants of the above formula in which R 1 is C 7 to C 13 , x is an integer from 16 to 28 and R 2 is C 8 to C 12 .
  • 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 up to 18 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 values between 0.5 and 1.5 and y for a value of at least 15.
  • the group of these nonionic surfactants includes, for example, the C 2-26 fatty alcohol (PO) 1 - (EO) 15 40 -2-hydroxyalkyl ethers, in particular also the C 8-10 fatty alcohol (PO) 1 - (EO) 22 -2- hydroxydecyl ether.
  • End group-capped poly (oxyalkylated) nonionic surfactants of the formula R 1 O [CH 2 CH 2 O] x [CH 2 CH (R 3 ) O] y CH 2 CH (OH) R 2 , in which R 1 and R 1 are also particularly preferred 2 independently of one another represents a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R 3 is selected independently of one another from -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , -CH (CH 3 ) 2 , but preferably stands for -CH 3 , and x and y independently of one another stand for values between 1 and 32, nonionic surfactants with R 3 -CH 3 and values for x of 15 to 32 and y of 0.5 and 1.5 are very particularly preferred.
  • nonionic surfactants are the end group-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 represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 3 represents H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2- Butyl or 2-methyl-2-butyl radical, x stand for values between 1 and 30, k and j stand for 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, radicals having 8 to 18 carbon atoms being particularly preferred.
  • H, -CH 3 or -CH 2 CH 3 are particularly preferred for the radical R 3 .
  • 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 can be different if x ⁇ 2.
  • the value 3 for x has been chosen here by way of example and may well be larger, the range of variation 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 stands for numbers 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 carbon atoms, R 3 represents H and x assumes values from 6 to 15.
  • the group of these nonionic surfactants includes, for example, the C 4-22 fatty alcohol (EO) 10-80 -2-hydroxyalkyl ethers, in particular also the C 8-12 fatty alcohol (EO) 22 -2-hydroxydecyl ether and the C 4-22 fatty alcohol (EO) 40-80 -2-hydroxyalkyl ether.
  • the corresponding non-end-capped hydroxy mixed ethers can also be used instead of the end-capped hydroxy mixed ethers defined above.
  • R 2 is hydrogen and R 1 , R 3 , A, A ', A ", A'", w, x, y and z are as defined above.
  • compositions described herein which comprise at least one nonionic surfactant, preferably a nonionic surfactant from the group of hydroxy mixed ethers, contain the surfactant in various embodiments in an amount based on the total weight of the composition of at least 2% by weight, preferably at least 5% by weight. %.
  • the absolute amounts used per application can be, for example, in the range of 0.5-10 g / job, preferably in the range of 0.5-5 g / job.
  • Nonionic surfactants which have a melting point above room temperature are particularly preferred.
  • anionic surface-active substances are suitable as anionic surfactants in dishwashing detergents. These are characterized by a water-solubilizing, anionic group such as. B. a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group with about 8 to 30 carbon atoms.
  • anionic group such as. B. a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group with about 8 to 30 carbon atoms.
  • glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups can be contained in the molecule.
  • Suitable anionic surfactants are preferably in the form of the sodium, potassium and ammonium and the mono-, di- and trialkanolammonium salts with 2 to 4 carbon atoms in the alkanol group, but also zinc, manganese (II), magnesium, calcium or Mixtures of these can serve as counterions.
  • Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids with 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule.
  • cationic and / or amphoteric surfactants such as betaines or quaternary ammonium compounds can also be used. However, it is preferred that no cationic and / or amphoteric surfactants are used.
  • the agents of the present invention preferably contain at least one enzyme preparation or enzyme composition which contains one or more enzymes.
  • Suitable enzymes include, but are not limited to, proteases, amylases, lipases, hemicellulases,
  • 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.
  • proteases are among the most technically significant enzymes. They are the longest established enzymes for detergents and cleaning agents and are found in practically all modern, powerful detergents and cleaning agents. They break down protein-based soiling on the items to be cleaned. Of these, proteases of the subtilisin type (subtilases, subtilopeptidases, EC 3.4.21.62) are particularly important, which are serine proteases due to the catalytically active amino acids. They act as non-specific endopeptidases and hydrolyze any acid amide bonds that are inside peptides or proteins. Their pH optimum is usually in the clearly alkaline range. An overview of this family can be found in the article " Subtilases: Subtilisin-like Proteases "by R.
  • Subtilisin enzymes edited by R. Bott and C. Betzel, New York, 1996 .
  • Subtilases are naturally formed by microorganisms. Among these, the subtilisins formed and secreted by Bacillus species are to be mentioned as the most important group within the subtilases.
  • proteases of the subtilisin type which are preferably used in washing and cleaning agents are the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the protease from Bacillus lentus, in particular from Bacillus lentus DSM 5483, Subtilisin DY and the subtilases, but no longer to the subtilisins in the narrower sense enzymes Thermitase, Proteinase K and the proteases TW3 and TW7, and variants of the proteases mentioned, which have an amino acid sequence which is different from that of the starting protease.
  • Proteases are changed in a targeted or random manner by methods known from the prior art and are thus optimized, for example, for use in detergents and cleaning agents. This includes point mutagenesis, deletion or insertion mutagenesis or fusion with other proteins or protein parts. Correspondingly optimized variants are known for most proteases known from the prior art.
  • amylases which can be used according to the invention are the ⁇ -amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae and the further developments of the aforementioned amylases which are improved for use in cleaning agents. Furthermore, the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).
  • Lipases or cutinases can also be used according to the invention, 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 obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L, T213R and / or N233R, particularly preferably all of the exchanges D96L, T213R and N233R.
  • 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 interacting with the enzymes are additionally added in order to increase the activity of the oxidoreductases in question (enhancers) or to ensure the flow of electrons (mediators) in the case of very different redox potentials between the oxidizing enzymes and the soiling.
  • a protein and / or enzyme can be protected against damage, such as inactivation, denaturation or decay, for example by physical influences, oxidation or proteolytic cleavage, especially during storage.
  • damage such as inactivation, denaturation or decay, for example by physical influences, oxidation or proteolytic cleavage, especially during storage.
  • the proteins and / or enzymes are obtained microbially, inhibition of proteolysis is particularly preferred, in particular if the agents also contain proteases.
  • Detergents can contain stabilizers for this purpose; the provision of such means is a preferred embodiment of the present invention.
  • Proteases and amylases that are active in cleaning are generally not provided in the form of the pure protein but rather in the form of stabilized preparations which can be stored and transported.
  • These prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, particularly 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 administration 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 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, bleaching agents or dyes, can additionally be applied in superimposed layers.
  • Capsules of this type are applied by methods known per se, for example by shaking or roll granulation or in fluid-bed processes. Such granules are advantageously low in dust, for example by applying polymeric film formers, and are stable on storage due to the coating.
  • the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations.
  • Protease and amylase preparations preferably used according to the invention contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, particularly preferably between 0.4 and 20% by weight and in particular between 0, 8 and 10% by weight of the enzyme protein.
  • cleaning agents which, based on their total weight, contain 0.1 to 12% by weight, preferably 0.2 to 10% by weight and in particular 0.5 to 8% by weight of enzyme preparations.
  • compositions described herein can also include enzyme stabilizers.
  • a group of stabilizers are reversible protease inhibitors. Benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are frequently used for this, including above all derivatives with aromatic groups, for example ortho-, meta- or para-substituted phenylboronic acids, in particular 4-formylphenyl-boronic acid, or the salts or Esters of the compounds mentioned.
  • Peptide aldehydes that is to say oligopeptides with a reduced C terminus, in particular those of 2 to 50 monomers, are also used for this purpose.
  • the peptide reversible protease inhibitors include, among others, ovomucoid and leupeptin. Specific, reversible peptide inhibitors for the protease subtilisin as well as fusion proteins from proteases and specific peptide inhibitors are also suitable for this.
  • Further enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and -propanolamine and their mixtures, aliphatic carboxylic acids up to C 12 , such as succinic acid, other dicarboxylic acids or salts of the acids mentioned. End-capped fatty acid amide alkoxylates are also suitable for this purpose. Further enzyme stabilizers are known to the person skilled in the art from the prior art.
  • the pH of the dishwashing detergent can be adjusted using conventional pH regulators, the pH being selected depending on the intended use.
  • the pH is in a range from 5.5 to 10.5, preferably 5.5 to 9.5, more preferably 7 to 9, in particular greater than 7, especially in the range 7.5 to 8.5 .
  • Acids and / or alkalis, preferably alkalis serve as pH adjusting agents.
  • Suitable acids are in particular organic acids such as acetic acid, citric acid, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid or amidosulfonic acid.
  • the mineral acids hydrochloric acid, sulfuric acid and nitric acid or mixtures thereof can also be used.
  • Suitable bases come from the group of alkali and alkaline earth metal hydroxides and carbonates, in particular alkali metal hydroxides, of which potassium hydroxide and especially sodium hydroxide is preferred.
  • alkali metal hydroxides of which potassium hydroxide and especially sodium hydroxide is preferred.
  • volatile alkali is particularly preferred, for example in the form of ammonia and / or alkanolamines, which can contain up to 9 carbon atoms in the molecule.
  • the alkanolamine is preferably selected from the group consisting of mono-, di-, triethanol- and -propanolamine and mixtures thereof.
  • the agent according to the invention can also contain one or more buffer substances (INCI buffering agents), usually in amounts of 0.001 to 5% by weight. Buffer substances which are at the same time complexing agents or even chelating agents (chelators, INCI chelating agents) are preferred. Particularly preferred buffer substances are citric acid and citrates, in particular sodium and potassium citrates, for example trisodium citrate ⁇ 2H 2 O and tripotassium citrate ⁇ H 2 O.
  • 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 content of zinc salt in automatic dishwashing detergents is preferably between 0.1 to 5% by weight, 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 and 1% by weight, preferably between 0.02 and 0.5% by weight and in particular between 0.04 and 0.2% by weight .-%, each based on the total weight of the glass corrosion inhibitor-containing agent.
  • Zn 2+ zinc in oxidized form
  • Salts in particular the zinc salts
  • BASF a polyethyleneimines
  • fragrance compounds e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used.
  • mixtures of different fragrances are preferably used, which together produce an appealing fragrance.
  • perfume oils can also contain natural fragrance mixtures as are available from plant sources, e.g. Pine, citrus, jasmine, patchouli, rose or ylang-ylang oil.
  • Preservatives can also be contained in the agents. Preservatives from the groups of alcohols, aldehydes, antimicrobial acids and / or their salts, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen and nitrogen acetals and formals, benzamidines, isothiazoles and their derivatives are suitable, for example such as isothiazolines and isothiazolinones, phthalimide derivatives, pyridine derivatives, antimicrobial surface-active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propynyl-butyl-carbamate, iodine, iodophores and peroxides.
  • Preferred antimicrobial agents are preferably selected from the group comprising ethanol, n-propanol, i-propanol, 1,3-butanediol, phenoxyethanol, 1,2-propylene glycol, glycerin, undecylenic acid, citric acid, lactic acid, benzoic acid, salicylic acid, thymol, 2- Benzyl-4-chlorophenol, 2,2'-methylene-bis- (6-bromo-4-chlorophenol), 2,4,4'-trichloro-2'-hydroxydiphenyl ether, N- (4-chlorophenyl) -N- ( 3,4-dichlorophenyl) urea, N, N '- (1,10-decanediyldi-1-pyridinyl-4-ylidene) bis (1-octanamine) dihydrochloride, N, N'-bis- (4- Chlorphenyl) -3,12-diimino-2,4,
  • particularly preferred preservatives are selected from the group comprising salicylic acid, quaternary surfactants, in particular benzalkonium chloride and isothiazoles and their derivatives such as isothiazolines and isothiazolinones.
  • the machine dishwashing detergents described here can be packaged in different ways.
  • the agents can be in solid or liquid as well as a combination of solid and liquid supply forms.
  • powders, granules, extrudates, compactates, in particular tablets are suitable as fixed supply forms.
  • the liquid supply forms based on water and / or organic solvents can be thickened, in the form of gels.
  • the agents can be packaged in the form of single-phase or multi-phase products.
  • the individual phases of multiphase agents can have the same or different physical states.
  • a phase in the sense of the present invention is a spatial area in which physical parameters and the chemical composition are homogeneous.
  • a phase differs from another phase by different features, for example ingredients, physical properties, external appearance, etc.
  • Different phases can preferably be distinguished optically.
  • the at least one first phase must be clearly distinguished from the at least one second phase. If the washing or cleaning agent according to the invention has more than one first phase, these can likewise be distinguished from one another with the naked eye, because they differ from one another, for example, in their coloring. The same applies if there are two or more second phases. In this case too, the phases can be optically distinguished, for example on the basis of a color or transparency difference.
  • Phases in the sense of the present invention are thus self-contained areas that can be visually distinguished from one another by the consumer with the naked eye.
  • the individual phases can have different properties, such as, for example, the speed at which the phase dissolves in water and thus the speed and the sequence in which the constituents contained in the respective phase are released.
  • the dishwashing detergents can be in the form of moldings.
  • disintegration aids so-called tablet disintegrants
  • Tablet disintegrants or accelerators of disintegration are understood to mean auxiliary substances which ensure the rapid disintegration of tablets in water or other media and the rapid release of the active substances.
  • Disintegration aids can preferably be used in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight, in each case based on the total weight of the agent containing disintegration aids.
  • the automatic dishwashing agents described herein are preferably prefabricated into dosing units. These metering units preferably comprise the amount of cleaning-active substances necessary for a cleaning cycle. Preferred metering units have a weight between 12 and 30 g, preferably between 14 and 26 g and in particular between 15 and 22 g.
  • the volume of the above-mentioned metering units and their spatial shape are selected with particular preference such that the pre-assembled units can be metered via the metering chamber of a dishwasher.
  • the volume of the dosing unit is therefore preferably between 10 and 35 ml, preferably between 12 and 30 ml.
  • the machine dishwashing detergents in particular the prefabricated metering units, particularly preferably have a water-soluble coating.
  • the water-soluble covering is preferably formed from a water-soluble film material which is selected from the group consisting of polymers or polymer mixtures.
  • the sheath can be formed from one or from two or more layers of the water-soluble film material.
  • the water-soluble film material of the first layer and the further layers, if present, can be the same or different. Films which, for example, can be glued and / or sealed to form packaging, such as hoses or pillows, are particularly preferred after they have been filled with an agent.
  • the water-soluble packaging can have one or more chambers.
  • the agent can be contained in one or more compartments, if any, of the water-soluble envelope.
  • the amount of agent preferably corresponds to the full or half dose required for a rinse cycle.
  • the water-soluble envelope contain polyvinyl alcohol or a polyvinyl alcohol copolymer.
  • Water-soluble coatings which contain polyvinyl alcohol or a polyvinyl alcohol copolymer have good stability with a sufficiently high water solubility, in particular cold water solubility.
  • Suitable water-soluble films for producing the water-soluble coating are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer, the molecular weight of which is in the range from 5,000 to 1,000,000 gmol -1 , preferably from 20,000 to 500,000 gmol -1 , particularly preferably from 30,000 to 100,000 gmol -1 and is in particular from 40,000 to 80,000 gmol -1 .
  • Polyvinyl alcohol is usually produced by hydrolysis of polyvinyl acetate, since the direct route of synthesis is not possible. The same applies to polyvinyl alcohol copolymers which are produced from polyvinyl acetate copolymers accordingly. It is preferred if at least one layer of the water-soluble covering comprises a polyvinyl alcohol, the degree of hydrolysis of which is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.
  • a polyvinyl alcohol-containing film material suitable for producing the water-soluble covering can additionally be a polymer selected from the group comprising (meth) acrylic acid-containing (co) polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers, polylactic acid or mixtures of the above Polymers can be added.
  • a preferred additional polymer is polylactic acid.
  • preferred polyvinyl alcohol copolymers comprise dicarboxylic acids as further monomers.
  • Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, itaconic acid being preferred.
  • polyvinyl alcohol copolymers include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its ester.
  • Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester or mixtures thereof.
  • the film material contains further additives.
  • the film material can contain, for example, plasticizers such as dipropylene glycol, ethylene glycol, diethylene glycol, propylene glycol, glycerin, sorbitol, mannitol or mixtures thereof.
  • Other additives include, for example, release aids, fillers, crosslinking agents, surfactants, antioxidants, UV absorbers, antiblocking agents, anti-adhesive agents or mixtures thereof.
  • Suitable water-soluble films for use in the water-soluble wrappings of the water-soluble packaging according to the invention are films which are sold by MonoSol LLC, for example under the name M8630, C8400 or M8900.
  • Other suitable films include films with the designation Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or the films VF-HP from Kuraray.
  • the multi-phase dishwashing detergent is closely enveloped by a water-soluble film
  • the water-soluble film which is preferably used in the tight wrapping, particularly preferably comprises polyvinyl alcohol, as described above, the starting thickness preferably being from 10 ⁇ m to 100 ⁇ m, in particular from 12 ⁇ m to 60 ⁇ m, particularly preferably from 15 ⁇ m to 50 ⁇ m, especially from 20 ⁇ m to 40 ⁇ m, in particular from 22 ⁇ m to 35 ⁇ m is used.
  • the coating lies tightly against the surface of the tablets at every point.
  • the casing is even under tension, but this is not absolutely necessary.
  • This tight fit of the casing is conducive to disintegration: the first time it comes into contact with water, the casing will let a small amount of water pass through at some point, although it does not need to dissolve at first. At this point, the disintegrant contained in the tablet begins to swell. This leads to the fact that the envelope is now due to the volume increase the tablet suddenly tears open and releases the tablet.
  • the mechanism described here will not work if the casing is not snug because the tablet can swell without the casing being blown up.
  • the use of a swellable disintegration agent is superior to a gas-generating system, since its explosive effect in any case leads to the casing being torn open. In a gas-generating system, the explosive effect can "dissipate" by the gas escaping from a leak in the casing.
  • Preferred detergent or cleaning agent disposable portions according to the invention are characterized in that the distance between the single portion and water-soluble coating over the entire area is 0.1 to 1000 ⁇ m, preferably 0.5 to 500 ⁇ m, particularly preferably 1 to 250 ⁇ m and in particular 2.5 to 100 ⁇ m.
  • the film wrapping is first loosely placed around a single portion of detergent or cleaning agent and welded and then shrunk onto it, so that there is close contact between the film packaging and the cleaning agent concentrate.
  • disposable detergent or cleaning agent portions according to the invention are characterized in that the wrapper is a film packaging shrunk onto it.
  • this wrapping can be carried out by placing a water-soluble bottom film on a transport chain or a mold (s), then placing one or more detergent or cleaning agent portions (s) on the bottom film; then a water-soluble top film is placed on the detergent or cleaning agent portion (s) on the bottom film and this is then fixed on the bottom film, including the detergent or cleaning agent portion (s),
  • this step can also be carried out using a single-strand film, which is then placed around the one-time portions as a tube.
  • the foils are then sealed and optionally cut.
  • the film can then be shrink-wrapped using hot air or infrared radiation, optionally with pressure.
  • Exemplary formulations of the agents according to the invention also include, in particular, phosphate-free dishwashing agents.
  • An exemplary formulation in which those described herein Polymers can be used as additional components in the specified amounts the following is: Table 1: Phosphate-free, solid dishwashing detergent formulation (tab), information on active substance in% by weight based on the total weight of the formulation (not according to the invention): raw material Quantity (% by weight) Na citrate 15.00-20.00 Phosphonate (e.g.
  • the corresponding use of the automatic dishwashing agents according to the invention is also an object of the invention.
  • the invention also relates to a dishwashing method, in particular machine dishwashing method, in which a dishwashing agent according to the invention is used.
  • the subject of the present application is therefore also a method for cleaning dishes in a dishwasher, in which the agent according to the invention during the running of a dishwasher program before the start of the Main wash or in the course of the main wash in the interior of a dishwasher.
  • the agent according to the invention can be metered into the interior of the dishwasher manually, but the agent is preferably metered into the interior of the dishwasher by means of the metering chamber.
  • Table 2 Comparative tests Active substance in% by weight based on the total weight of the formulation: raw materials Standard formula Standard formula + combination of sulfopolymer + polyacrylate (E1) Standard formula + sulfopolymer (V1) Standard formula + polyacrylate (V2) % * g / job addition addition addition from to from to g / job g / job g / job Na citrate / citric acid 15 20 2nd 4th Citric acid (pH adjusting agent) 1 1.5 0.2 0.3 Phosphonate 2.5 7.5 0.5 1.50 silicate 5 35 1 7 soda 12.5 25th 2.5 5.00 Na percarbonate 10th 15 2.00 3.00 Bleaching catalyst 0.02 0.5 0.00 3 0.1 TAED 2.0 3.0 0.40 0.60
  • the cleaning performance was determined in Bosch dishwashers in the 40 ° C program. Water hardness 21 ° dH. For this, 20 g of the above recipes (tab) were used. At the end of the wash cycle, the dishes were visually checked on a scale of 1-10. The higher the value, the better the cleaning performance. It can be seen that the recipe according to the invention, which contains both polymers, shows better cleaning performance on various soils, in particular on tea, compared to the comparative recipes, which only contain one of the polymers (Table 3). Table 3: Cleaning performance ADW product Tea (Assam) Creme brulee Minced meat V1 4.9 7.1 4.2 V2 5.7 6.2 4.8 E1 6.7 7.3 5.4

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Claims (10)

  1. Détergent pour lave-vaisselle contenant moins de 1 % en poids de phosphate, caractérisé en ce que le détergent pour lave-vaisselle contient :
    (i) au moins un agent de blanchiment ;
    (ii) au moins un catalyseur de blanchiment ;
    (iii) au moins un homopolymère d'acides carboxyliques à insaturation α,β-éthylénique ; et
    (iv) au moins un copolymère contenant au moins un monomère contenant des groupes acide sulfonique et au moins un monomère du groupe des acides carboxyliques à insaturation α,β-éthylénique,
    l'au moins un homopolymère et l'au moins un copolymère étant respectivement contenus en une quantité de 0,5 à 5 % en poids, sur la base du poids total du détergent pour lave-vaisselle.
  2. Détergent pour lave-vaisselle selon la revendication 1, caractérisé en ce que l'au moins un homopolymère est un polymère d'un acide carboxylique à insaturation α,β-éthylénique de formule R1(R2)C=C(R)COOH, où R1 à R3 représentent, indépendamment les uns des autres, -H, -CH3, un radical alkyle saturé linéaire ou ramifié comportant 2 à 12 atomes de carbone, un radical alcényle linéaire ou ramifié, mono- ou polyinsaturé, comportant 2 à 12 atomes de carbone, des radicaux alkyle ou alcényle substitués par -NH2, -OH ou -COOH tels que définis ci-dessus, ou représentent -COOH ou - COOR, où R4 est un radical hydrocarboné linéaire ou ramifié, saturé ou insaturé, comportant 1 à 12 atomes de carbone, en particulier l'acide acrylique.
  3. Détergent pour lave-vaisselle selon la revendication 1 ou 2, caractérisé en ce que l'au moins un copolymère est un copolymère constitué
    (i) d'au moins un monomère du groupe des acides carboxyliques à insaturation α,β-éthylénique de formule R1(R2)C=C(R3)COOH, où R1 à R3 représentent, indépendamment les uns des autres, -H, -CH3, un radical alkyle saturé linéaire ou ramifié comportant 2 à 12 atomes de carbone, un radical alcényle linéaire ou ramifié, mono- ou polyinsaturé, comportant 2 à 12 atomes de carbone, des radicaux alkyle ou alcényle substitués par -NH2, -OH ou -COOH tels que définis ci-dessus, ou représentent -COOH ou -COOR4, où R4 est un radical hydrocarboné linéaire ou ramifié, saturé ou insaturé, comportant 1 à 12 atomes de carbone, en particulier l'acide acrylique ; et
    (ii) d'au moins un monomère contenant des groupes acide sulfonique de formule R5(R6)C=C(R7)-X-SO3H, où R5 à R7 représentent indépendamment les uns des autres -H, -CH3, un radical alkyle saturé linéaire ou ramifié comportant 2 à 12 atomes de carbone, un radical alcényle mono- ou polyinsaturé linéaire ou ramifié comportant 2 à 12 atomes de carbone, des radicaux alkyle ou alcényle substitués par -NH2, -OH ou -COOH, ou représentent -COOH ou -COOR1, où R4 est un radical hydrocarboné linéaire ou ramifié, saturé ou insaturé, comportant 1 à 12 atomes de carbone, et X représente un groupe espaceur éventuellement présent qui est choisi parmi -(CH2)n- mit n = 0 bis 4, -COO-(CH2)k- mit k = 1 bis 6, -C(O)-NH-C(CH3)2-, - C(O)-NH-C(CH3)2-CH2- et -C(O)-NH-CH(CH3)-CH2-, de préférence au moins un monomère de formule H2C=CH-X-SO3H, H2C=C(CH3)-X-SO3H et HO3S-X-(R6)C=C(R7)-X-SO3H, où R6 et R7 sont choisis indépendamment l'un de l'autre parmi -H, -CH3, -CH2CH3, -CH2CH2CH3 et -CH(CH3)2, et X représente un groupe espaceur éventuellement présent qui est choisi parmi -(CH2)n- avec n = 0 à 4, -COO-(CH2)k-avec k = 1 à 6, -C(O)-NH-C(CH3)2-, -C(O)-NH-C(CH3)2-CH2- et -C(O)-NH-CH(CH3)-CH2-, plus préférablement un monomère choisi dans le groupe constitué par l'acide 1-acrylamido-1-propanesulfonique, l'acide 2-acrylamido-2-propanesulfonique, l'acide 2-acrylamido-2-méthyl-1-propanesulfonique, l'acide 2-méthacrylamido-2-méthyl-1-propanesulfonique, l'acide 3-méthacrylamido-2-hydroxypropanesulfonique, l'acide allylsulfonique, l'acide méthallylsulfonique, l'acide allyloxybenzènesulfonique, l'acide méthallyloxybenzènesulfonique, l'acide 2-hydroxy-3-(2-propényloxy)propanesulfonique, l'acide 2-méthyl-2-propène-1-sulfonique, l'acide styrène sulfonique, l'acide vinyl sulfonique, l'acrylate de 3-sulfopropyle, le méthacrylate de 3-sulfopropyle, le sulfométhacrylamide et le sulfométhylméthacrylamide, de préférence l'acide 2-acrylamido-2-méthyl-1-propanesulfonique ; et
    (iii) éventuellement d'au moins un monomère contenant un groupe ester d'acide carboxylique à insaturation α,β-éthylénique de formule R1(R2)C=C(R3)COOR4, où R1 à R3 sont tels que définis ci-dessus, et R4 est un radical hydrocarboné linéaire ou ramifié, saturé ou insaturé, comportant 1 à 12 atomes de carbone, en particulier un alkylester d'acide acrylique, de manière particulièrement préférée l'acrylate d'éthyle.
  4. Détergent pour lave-vaisselle selon l'une des revendications 1 à 3, caractérisé en ce que
    (i) l'au moins un homopolymère présente une masse molaire Mn dans la plage de 1000 à 20 000 g/mol, plus préférablement de 1100 à 10 000 g/mol et de manière particulièrement préférée de 1200 à 5000 g/mol ; et/ou
    (ii) l'au moins un copolymère présente une masse molaire Mn de 2000 à 200 000 g/mol, de préférence de 4000 à 25 000 g/mol et en particulier de 5000 à 15 000 g/mol.
  5. Détergent pour lave-vaisselle selon l'une des revendications 1 à 4, caractérisé en ce que le rapport massique de l'au moins un homopolymère et de l'au moins un copolymère est de 5:1 à 1:5, de préférence de 2:1 à 1:2.
  6. Détergent pour lave-vaisselle selon l'une des revendications 1 à 5, caractérisé en ce que le catalyseur de blanchiment est choisi dans le groupe des sels de métaux de transition améliorant le blanchiment et des complexes de métaux de transition, de préférence des complexes de manganèse à l'état d'oxydation II, III, IV ou IV, lesquels contiennent un ou plusieurs ligands macrocycliques comportant les fonctions donneurs N, NR, PR, O et/ou S, de manière particulièrement préférée les ligands macromoléculaires 1,4,7-triméthyl-1,4,7-triazacyclononane (Me-TACN), 1,4,7-triazacyclononane (TACN), 1,5,9-triméthyl-1,5,9-triazacyclododécane (Me-TACD), 2-méthyl-1,4,7-triméthyl-1,4,7- triazacyclononane (Me/Me-TACN) et/ou 2-méthyl-1,4,7-triazacyclononane (Me/TACN), tout particulièrement les ligands 1,4,7-triméthyl-1,4,7-triazacyclononane (Me-TACN) ou 1,2,4,7-tétraméthyl-1,4,7-triazacyclononane (Me/Me-TACN).
  7. Détergent pour lave-vaisselle selon l'une des revendications 1 à 6, caractérisé en ce que le catalyseur de blanchiment est contenu en une quantité de 0,001 à 0,1 % en poids, de préférence 0,01 à 0,05 % en poids, sur la base du poids total du détergent pour lave-vaisselle.
  8. Détergent pour lave-vaisselle selon l'une des revendications 1 à 7, caractérisé en ce que
    (1) l'au moins un agent de blanchiment est choisi dans le groupe constitué par le percarbonate de sodium, le perborate de sodium tétrahydraté, le perborate de sodium monohydraté, les peroxypyrophosphates, les citrate perhydrates, les perbenzoates, les peroxophtalates, l'acide dipérazélaïque, le phtaloiminoperacide, le diacide de diperdodécane, les peroxydes de diacyle, les acides d'alkyl peroxy et les acides d'aryl peroxy, de préférence le carbonate de sodium, le percarbonate de sodium tétrahydraté et le perborate de sodium monohydraté, plus préférablement le percarbonate de sodium ; et/ou
    (2) l'au moins un agent de blanchiment est contenu en une quantité de 1 à 35 % en poids et plus préférablement de 2 à 30 % en poids, de 3,5 à 25 % en poids, de 4 à 20 % en poids et de manière particulièrement préférée de 5 à 15 % en poids, dans le détergent pour lave-vaisselle, sur la base, dans chaque cas, du poids total du détergent pour lave-vaisselle ; et/ou
    (3) le détergent pour lave-vaisselle se présente sous forme solide ; et/ou
    (4) le détergent pour lave-vaisselle se présente sous forme prédosée ; et/ou
    (5) le détergent pour lave-vaisselle présente une pluralité de compositions séparées les unes des autres dans l'espace, au moins l'une des compositions étant solide et/ou au moins l'une des compositions étant liquide ; et/ou
    (6) le détergent pour lave-vaisselle contient au moins un activateur de blanchiment ; et/ou
    (7) le détergent pour lave-vaisselle contient au moins un autre constituant, de préférence au moins deux autres constituants, choisis dans le groupe comprenant les constructeurs, les tensioactifs, les enzymes, les inhibiteurs de corrosion, les inhibiteurs de corrosion du verre, les auxiliaires de désintégration, les parfums et les supports de parfum.
  9. Utilisation d'un détergent pour lave-vaisselle selon l'une des revendications 1 à 8 dans un procédé de lavage automatique de vaisselle.
  10. Procédé de lavage automatique de vaisselle, caractérisé en ce qu'un détergent pour lave-vaisselle est utilisé selon l'une des revendications 1 à 8.
EP16741023.2A 2015-07-23 2016-07-20 Lessive lave-vaisselle contenant des agents de blanchiment et des polymères Revoked EP3325596B1 (fr)

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US10696925B2 (en) * 2017-03-30 2020-06-30 Dow Global Technologies Llc Automatic dishwashing compositions with dispersant blend
CN110603312B (zh) 2017-05-04 2021-10-15 联合利华知识产权控股有限公司 洗涤剂组合物
CN111201254B (zh) * 2017-10-23 2022-06-17 陶氏环球技术有限责任公司 用于自动洗碗系统中的梯度共聚物
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WO2017013158A1 (fr) 2017-01-26
ES2820324T3 (es) 2021-04-20
PL3325596T3 (pl) 2020-12-28
EP3325596A1 (fr) 2018-05-30

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