WO2016198446A1 - Lessive liquide pour lave-vaisselle, exempte de phosphates - Google Patents

Lessive liquide pour lave-vaisselle, exempte de phosphates Download PDF

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Publication number
WO2016198446A1
WO2016198446A1 PCT/EP2016/063023 EP2016063023W WO2016198446A1 WO 2016198446 A1 WO2016198446 A1 WO 2016198446A1 EP 2016063023 W EP2016063023 W EP 2016063023W WO 2016198446 A1 WO2016198446 A1 WO 2016198446A1
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composition
acid
weight
free
total weight
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PCT/EP2016/063023
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German (de)
English (en)
Inventor
Thomas Weber
Sven Müller
Hans Hartmut Janke
Johannes Zipfel
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Henkel Ag & Co. Kgaa
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Publication of WO2016198446A1 publication Critical patent/WO2016198446A1/fr

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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
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38663—Stabilised liquid enzyme compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • 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
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • 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
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/361—Phosphonates, phosphinates or phosphonites

Definitions

  • the present invention relates to a phosphate-free, liquid dishwashing detergent which exhibits improved stability and cleaning performance, in particular of enzyme-sensitive soiling, the use of this dishwashing detergent and a method for machining
  • a dishwashing detergent requires alkalinity.
  • Many other dried-on food residues require enzymes, such as amylases and proteases.
  • alkalinity and enzymes together can not be stably formulated.
  • Liquid dishwashing detergents also require special stabilizers to stabilize the enzymes. These include, inter alia, calcium salts and especially for proteases additionally polyols and / or boric acid.
  • Aminocarboxylates in particular glutamic diacetic acid (GLDA) or methylglycinediacetic acid (MGDA), and complexing agents required.
  • complexing agents in particular phosphonates, such as 1-hydroxyethane (1, 1-diphosphonic acid) (HEDP), are suitable.
  • HEPP is formulated with a calcium salt in a phosphate-free formulation
  • calcium phosphonate may precipitate. This is undesirable on the one hand for aesthetic reasons, because the appearance of the product suffers from the white precipitates, and on the other hand, the reduced Enzyme performance through the loss of enzyme stabilizer.
  • the object of the present invention was therefore to provide a phosphate-free, liquid dishwashing detergent which overcomes the stated stability problems and has a good cleaning performance.
  • Dishwashing agent formulation can be provided when the phosphonate used as a complexing agent is formulated spatially separated from enzymes and enzyme stabilizers and has a specific composition.
  • a first subject of the present invention is therefore a phosphate-free, liquid
  • Dishwashing detergent preferably automatic dishwashing detergent, characterized in that the automatic dishwashing detergent comprises two spatially separate liquid
  • compositions A and B wherein
  • Composition A is phosphonate-free, has a pH of less than 8.5, preferably 8 or less, more preferably 7 to 8, in particular about 7.5, and comprises:
  • Enzyme stabilizer based on the total weight of
  • Composition A comprises less than 0.1% by weight of boric acid and / or borate, preferably is free from boric acid and / or borate;
  • composition A comprises less than 9 wt .-% glutamic diacetic acid (GLDA), preferably less than 5% by weight, in particular free of GLDA, and wherein the at least one builder preferably comprises methylglycinediacetic acid (MGDA); and
  • Composition B is enzyme- and calcium-free, has a pH greater than 9, preferably greater than 10, in particular greater than 10 to less than 11.5, and comprises:
  • HEDP 1-hydroxyethane- (1, 1-diphosphonic acid
  • At least one builder wherein the at least one builder based on the total weight of composition A comprises less than 3% by weight of glutamic diacetic acid (GLDA), preferably is free of GLDA, and wherein the at least one builder is preferably selected from methylglycinediacetic acid (MGDA), soda, citrate and combinations thereof.
  • GLDA glutamic diacetic acid
  • MGDA methylglycinediacetic acid
  • a dishwashing agent according to the invention in a machine dishwashing process, in particular the use for improving the cleaning performance of enzyme-sensitive soiling on dishes during its cleaning in an automatic dishwashing machine.
  • the present invention is also directed to a machine dishwashing process in which a dishwashing composition according to the invention, in particular for the purpose, the
  • At least one as used herein includes, but is not limited to, 1, 2, 3, 4, 5, 6 and more.
  • the indication refers to the type of ingredient, not the absolute number
  • at least one builder means at least one type of builder, that is, one type of builder or a mixture of several different builders.
  • weight refers to all compounds of the type indicated, those in the composition / mixture ie that the composition contains no further compounds of this type beyond the indicated 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 GPC, as described for M n .
  • phosphate-free or phosphonate-free means that the composition in question is substantially free of phosphates or phosphonates, i.
  • phosphates or phosphonates in particular phosphates or phosphonates in amounts less than 0.1 wt .-%, preferably less than 0.01 wt .-%, based on the respective composition contains.
  • Substantially free of calcium salts i. in particular calcium salts in amounts less than 0.1 wt .-%, preferably less than 0.07 wt .-%, more preferably less than 0.05 wt .-%, preferably less than 0.03 wt .-%, particularly preferably less than 0.01 wt .-%, based on the composition B contains.
  • Enzyme-free as used herein means that the corresponding composition is substantially free of enzymes, ie in particular enzymes or enzyme preparations or preparations in amounts less than 0.1% by weight, preferably less than 0.05% by weight. -%, preferably less than 0.01 wt .-%, in particular less than 0.001 wt .-% based on the respective composition, here composition B contains.
  • Boate or boric acid free means that the composition in question is substantially free of borates or boric acid, ie in particular borates or boric acid in amounts less than 0.05% by weight, preferably less than 0.01% by weight .-%, in particular less than 0.001 wt .-% based on the composition.
  • GLDA-free or "free of GLDA” as used herein means that the subject
  • Composition is substantially free of glutamic diacetic acid (GLDA), ie in particular GLDA in amounts less than 1 wt .-%, preferably less than 0.1 wt .-%, in particular less than 0.01 wt .-% based on the composition ,
  • GLDA glutamic diacetic acid
  • “Monoethanolamine-free” as used herein means that the composition in question is substantially free of ethanolamine, ie in particular ethanolamine in amounts less than 0.1% by weight, preferably less than 0.01% by weight, in particular less than Contains 0.001 wt .-% based on the composition.
  • the composition contains NaOH in amounts less than 0.5% by weight, preferably less than 0.1% by weight of the particular composition. However, it is to be understood that these amounts do not refer to agents or compositions in which sodium and hydroxide ions are dissociated and in which the corresponding ions may also be derived, for example, from KOH and sodium citrate.
  • Liquid as used herein includes liquids and gels.
  • Embodiments refers to the pH measured with a standard electrode in the undiluted state at 25 ° C.
  • the term "spatially separated" with respect to the compositions as used herein means that the compositions can not come into contact with each other prior to use.
  • the dishwashing detergent is provided in a multi-compartment package such as a bottle or pouch for this purpose. in particular a two-chamber bottle or a Zweichammerpouch, wherein the respective composition is separate from the other composition (s) in a separate chamber.
  • composition A contains at least one amylase and at least one protease.
  • composition A additionally contains at least one further enzyme.
  • Suitable enzymes include, but are not limited to, proteases, lipases, hemicellulases, particularly pectinases and / or mannanases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof.
  • Dishwashing improved variants are available, which are used according to preferred.
  • Dishwashing compositions according to the invention preferably contain the respective enzymes in total amounts of from 1 ⁇ 10 -6 to 5% by weight, based in each case on active protein and the
  • the protein concentration can help with known methods, for example the BCA method or the biuret method.
  • proteases are among the most technically important enzymes of all. For detergents and dishwashing detergents, they are the longest established enzymes and contained in virtually all modern, powerful detergents and dishwashing detergents. They cause the degradation of protein-containing stains on the items to be cleaned. Of these, in turn, proteases of the subtilisin type (subtilases, subtilopeptidases, EC 3.4.21.62) are particularly important, which are due to the catalytically active amino acids serine proteases. They act as nonspecific endopeptidases and hydrolyze any acid amide linkages that are internal to peptides or proteins. Their pH optimum is usually in the clearly alkaline range.
  • Subtilases Subtilisin-like Proteases
  • R. Siezen pages 75-95 in "Subtilisin enzymes", edited by R. Bott and C. Betzel, New York, 1996.
  • Subtilases are naturally occurring formed by microorganisms. Of these, in particular, the subtilisins formed and secreted by Bacillus species are to be mentioned as the most important group within the subtilases.
  • subtilisin-type proteases preferably used in washing and dishwashing detergents 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,
  • Proteases are selectively or randomly modified by methods known from the prior art and thus optimized, for example, for use in detergents and dishwashing detergents. These include point mutagenesis, deletion or insertion mutagenesis or fusion with other proteins or protein parts. Thus, 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, B. amyloliquefaciens, B. stearothermophilus, Aspergillus niger and A. oryzae and the further developments of the aforementioned amylases which are improved for use in dishwashing detergents. Furthermore, for this purpose, the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and cyclodextrin glucanotransferase (CGTase) from B. agaradherens
  • lipases or cutinases are also usable according to the invention.
  • these include, for example, the lipases which are obtainable or further developed from Humicola lanuginosa (Thermomyces lanuginosus), in particular those having one or more of the following amino acid exchanges starting from said lipase in positions D96L, T213R and / or N233R, particularly preferably T213R and N233R.
  • enzymes can be used which are termed hemicellulases
  • Oxidoreductases for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention to increase the bleaching effect.
  • Cleaning-active proteases and amylases are generally not provided in the form of the pure protein but rather in the form of stabilized, storage and transportable preparations.
  • Such prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or added with stabilizers or further auxiliaries.
  • the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core with a water, air and / or
  • Chemical-impermeable protective layer is coated.
  • further active ingredients for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied.
  • Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes.
  • such granules for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.
  • Protease and amylase preparations preferably used according to the invention each contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, more preferably between 0.4 and 20% by weight and
  • composition A which, based in each case on their total weight, contains from 0.1 to 12% by weight, preferably from 0.2 to 10% by weight and in particular from 0.5 to 8% by weight contain each enzyme preparation.
  • a protein and / or enzyme may be particularly protected during storage against damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage.
  • damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage.
  • inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases.
  • the dishwashing agents may contain, for example, calcium salts as stabilizers.
  • Water-soluble calcium salts useful as enzyme stabilizers include, but are not limited to, calcium chloride (CaCk), calcium lactate or calcium acetate. Also suitable are other salts of calcium with alpha-hydroxycarboxylic acids or alpha-amino acids.
  • Suitable calcium salts for stabilizing enzymes are in various aspects.
  • Embodiments in Composition A in an amount of 0.05 to 2 wt .-%, in particular 0.1 to 0.6 wt .-%, based on the total weight of the composition A included.
  • the dishwashing detergent may comprise further stabilizers, in particular selected from boronic acids, their salts and esters, peptides, peptide derivatives, peptide adducts, polyols and combinations of the abovementioned.
  • Preferred polyols are in particular glycerol, propylene glycol and / or sorbitol.
  • Boronic acid compounds are phenylboronic acid derivatives, in particular the phenylboronic acid derivative 4-formyl-phenylboronic acid (4-FPBA). Further preferred phenylboronic acid derivatives may also have further chemical modifications on the phenyl ring, in particular they may contain one or more methyl, amino, nitro, chloro, fluoro, bromo, hydroxyl, formyl, ethyl , Acetyl, t-butyl, anisyl, benzyl, trifluoroacetyl, N-hydroxysuccinimide, t-butyloxycarbonyl, benzoyl, 4-methylbenzyl, thioanizyl, thiocresyl, benzyloxymethyl, 4-nitrophenyl,
  • boronic acids as used herein includes all compounds of the formula R-B (OH) 2 in which R is an organic radical and salts and esters thereof in which one or both of the hydrogens are cations or an organic radical are replaced.
  • the compounds of the general structural formula can furthermore be used as enzyme stabilizers
  • A is an amino acid residue
  • A is selected from Ala, Gly, Val, Ile, Leu, Phe, Lys
  • Y is -C (O) -X or CHOH-SOsB
  • B is hydrogen or a suitable cation, in particular (alkali) metal cation
  • X is hydrogen or CF 3
  • Z is an N-capping moiety selected from phosphoramidate [(R'O) 2 (O) P-], sulfenamide [(SR ') 2-],
  • R is selected from straight-chain or branched C1-C6 unsubstituted alkyl, phenyl and C7-C9 alkylaryl radicals, in particular -CH2-phenyl or -CH2- (4-hydroxyphenyl); and
  • n is 0, 1 or 2, preferably 0 or 1, wherein when n is not 0 the amino acids are linked via a peptide bond.
  • Preferred radicals R are selected from methyl, isopropyl, sec-butyl, isobutyl, C6H5, -CH2-C6H5, -CH2-C6H4OH (in particular CH2- (4-hydroxyphenyl), and -CH2-CH2-C6H5, such that the -NH-CH (R) -Y portion of the compound of formula (I) is derived from the amino acids Ala, Val, Ile, Leu, Tyr, PGIy (phenylglycine), Phe and HPhe (homophenylalanines) by the carboxyl group Although such residues are therefore not amino acids (although they may be synthesized from an amino acid precursor), for convenience herein exemplified enzyme stabilizers are the aldehyde moiety of the inhibitors.
  • the one of the corresponding amino acids is denoted by the suffix "H” after the analogous amino acid (eg, "-AlaH” represents the radical "-NHCH (CH 3 ) C (O) H”).
  • Trifluoromethylketone are likewise characterized by the additive "CF3” after the analogous amino acid (eg, standing “-AlaCF 3” for the radical "-NHCH (CH3) C (0) CF 3”).
  • the bisulfite adducts of aldehydes by adding "SO3H” or "S0 3 Na” after the analogous amino acid referred to (for example, "-TyrSOsH” represents the radical "-NHCH (CH2C6H 4 OH) CHOH-S0 3 H” ).
  • the aldehydes of the present invention can be prepared from the corresponding amino acids by converting the C-terminal carboxyl group of the amino acid into an aldehyde group.
  • Such aldehydes may be prepared by known methods, e.g. in U.S. Pat. Pat. No. 5015627, EP 0 185 930, EP 0 583 534 and DE 3200812.
  • the trifluoromethyl ketones can also be prepared from the corresponding amino acids by converting the C-terminal carboxyl group into a trifluoromethyl ketone group.
  • Such trifluoromethyl ketones can be prepared by known methods, for example as described in EP 0 583 535.
  • the N-terminal end of the enzyme stabilizers is protected by a protecting group capping the N-terminus, the group being selected from carbamates, ureas,
  • the N-terminal end is replaced by a methyl, ethyl or benzyl carbamate group [CH 3 O- (O) C-; CH 3 CH 2 O- (0) C-; or C 6 H 5 CH 2 O- (O) C-], a methyl, ethyl or benzyl urea group [CH 3 NH- (O) C-; CH 3 CH 2 NH- (O) C-; or CeH 5 CH 2 NH- (O) C-], a methyl, ethyl or
  • Benzylsulfonamide group [CH 3 S0 2 -; CH 3 CH 2 S0 2 -; or CeHsChhSOH, or a methyl, ethyl or benzylamidophosphate group [CH 3 O (OH) (O) P-; CH 3 CH 2 0 (OH) (0) P-; or C 6 H 5 CH 2 O (OH) (O) P-].
  • N-capping groups can be found in the following documents: Protective Groups in Organic Chemistry, Greene, T., Wuts, P., John Wiley & Sons, New York, 1991, pp 309-405; March, J, Advanced Organic Chemistry, Wiley Interscience, 1985, pp. 445, 469, Carey, F. Sundberg, R., Advanced Organic Chemistry, Part B, Plenum Press, New York, 1990, p. 686-89; Atherton, E., Sheppard, R., Solid Phase Peptide Synthesis, Pierce Chemical, 1989, pp. 3-4; Grant, G., Synthetic Peptides, W.H. Freeman & Co. 1992, pp.
  • Exemplary enzyme stabilizers that can be used in the present invention include, but are not limited to: CH 3 O- (0) C-Leu-LeuH; CH 3 0- (0) C-Ala-LeuH; CH 3 CH 2 0- (0) C-Ala-LeuH; C6H 5 CH 2 0- (0) C-Ala-LeuH; CH 3 O- (0) C-Ala-Leu CF 3 ; CH 3 CH 2 0- (0) C-Ala-LeuCF 3;
  • the invention also encompasses all stereoisomers
  • the peptide derivatives and peptide adducts used as stabilizers can be selected from those disclosed in the patent publications WO 2013/004636 A1, WO 2014/173980 A2, WO 2013/004635 A1, WO2014 / 124927 A2, WO2009 / 118375 A2, US Pat. No. 6,165,966 and US Pat
  • the agents of the invention contain based on the total weight of the agents
  • Composition A less than 0.3 wt .-% boric acid and / or borate, in particular less than 0.1 wt .-% boric acid and / or borate, preferably they are free of boric acid and / or borate.
  • Particularly preferred according to the invention is the use of calcium salts, polyols, boronic acids and / or peptide derivatives / adducts, in particular a combination of
  • Calcium salts in particular calcium chloride, and polyols, in particular sorbitol, with
  • Calcium salts are used in the amounts described above.
  • the polyols are usually used in amounts of 5-10% by weight, based on the total weight of the composition, of the boronic acids / peptide adducts in amounts of up to 1% by weight,
  • Phosphonates can be used.
  • the phosphonate compound used is preferably a hydroxyalkane and / or aminoalkane phosphonate.
  • the hydroxyalkane phosphonates the 1-hydroxyethane-1, 1-diphosphonate (HEDP) is of particular importance.
  • Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs.
  • Phosphonates are present in the compositions preferably in amounts of from 0.5 to 3% by weight, in particular in amounts of from 1 to 2.6% by weight, in each case based on the total weight of the composition B. In preferred embodiments, the amount is not more than 300 mg phosphorus / job.
  • dishwashing agents described herein are of a liquid nature and may, in particular, be present as homogeneous solutions or suspensions. In a further preferred
  • the dishwashing detergent is in a pre-portioned form.
  • the automatic dishwashing detergent has several spatially separate compositions, making it possible, on the one hand, to separate incompatible ingredients from one another, and, on the other hand, to offer compositions in combination which are used at different times in the dishwasher.
  • the dishwashing agents further comprise at least one builder in the form that composition A contains at least one builder, wherein the at least one builder based on the total weight of the composition A less than 9 wt .-%
  • Glutamic diacetic acid (GLDA) or salts thereof preferably less than 5% by weight, in particular less than 2% by weight glutamine diacetic acid (GLDA) or its salts, and very particularly preferably is free from GLDA
  • composition B contains at least one builder in which the at least one builder, based on the total weight of the composition A, comprises less than 3% by weight, in particular less than 2% by weight of glutamic diacetic acid (GLDA) or salts thereof, preferably is free of GLDA.
  • usable builders include in particular carbonates, citrates, phosphonates, organic builders and silicates.
  • Total weight of compositions according to the invention is preferably 10 to 80 wt .-%, more preferably 15 to 70 wt .-% and in particular 20 to 50 wt .-%.
  • Suitable organic builders according to the invention are, for example, the polycarboxylic acids 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
  • Preferred polycarboxylic acids are thus dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids and pentacarboxylic acids, in particular di-, tri- and tetracarboxylic acids.
  • the polycarboxylic acids may carry further functional groups, such as hydroxyl or amino groups.
  • these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids (preferably aldaric acids, for example galactaric acid and
  • Glucaric acid aminocarboxylic acids, in particular aminodicarboxylic acids, aminotricarboxylic acids, aminotetracarboxylic acids, such as nitrilotriacetic acid (NTA), methylglycinediacetic acid (MGDA), aspartic diacetate (ASDA), hydroxyethyliminodiacetate (HEIDA), iminodisuccinate (IDS) and ethylenediamine disuccinate (EDDS), and derivatives thereof, and mixtures of this, wherein glutamine-N, N-diacetic acid (also referred to as N, N-bis (carboxymethyl) -L-glutamic acid or GLDA) as described above is preferably excluded.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, MGDA and mixtures thereof.
  • polymeric polycarboxylates organic polymers having a multiplicity of (in particular greater than 10) carboxylate functions in the
  • the free acids typically also have the property of an acidifying component and can thus also serve to adjust the pH.
  • citric acid succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
  • the at least one builder is in
  • Composition A and / or B methylglycinediacetic acid (MGDA).
  • MGDA methylglycinediacetic acid
  • composition B contains two or more builders, such as soda and / or citrate, optionally in combination with MGDA.
  • MGDA as used herein, encompasses both the free acid and the corresponding salts.
  • dishwasher detergents according to the invention contain as one of their essential builders one or more salts of citric acid, ie citrates, for example sodium or potassium citrate. These are preferably in a proportion of 2 to 40 wt .-%, in particular from 5 to 30 wt .-%, particularly from 7 to 25 wt .-%, particularly preferably 10 to 20 wt .-%, most preferably 12 to 17 wt .-%, each based on the total weight of the respective composition A or B. In various embodiments, composition A contains no citrate. In different others
  • Embodiments comprises composition B citrate, especially sodium citrate, preferably in an amount of 10 to 20% by weight, in particular 12 to 17% by weight, for example about 14% by weight.
  • composition A contains no
  • Carbonate / bicarbonate Contains in various other embodiments
  • Composition B Carbonates / bicarbonates, in particular soda, preferably in an amount of 6 to 15 wt .-%, in particular 7 to 12 wt .-%.
  • dishwashing agents preferably mechanical
  • composition B contains at least two builders from the group of silicates, phosphonates, carbonates, MGDA and citrates, wherein the weight fraction of these builders, based on the total weight of
  • Composition preferably 5 to 70 wt .-%, preferably 10 to 50% by weight and in particular 15 to 40 wt .-% is.
  • the combination of two or more builders from the above-mentioned group has for the cleaning and rinsing performance according to the invention Detergents, in particular dishwashing detergents, preferably automatic dishwasher detergents, have proven to be advantageous. In addition to the builders mentioned here, one or more other builders may additionally be present.
  • Preferred dishwashing detergents are characterized by a builder combination in composition B of citrate and carbonate and / or bicarbonate.
  • a mixture of carbonate and citrate is used, wherein the amount of carbonate preferably 3 to 30 wt .-% and in particular from 4 to 20 wt .-%, most preferably 5 to 15 wt .-%, and the amount to citrate preferably from 2 to 40 wt .-%, in particular from 3 to 30 wt .-%, particularly from 4 to 25 wt .-%, particularly preferably 5 to 20 wt .-%, most preferably 7 to 17 wt. -%, in each case based on the total weight of
  • Composition B is, wherein the total amount of these two builders is preferably 10 to 40 wt .-%, more preferably 15 to 30 wt .-%, in particular not more than 25 wt .-%.
  • composition B additionally contains MGDA in addition to the citrate and the soda.
  • MGDA wt .-% - proportion of MGDA in such
  • Compositions B is preferably 0 to 20 wt .-%, in particular 1 to 15 wt .-%, especially 2 to 8 wt .-%. In various embodiments of the invention contains
  • Composition B up to 5 wt .-%, for example 2 to 4 wt .-% MGDA.
  • the particularly preferred amounts of citrate and soda are as described in the preceding paragraph.
  • Composition A in various embodiments contains at least one builder, which builder is MGDA.
  • Composition A may contain additional builders, in particular citrate, but in various embodiments no further builder is included.
  • the amount of MGDA in Composition A is preferably up to 25% by weight, more preferably 2 to 20% by weight, especially 8-15% by weight. In certain embodiments
  • Composition A up to 13% by weight of MGDA.
  • polymeric polycarboxylates are furthermore suitable; these are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol.
  • Suitable polymers are, in particular, polyacrylates, which are preferably a
  • Geschirr Cyprusmitte according to the invention can as a builder also crystalline layered silicates of general formula NaMSix02x + i ⁇ y H2O wherein M is sodium or hydrogen, x is a number from 1, 9 to 22, preferably from 1: 9 to 4, particularly preferred values for x 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20.
  • amorphous sodium silicates having a modulus Na 2 O: SiO 2 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 are preferably delayed in dissolution and secondary wash properties.
  • dishwashing detergents preferably dishwasher detergents
  • the content of silicates, based on the total weight of the detergent is limited to amounts below 10% by weight, preferably below 5% by weight and in particular below 2% by weight
  • the agents are free of silicates, "free" in this context meaning that the amount is limited to less than 0.1% by weight.
  • Dishwashing agent in particular composition B, further alkali metal hydroxides as alkali source.
  • These alkali carriers are particularly preferred in the compositions and especially in the second phases (composition B) only in small amounts, preferably in amounts below 10 wt .-%, preferably below 6 wt .-%, preferably below 5 wt .-% between 0.1 and 5 wt .-% and in particular between 0.5 and 5 wt .-%, each based on the total weight of the composition used.
  • Composition B contains less than 1.71% by weight, based on the total weight of Composition B, of NaOH, preferably less than 1.0% by weight of NaOH, more preferably Composition B is free of NaOH.
  • Embodiments therefore contain composition B instead of NaOH potassium hydroxide (KOH) as alkali source, preferably in the amounts indicated above, in particular up to 3.5 wt .-%.
  • the alkali metal hydroxides, especially KOH are used in amounts such that the pH values of the compositions according to the invention are achieved.
  • the dishwashing agents preferably also contain at least one surfactant.
  • the surfactants may be contained both in composition A and in composition B or both.
  • the at least one surfactant is preferably present in composition A, most preferably in amounts of up to 4% by weight, based on the total weight of composition A.
  • the surfactants contained are preferably nonionic surfactants.
  • nonionic surfactants it is possible to use all nonionic surfactants known to the person skilled in the art.
  • Low-foaming nonionic surfactants are preferably used, in particular alkoxylated, especially ethoxylated, low-foaming nonionic surfactants.
  • the automatic dishwashing detergents contain nonionic surfactants from the group of the alkoxylated alcohols.
  • nonionic surfactants which have a melting point above
  • Nonionic (s) surfactants having a melting point above 20 ° C, preferably above 25 ° C, more preferably between 25 and 60 ° C and especially between 26.6 and 43.3 ° C, is / are particularly preferred.
  • 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.
  • nonionic surfactants have been low-foaming nonionic surfactants which contain alternating ethylene oxide and ethylene oxide
  • 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.
  • R is a straight-chain or branched, saturated or mono- or polyunsaturated Ce-24-alkyl or alkenyl radical; each group R 2 or R 3 is independently selected from -Chta, -CH 2 CH 3, -CH 2 CH 2 -CH 3, CH (CH 3) 2 and the indices w, x, y, z independently represent integers from 1 to 6.
  • nonionic surfactants having a C9-alkyl group with 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units, followed by 1 to 4
  • Preferred nonionic surfactants here are those of the general formula R -CH (OH) CH 2 O- (AO) w- (AO) x- (A "O) y - (A"'O) z R 2 , in which
  • R is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24-alkyl or alkenyl radical
  • R 2 is H or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
  • A, ⁇ ', A "and A'" independently of one another are radicals 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 ),
  • w, x, y and z are values between 0.5 and 120, where x, y and / or z can also be 0.
  • Preparations are significantly improved both in comparison to surfactant-free system as well as compared to systems containing alternative nonionic surfactants, for example from the group of polyalkoxylated fatty alcohols.
  • Hydrocarbon radicals having 2 to 30 carbon atoms, preferably 4 to 22
  • Carbon atoms further having a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R 2 having 1 to 30 carbon atoms, wherein x for values between 1 and 90, preferably for values between 30 and 80 and in particular for values between 30 and 60 stands.
  • surfactants of the formula R 0 [CH 2 CH (CH 3) O] x [CH 2 CH 2 O] yCH 2 CH (OH) R 2 in which R is a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R 2 is a linear one or branched
  • Hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1, 5 and y is a value of at least 15 stands.
  • nonionic surfactants include, for example, the C2-26 fatty alcohol (PO) i (EO) iso-4o-2-hydroxyalkyl ethers, in particular also the ceria fatty alcohol (PO) i (EO) 22-2-hydroxydecyl ethers ,
  • nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 0 [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] jOR 2 where R 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 is Values between 1 and 30, k and j represent values between 1 and 12, preferably between 1 and 5.
  • k and j represent values between 1 and 12, preferably between 1 and 5.
  • R 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 are particularly preferred.
  • R 3 H, -Chta 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.
  • R 1 RO [CH 2 CH (R 3 ) O] x CH 2 CH (OH) CH 2 OR 2 simplified.
  • 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 and R 2 Have 9 to 14 carbon atoms, R 3 is H and x assume values of 6 to 15.
  • nonionic surfactants of the general formula R -CH (OH) CH 2 O- (AO) wR 2 have proven to be particularly effective, in which
  • R for a straight-chain or branched, saturated or on or
  • R 2 is a linear or branched hydrocarbon radical having 2 to 26
  • A is a radical from the group CH 2 CH 2 , CH 2 CH 2 CH 2 , CH 2 CH (CH 3 ),
  • w stands for values between 1 and 120, preferably 10 to 80, in particular 20 to 40
  • the group of these nonionic surfactants includes, for example, the C4-22 fatty alcohol (EO) io-8o-2-hydroxyalkyl ethers, in particular also the C8-12 fatty alcohol (EO) 22-2-hydroxydecyl ethers and the C4-22 fatty alcohol (EO) 4o 8o-2-hydroxyalkyl ethers.
  • R 2 is hydrogen and R, R 3 , A, ⁇ ', A ", A'", w, x, y and z are as defined above.
  • dishwashing detergents are characterized in that the dishwashing detergent contains at least one nonionic surfactant, preferably a nonionic surfactant from the group of hydroxy mixed ethers, wherein the weight fraction of the nonionic surfactant on the dishwashing detergent.
  • Total weight of the dishwashing agent is preferably 0.1 to 10 wt .-%, preferably 0.5 to 8.0 wt .-% and in particular 1, 0 to 4.0 wt .-%.
  • composition A may further comprise at least one sulfopolymer.
  • the proportion by weight of the sulfopolymer in the total weight of the composition is preferably from 0.1 to 20 wt .-%, in particular from 0.5 to 15 wt .-%, particularly preferably 1, 0 to 10 wt .-%, in particular from 2 to 8 Wt .-%, especially from 3 to 6 wt .-%.
  • Very particular preference is given to compositions which contain up to 6% by weight of sulfopolymer.
  • the sulfopolymer is usually used in the form of an aqueous solution, the aqueous solutions typically containing 20 to 70 wt .-%, in particular 30 to 50 wt .-%, preferably about 35 to 40 wt .-% sulfopolymers.
  • the sulfopolymer used is preferably a copolymeric polysulfonate, preferably a hydrophobically modified copolymeric polysulfonate.
  • the copolymers may have two, three, four or more different monomer units.
  • Preferred copolymeric polysulfonates contain sulfonic acid group-containing (s)
  • Monomer (s) at least one monomer from the group of unsaturated carboxylic acids.
  • unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, ⁇ -cyanoacrylic acid, crotonic acid, ⁇ -phenyl-acrylic acid, maleic acid,
  • R 5 (R 6 ) C C (R 7 ) -X-SO 3 H in which R 5 to R 7 independently of one another are -H, -CH 3, a 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, or -COOH or -COOR 4 , wherein R 4 is a saturated or unsaturated, straight-chain or branched
  • 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-sulfo - Propylmethacrylat, sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of said acids or their water-
  • the sulfonic acid groups may be wholly or partially in neutralized form, i. the acidic acid of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions.
  • metal ions preferably alkali metal ions and in particular for sodium ions.
  • the monomer distribution of the copolymers preferably used according to the invention in the case of copolymers containing only monomers containing carboxylic acid groups and monomers containing sulfonic acid groups is preferably from 5 to 95% by weight, more preferably from 50 to 90% by weight of the sulfonic acid group-containing monomer. % and the share of
  • 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 dishwashing detergents are characterized in that the copolymers have molar masses of 2000 to 200,000 gmol -1 , preferably of 4,000 to 25,000 gmol and in particular of 5,000 to 15,000 gmol -1 .
  • the copolymers include besides
  • Carboxyl-containing monomer and sulfonic acid-containing monomer further at least one nonionic, preferably hydrophobic monomer.
  • the use of these hydrophobically modified polymers has made it possible in particular to improve the rinse aid performance of automatic dishwashing detergents according to the invention.
  • Anionic copolymers comprising monomers containing carboxylic acid groups, monomers containing sulfonic acid groups and nonionic monomers, in particular hydrophobic monomers, are therefore preferred according to the invention.
  • nonionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 , 4-trimethylpentene-1, 2,4,4-trimethylpentene-2,3,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethlyhexene-1,3,5-dimethylhexene-1,4 , 4-dimethylhexane-1, ethylcyclohexyne, 1-octene, alpha-olefins having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and
  • Acrylic acid hexyl ester methyl methacrylate, N- (methyl) acrylamide, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, N- (2-ethylhexyl) acrylamide, octyl acrylate, octyl methacrylate, N- (octyl) acrylamide, lauryl acrylate, lauryl methacrylate, N- (meth) acrylate.
  • the monomer distribution of the hydrophobically modified copolymers preferably used according to the invention is preferably in each case from 5 to 80% by weight, with respect to the sulfonic acid group-containing monomer, the hydrophobic monomer and the carboxylic acid group-containing monomer, the proportion of the sulfonic acid group-containing monomer and of the each hydrophobic monomer 5 to 30 wt .-% and the proportion of the carboxylic acid group-containing monomer 60 to 80 wt .-%, the monomers are in this case preferably selected from the aforementioned.
  • the pH of the dishwashing detergent can be adjusted by means of customary pH regulators.
  • the pH (neat, measured at 25 ° C.) of the composition A is in a range from 5.5 to 8.5, preferably 6.5 to 8.0, particularly preferably from 7.0 to 8, 0, in particular at about 7.5
  • the pH of the composition B is in a range of 9.0 to 12, preferably 10.0 to 11, 5, preferably greater than 10, in particular 10.5 to 11, 5
  • the pH adjusting agents used are acids and / or alkalis, preferably Alkalis. 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.
  • mineral acids such as sodium tartaric acid, sodium tartaric acid, sodium tartaric acid, sodium tartaric acid, sodium tartaric acid and sodium gluconic acid or amidosulfonic acid.
  • Hydrochloric acid, sulfuric acid and nitric acid or mixtures thereof are used.
  • Suitable bases are selected from the group of alkali and alkaline earth metal hydroxides
  • alkali metal hydroxides of which potassium hydroxide is preferred.
  • the above-described alkali source is used to adjust the pH. Even if volatile alkali, for example in the form of ammonia and / or
  • Alkanolamines which may contain up to 9 carbon atoms in the molecule can be used to adjust the pH, wherein the alkanolamine is hereby selected from the group consisting of mono-, di-, triethanol- and -propanolamine and their Mixtures, is preferably dispensed with such volatile alkali, in particular ethanolamines.
  • the compositions contain less than 1.75% by weight of alkanolamine, especially monoethanolamine, most preferably they are free thereof. It has been found that omitting such alkanolamines, the stability of the
  • the composition according to the invention may contain one or more buffer substances (INCI Buffering Agents), usually in amounts of from 0.001 to 5% by weight. Preference is given to buffer substances which at the same time complexing agents or even
  • Chelating agents are.
  • Particularly preferred buffer substances are citric acid or citrates, in particular the sodium and potassium lead,
  • trisodium citrate2H20 and tripotassium citrate ⁇ 2 ⁇ for example, trisodium citrate2H20 and tripotassium citrate ⁇ 2 ⁇ .
  • the agents according to the invention preferably comprise at least one further constituent, preferably selected from the group consisting of anionic, cationic and amphoteric surfactants, in particular anionic surfactants, bleaching agents, bleach activators,
  • Bleach catalysts thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular silver protectants, glass corrosion inhibitors, foam inhibitors, dyes, fragrances, bitter substances and antimicrobial agents.
  • Preferred anionic surfactants are fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates, alkylbenzenesulfonates, olefinsulfonates, alkanesulfonates, ether sulfonates, n-alkyl ether sulfonates, ester sulfonates and lignosulfonates.
  • fatty acid cyanamides especially sulfosuccinates (sulfosuccinic esters), especially sulfosuccinic acid mono- and di-Cs-O-alkyl esters, sulfosuccinamates,
  • Fatty acid sarcosinates Fatty acid sarcosinates, ether carboxylic acids and alkyl (ether) phosphates and ⁇ -sulfofatty acid salts, acylglutamates, monoglyceride disulfates and alkyl ethers of glycerol disulfate.
  • the anionic surfactants are preferably used as sodium salts, but may also be present as other alkali or alkaline earth metal salts, for example potassium or magnesium salts, and in the form of ammonium or mono-, di-, tri- or tetraalkylammonium salts, in the case of the sulfonates also in the form of their corresponding acid, eg Dodecylbenzenesulfonic.
  • Suitable amphoteric surfactants are, for example, betaines of the formula (R ⁇ XR ⁇ XR ⁇ N + ChhCOO- in which R i is an optionally interrupted by hetero atoms or hetero atom groups alkyl radical having 8 to 25, preferably 10 to 21 carbon atoms and R iv and R v are identical or different Alkyl radicals having 1 to 3 carbon atoms, in particular Cio-Cis-alkyl dimethylcarboxymethylbetain and Cn-Ci7-alkylamidopropyl-dimethylcarboxymethylbetain.
  • Suitable cationic surfactants are i.a. the quaternary ammonium compounds of the formula
  • R VI (R VI ) (R vii ) (R viii ) (R ix ) N + X "
  • R vi to R ix for four identical or different, in particular two long and two short-chain, alkyl radicals and X " for an anion , in particular a halide ion, for example, didecyl-dimethyl-ammonium chloride, alkyl-benzyl-didecyl-ammonium chloride and mixtures thereof.
  • Suitable cationic surfactants are the quaternary
  • surface-active compounds in particular with a sulfonium, phosphonium, iodonium or arsonium group, which are also known as antimicrobial agents.
  • the agent can be designed with an antimicrobial effect or its possibly existing antimicrobial effect due to other ingredients can be improved.
  • Glass corrosion inhibitors prevent the occurrence of haze, streaks and scratches, but also iridescence of the glass surface of machine-cleaned glasses.
  • Preferred glass corrosion inhibitors come from the group of bismuth, magnesium and zinc salts as well as the magnesium and zinc complexes.
  • the content of zinc salt in dishwashing detergents is preferably between 0.1 and 5 wt.%, Preferably between 0.2 and 4 wt.% And in particular between 0.4 and 3 wt.
  • the content of zinc in oxidized form (calculated as Zn 2+ ) is between 0.01 to 1 wt.%, preferably between 0.02 and 0.5 wt.% and in particular between 0.04 and 0.2 wt.
  • polyethyleneimines such as are obtainable, for example, under the name Lupasol® (BASF), preferably in an amount of 0 to 5 wt .-%, in particular 0.01 to 2 wt .-%, as
  • 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, patchouli, rose or ylang-ylang oil.
  • the thickeners used are preferably xanthan or polyacrylates.
  • at least one of the compositions, preferably both, contains at least one thickener, for example a polyacrylate, typically in an amount sufficient to adjust the desired viscosity, for example, in an amount of from 0.5 to 1.5 wt. %, preferably 0.75 to 1, 0 wt .-% based on the total weight of
  • composition A contains:
  • composition A Composition A; and (v) at least one sulfopolymer, preferably in an amount of up to 6% by weight based on the total weight of the composition A.
  • thickeners, dyes, perfume, corrosion inhibitors and / or preservatives and small amounts of pH adjusters may also be included be.
  • composition B contains:
  • Builder in the form of a combination of citrate, soda and MGDA, especially in amounts of up to 17% by weight, up to 15% by weight or up to 5% by weight, (iii) adjusting an alkali source, preferably KOH, in an amount corresponding to the pH, and optionally also (iv ) a rinse aid polymer, in particular a cationic polyacrylate (ie a copolymer which in addition to acrylic acid as a monomer and cationically charged monomers, in particular
  • Diallyldialkylammonium compounds Diallyldialkylammonium compounds.
  • thickeners, dyes, perfume, corrosion inhibitors and / or preservatives may be included.
  • dishwashing agents described herein can take place in different ways.
  • Solvents may be thickened, in the form of gels.
  • the detergent immediately after production has a viscosity above 2000 mPas (Brookfield Viscometer DV-II + Pro, spindle 25, 30 rpm, 20 ° C), in particular between 2000 and 10,000 mPas.
  • the viscosity may be higher, for example greater than 10,000 mPas, for example in the range 10000-50000 mPas,
  • the dishwashing agents described herein are preferably packaged in a multi-chamber bottle, in particular in a two-chamber bottle, and dosed out of this, preferably into the dosing chamber of the dishwasher.
  • the dishwashing agent is preferably prefabricated into metering units. These metering units preferably comprise the necessary for a cleaning cycle amount of washing or cleaning-active substances. Preferred metering units have a weight between 12 and 30 g, preferably between 14 and 26 g and in particular between 16 and 22 g.
  • the volume of the dosing unit is therefore preferably between 10 and 35 ml, preferably between 12 and 30 ml.
  • the dishwashing agents in the prefabricated metering units have a water-soluble sheath with particular preference.
  • the water-soluble coating is preferably formed from a water-soluble film material selected from the group consisting of polymers or polymer blends.
  • the wrapper may be formed of one or 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, may be the same or different. Particularly preferred are films which, for example, can be glued and / or sealed to packages such as hoses or cushions after being filled with an agent. In different
  • the films have the form of Mehrschpouches, wherein the
  • compositions A and B are spatially separated in different chambers of a pouch made of a water-soluble film.
  • the water-soluble coating be polyvinyl alcohol or a
  • Water-soluble coatings containing polyvinyl alcohol or a polyvinyl alcohol copolymer have a good stability with a sufficiently high water solubility, in particular cold water solubility on.
  • Suitable water-soluble films for producing the water-soluble coating are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose
  • Molecular weight in the range of 10,000 to 1,000,000 gmol "1 , preferably from 20,000 to 500,000 gmol, more preferably from 30,000 to 100,000 gmol " 1 and in particular from 40,000 to 80,000 gmol 1 .
  • polyvinyl alcohol is usually carried out by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible.
  • polyvinyl alcohol copolymers which are prepared from correspondingly polyvinyl acetate copolymers. It is preferred if at least one layer of the water-soluble coating comprises a polyvinyl alcohol whose degree of hydrolysis makes up 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.
  • a polymer selected from the group comprising a polyvinyl alcohol-containing sheet material suitable for producing the water-soluble sheath is selected from the group comprising a polyvinyl alcohol-containing sheet material suitable for producing the water-soluble sheath
  • (Meth) acrylic acid-containing (co) polymers polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers, polylactic acid or mixtures of the above polymers may be added.
  • a preferred additional polymer is polylactic acids.
  • Preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, dicarboxylic acids as further monomers. Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, with itaconic acid being preferred. Likewise preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its esters. Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylates, methacrylates or mixtures thereof.
  • the film material contains further additives.
  • the film material may include, for example, plasticizers such as dipropylene glycol, ethylene glycol, diethylene glycol,
  • Additives include, for example, release aids, fillers, crosslinking agents, surfactants, antioxidants, UV absorbers, antiblocking agents, detackifiers, or mixtures thereof.
  • water-soluble packaging according to the invention are films marketed by MonoSol LLC, for example under the designation M8630, C8400 or M8900.
  • Other suitable films include films named Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or the films VF-HP from Kuraray.
  • the corresponding use of the automatic dishwasher detergents according to the invention is likewise an object of the invention.
  • the invention likewise relates to a dishwashing process, in particular a machine dishwashing process, in which a dishwashing detergent according to the invention is used.
  • the subject matter of the present application is therefore furthermore a process for the cleaning of dishes in a dishwashing machine, in which the
  • Dishwasher is metered.
  • the metering or the entry of the agent according to the invention into the interior of the dishwasher can be done manually, but preferably the agent is metered by means of the metering chamber into the interior of the dishwasher.
  • Table 1 Composition of the automatic dishwashing agent (% by weight of active substance)
  • Residues (perfume, dyes, preservatives, ad 100 ad 100 ad 100 ad 100 water, etc.) (wt .-%)

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Abstract

La présente invention concerne une lessive liquide, exempte de phosphates, pour lave-vaisselle, qui présente une stabilité et un pouvoir nettoyant améliorés, en particulier pour les salissures sensibles aux enzymes; l'utilisation de cette lessive pour lave-vaisselle, et un procédé de lavage de vaisselle à la machine utilisant ladite lessive pour lave-vaisselle.
PCT/EP2016/063023 2015-06-12 2016-06-08 Lessive liquide pour lave-vaisselle, exempte de phosphates WO2016198446A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102015210828.7 2015-06-12
DE102015210828.7A DE102015210828A1 (de) 2015-06-12 2015-06-12 Phosphatfreies flüssiges Geschirrspülmittel

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WO2016198446A1 true WO2016198446A1 (fr) 2016-12-15

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Publication number Priority date Publication date Assignee Title
EP3835397A1 (fr) * 2019-12-12 2021-06-16 Henkel AG & Co. KGaA Produit de nettoyage

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