EP2118255B2 - Composition detergente - Google Patents

Composition detergente Download PDF

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Publication number
EP2118255B2
EP2118255B2 EP07847823.7A EP07847823A EP2118255B2 EP 2118255 B2 EP2118255 B2 EP 2118255B2 EP 07847823 A EP07847823 A EP 07847823A EP 2118255 B2 EP2118255 B2 EP 2118255B2
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Prior art keywords
weight
carbon atoms
acid
automatic dishwashing
monomers
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German (de)
English (en)
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EP2118255A1 (fr
EP2118255B1 (fr
Inventor
Nadine Warkotsch
Johannes Zipfel
Arnd Kessler
Christian Nitsch
Arno DÜFFELS
Thomas Holderbaum
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/042—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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/06—Phosphates, including polyphosphates
    • C11D3/075—Phosphates, including polyphosphates in admixture with ethers of polyoxyalkylenes
    • 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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/378—(Co)polymerised monomers containing sulfur, e.g. sulfonate
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • 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
    • C11D3/3942—Inorganic per-compounds

Definitions

  • the present patent application describes cleaning agents, in particular cleaning agents for the machine cleaning of dishes.
  • the subject matter of this application is in particular phosphate-free machine dishwashing detergents.
  • Dishwasher detergents intended for private end users contain builders as an essential component for cleaning and rinse success. These builders increase the alkalinity of the cleaning solution, whereby fats and oils are emulsified and saponified as alkalinity increases, and they also reduce the water hardness of the cleaning solution by complexing the calcium ions contained in the aqueous solution. Alkali metal phosphates have proven to be particularly effective builders, which is why they are the main component of the majority of commercially available dishwasher detergents.
  • phosphates are highly valued for their beneficial effect as a component of automatic dishwashing detergents, their use is not without problems from an environmental protection perspective, as a significant proportion of the phosphate enters the waterways via household wastewater and plays a worrying role in over-fertilizing standing waters (lakes, dams), in particular.
  • this phenomenon also known as eutrophication, the use of pentasodium triphosphate in textile detergents has been considerably reduced by law in a number of countries, e.g. the USA, Canada, Italy, Sweden and Norway, and is completely prohibited in Switzerland. In Germany, detergents may contain a maximum of 20% of this builder since 1984.
  • sodium aluminum silicates zeolites
  • these substances are not suitable for use in automatic dishwashing detergents for various reasons. A number of substitutes are therefore discussed in the literature as alternatives to the alkali metal phosphates in automatic dishwashing detergents, of which citrates are particularly noteworthy.
  • Phosphate-free dishwasher detergents which contain carbonates, bleaches and enzymes in addition to citrate, are, for example, covered by the European patents EP 662 117 B1 (Henkel KGaA) and EP 692 020 B1 (Henkel KGaA).
  • MGDA methylglycinediacetic acid
  • Dishwashing detergents containing MGDA are described, for example, in the European patent EP 906 407 B1 (Reckitt Benckiser ) or in the European patent application EP 1 113 070 A2 (Reckitt Benckiser ) described.
  • EP-A-1721962 describes phosphate-free, automatic dishwashing detergents that contain non-ionic surfactants, MGDA, percarbonate and citrate, but no copolymers containing sulfonic acid groups.
  • WO 2006/106332 describes phosphate-free, automatic dishwashing detergents that contain non-ionic surfactants, MGDA, citrate and sulfonic acid group-containing copolymers, but no bleach.
  • WO 2005/090541 discloses, among other things, a phosphate-free automatic dishwashing detergent which contains surfactants, citrate, bleach and sulfonic acid group-containing copolymers, but no MGDA.
  • the object of the present application was therefore to provide a phosphate-free automatic dishwashing detergent which is comparable to or even surpasses conventional phosphate-containing detergents in terms of its cleaning performance as well as its rinsing results and its performance with regard to deposit inhibition.
  • the copolymers a) can have two, three, four or more different monomer units.
  • 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-propen1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of the acids mentioned or their water-
  • the sulfonic acid groups can be present in completely or partially neutralized form, i.e. the acidic hydrogen atom of the sulfonic acid group in some or all of the sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions.
  • metal ions preferably alkali metal ions and in particular for sodium ions.
  • partially or fully neutralized copolymers containing sulfonic acid groups is preferred according to the invention.
  • the monomer distribution of the copolymers preferably used according to the invention is, for copolymers which contain only monomers from groups i) and ii), preferably 5 to 95% by weight of i) or ii), particularly preferably 50 to 90% by weight of monomer from group i) and 10 to 50% by weight of monomer from group ii), in each case based on the polymer.
  • the molecular weight 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 intended use.
  • Preferred automatic dishwashing detergents are characterized in that the copolymers have molecular weights of 2000 to 200,000 gmol -1 , preferably of 4000 to 25,000 gmol -1 and in particular of 5000 to 15,000 gmol -1 .
  • carboxyl group-containing monomers are acrylic acid, methacrylic acid, ethacrylic acid, chloroacrylic acid, cyanoacrylic acid, crotonic acid, phenylacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof.
  • the machine dishwashing detergents according to the invention contain methylglycinediacetic acid (MGDA) as a second essential component.
  • MGDA methylglycinediacetic acid
  • the methylglycinediacetic acid can be present in the detergents according to the invention in the form of the free acid, as a partial neutralizer or completely neutralized.
  • the methylglycinediacetic acid is present in the form of an alkali metal salt.
  • automatic dishwashing detergents preferably contain one or more builders as a further essential component.
  • the builders include in particular silicates, carbonates and organic cobuilders.
  • Organic cobuilders include, in particular, polycarboxylates/polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders and phosphonates. These classes of substances are described below.
  • Useful organic builders are, for example, polycarboxylic acids that can be used in the form of the free acid and/or their sodium salts, whereby polycarboxylic acids are understood to be carboxylic acids that have more than one acid function.
  • examples of these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons, and mixtures of these.
  • the free acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH value of washing or cleaning agents.
  • Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these are particularly worth mentioning here.
  • Such automatic dishwashing detergents according to the invention contain citrate as one of their essential builders. Automatic dishwashing detergents characterized in that they contain 5 to 60% by weight, preferably 10 to 50% by weight and in particular 15 to 40% by weight of citrate are preferred according to the invention. Citrate or citric acid have proven to be the most effective builders in combination with MGDA and the copolymers containing sulfonic acid groups in terms of cleaning performance and rinsing performance.
  • Machine dishwashing detergents according to the invention preferably contain, as a builder, crystalline layered silicates of the general formula NaMSi x O 2x+1 ⁇ y H 2 O, in which M represents sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, particularly preferred values for x being 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20.
  • amorphous sodium silicates with a Na 2 O : SiO 2 modulus of 1:2 to 1:3.3, preferably 1:2 to 1:2.8 and in particular 1:2 to 1:2.6, which preferably have delayed dissolution and secondary washing properties.
  • preferred automatic dishwashing detergents contain 2 to 15% by weight, preferably 3 to 12% by weight and in particular 4 to 8% by weight of silicate(s).
  • Polymeric polycarboxylates are also suitable as builders, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular mass of 500 up to 70000 g/mol.
  • Suitable polymers are in particular polyacrylates, which preferably have a molecular mass of 2000 to 20,000 g/mol. Due to their superior solubility, the short-chain polyacrylates from this group, which have molecular masses of 2000 to 10,000 g/mol, and particularly preferably of 3000 to 5000 g/mol, may be preferred.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven particularly suitable.
  • Their relative molecular mass, based on free acids, is generally 2000 to 70,000 g/mol, preferably 20,000 to 50,000 g/mol and in particular 30,000 to 40,000 g/mol.
  • the (co)polymeric polycarboxylates can be used either as a powder or as an aqueous solution.
  • the (co)polymeric polycarboxylates content of the automatic dishwashing detergents is preferably 0.5 to 20% by weight and in particular 3 to 10% by weight.
  • Suitable builders are phosphonates.
  • the complex-forming phosphonates include a number of different compounds such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or diethylenetriaminepenta(methylenephosphonic acid) (DTPMP).
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • DTPMP diethylenetriaminepenta(methylenephosphonic acid)
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • DTPMP diethylenetriaminepenta(methylenephosphonic acid)
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • It is preferably used as the sodium salt, with the disodium salt being neutral and the tetrasodium salt being alkaline (pH 9).
  • Preferred aminoalkanephosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues. They are preferably used in the form of the neutrally reacting sodium salts, e.g. B. as the hexasodium salt of EDTMP or as the hepta- and octa-sodium salt of DTPMP. HEDP is the preferred builder from the class of phosphonates.
  • the aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned, especially if the agents also contain bleach.
  • automatic dishwashing detergents which contain 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or diethylenetriaminepenta(methylenephosphonic acid) (DTPMP) as phosphonates.
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • DTPMP diethylenetriaminepenta(methylenephosphonic acid)
  • the automatic dishwashing detergents according to the invention can contain two or more different phosphonates.
  • Particularly preferred are those automatic dishwashing detergents which contain both 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and diethylenetriaminepenta(methylenephosphonic acid) (DTPMP) as phosphonates, the weight ratio of HEDP to DTPMP being between 20:1 and 1:20, preferably between 15:1 and 1:15 and in particular between 10:1 and 1:10.
  • the weight proportion of the phosphonate(s) in the total weight of the automatic dishwashing detergent is less than the weight proportion of the polymer(s) a).
  • particularly preferred detergents are those in which the ratio of the weight proportion of polymer a) to the weight proportion of the phosphonate is 200:1 to 2:1, preferably 150:1 to 2:1, particularly preferably 100:1 to 2:1, very particularly preferably 80:1 to 3:1 and in particular 50:1 to 5:1.
  • Preferred machine dishwashing detergents according to the invention also contain one or more bleaching agents.
  • bleaching agents include sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are particularly important.
  • Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and peracidic salts or peracids which provide H 2 O 2 , 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 diacyl peroxides, such as dibenzoyl peroxide.
  • Other typical organic bleaching agents are peroxyacids, with alkyl peroxyacids and aryl peroxyacids being particularly examples.
  • Automatic dishwashing detergents characterized in that they contain 1 to 20 wt.%, preferably 2 to 15 % by weight and in particular 4 to 12 % by weight of sodium percarbonate are preferred according to the invention.
  • Suitable chlorine or bromine-releasing materials include heterocyclic N-bromo- and N-chloroamides, 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 machine dishwashing detergents according to the invention can additionally contain bleach activators.
  • bleach activators Compounds which, under perhydrolysis conditions, produce aliphatic peroxocarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and/or optionally substituted perbenzoic acid, can be used as bleach activators.
  • Substances which carry O- and/or N-acyl groups of the stated number of C atoms and/or optionally substituted benzoyl groups are suitable.
  • Multiply acylated alkylenediamines are preferred, with tetraacetylethylenediamine (TAED) proving to be particularly suitable.
  • TAED tetraacetylethylenediamine
  • bleach activators in particular TAED, are preferably used in amounts of up to 10% by weight, in particular 0.1% by weight to 8% by weight, particularly 2 to 8% by weight and particularly preferably 2 to 6% by weight, each based on the total weight of the bleach activator-containing agents.
  • bleach catalysts can also be used. These substances are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo salen complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.
  • complexes of manganese in the oxidation state II, III, IV or IV which preferably contain one or more macrocyclic ligands with the donor functions N, NR, PR, O and/or S.
  • ligands are used which have nitrogen donor functions.
  • bleach catalyst(s) in the agents according to the invention which contain 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN), 1,4,7-triazacyclononane (TACN), 1,5,9-trimethyl-1,5,9-triazacyclododecane (Me-TACD), 2-methyl-1,4,7-trimethyl-1,4,7-triazacyclononane (Me/Me-TACN) and/or 2-methyl-1,4,7-triazacyclononane (Me/TACN) as macromolecular ligands.
  • Me-TACN 1,4,7-trimethyl-1,4,7-triazacyclononane
  • TACN 1,4,7-triazacyclononane
  • TACD 1,5,9-trimethyl-1,5,9-triazacyclododecane
  • Automatic dishwashing detergents characterized in that they further contain a bleach catalyst selected from the group of bleach-enhancing transition metal salts and transition metal complexes, preferably from the group of complexes of manganese with 1,4,7-trimethyl-1,4,7-triazacyclononane (Me 3 -TACN) or 1,2, 4,7-tetramethyl-1,4,7-triazacyclononane (Me 4 -TACN), are preferred according to the invention, since the aforementioned bleach catalysts in particular can significantly improve the cleaning result.
  • a bleach catalyst selected from the group of bleach-enhancing transition metal salts and transition metal complexes, preferably from the group of complexes of manganese with 1,4,7-trimethyl-1,4,7-triazacyclononane (Me 3 -TACN) or 1,2, 4,7-tetramethyl-1,4,7-triazacyclononane (Me 4 -TACN)
  • the aforementioned bleach-enhancing transition metal complexes in particular with the central atoms Mn and Co, are used in conventional amounts, preferably in an amount of up to 5% by weight, in particular from 0.0025% by weight to 1% by weight and particularly preferably from 0.01% by weight to 0.30% by weight, in each case based on the total weight of the bleach activator-containing agents. In special cases, however, more bleach activator can also be used.
  • the agents according to the invention also contain surfactants.
  • the group of surfactants includes non-ionic, anionic, cationic and amphoteric surfactants.
  • Automatic dishwashing detergents characterized in that they contain nonionic surfactant(s) in amounts of 1 to 10 wt.%, preferably 2 to 8 wt.% and in particular 3 to 6 wt.%, are preferred according to the invention.
  • 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 in the 2-position, aliphatic radical having 8 to 22, preferably 12 to 18 C atoms and G is the symbol which stands for a glycose unit having 5 or 6 C atoms, preferably glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
  • Non-ionic surfactants of the amine oxide type for example N-cocoalkyl-N,N-dimethylamine oxide and N-tallowalkyl-N,N-dihydroxyethylamine oxide, and fatty acid alkanolamides may also be suitable.
  • the amount of these non-ionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of that.
  • nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain.
  • washing or cleaning agents in particular cleaning agents for machine dishwashing, particularly preferably contain nonionic surfactants from the group of alkoxylated alcohols.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or can contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates with linear radicals from alcohols of native origin with 12 to 18 carbon atoms e.g. from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 moles of EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohol with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 alcohol with 3 EO and C 12-18 alcohol with 5 EO.
  • the stated degrees of ethoxylation represent statistical averages which can correspond to a whole or fractional number for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • ethoxylated nonionic surfactants obtained from C 6-20 monohydroxyalkanols or C 6-20 alkylphenols or C 16-20 fatty alcohols and more than 12 moles, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol.
  • a particularly preferred nonionic surfactant is obtained from a straight-chain fatty alcohol with 16 to 20 carbon atoms (C 16-20 alcohol), preferably a C 18 alcohol and at least 12 moles, preferably at least 15 moles and in particular at least 20 moles of ethylene oxide.
  • C 16-20 alcohol straight-chain fatty alcohol with 16 to 20 carbon atoms
  • C 18 alcohol preferably a C 18 alcohol and at least 12 moles, preferably at least 15 moles and in particular at least 20 moles of ethylene oxide.
  • the so-called “narrow range ethoxylates” are particularly preferred.
  • Combinations of one or more tallow fatty alcohols with 20 to 30 EO and silicone defoamers are also particularly preferred.
  • nonionic surfactants which have a melting point above room temperature.
  • Suitable nonionic surfactants that have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants that can be solid or highly viscous at room temperature. If nonionic surfactants that are highly viscous at room temperature are used, it is preferred that they have a viscosity above 20 Pa ⁇ s, preferably above 35 Pa ⁇ s and in particular above 40 Pa ⁇ s. Nonionic surfactants, which have a waxy consistency at room temperature, are also preferred depending on their intended use.
  • Nonionic surfactants from the group of alkoxylated alcohols particularly preferably from the group of mixed alkoxylated alcohols and in particular from the group of EO-AO-EO nonionic surfactants, are also used with particular preference.
  • the nonionic surfactant which is solid at room temperature, preferably has propylene oxide units in the molecule.
  • such PO units make up to 25% by weight, particularly preferably up to 20% by weight and in particular up to 15% by weight of the total molar mass of the nonionic surfactant.
  • Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols, which additionally have polyoxyethylene-polyoxypropylene block copolymer units.
  • the alcohol or alkylphenol portion of such nonionic surfactant molecules preferably makes up more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70% by weight of the total molar mass of such nonionic surfactants.
  • Preferred agents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule make up to 25% by weight, preferably up to 20% by weight and in particular up to 15% by weight of the total molar mass of the nonionic surfactant.
  • Surfactants that are preferably used come from the group of alkoxylated nonionic surfactants, in particular 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 also characterized by good foam control.
  • Nonionic surfactants with melting points above room temperature contain 40 to 70% of a polyoxypropylene/polyoxyethylene/polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.
  • nonionic surfactants in the context of the present invention are low-foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units.
  • surfactants with EO-AO-EO-AO blocks are preferred, with one to ten EO or AO groups being bonded to one another before a block of the other groups follows.
  • the preferred nonionic surfactants of the above formula can be prepared by known methods from the corresponding alcohols R 1 -OH and ethylene or alkylene oxide.
  • the radical R 1 in the above formula can vary depending on the origin of the alcohol. If native sources are used, the radical R 1 has an even number of carbon atoms and is generally unbranched, with linear radicals from alcohols of native origin with 12 to 18 carbon atoms, e.g. from coconut, palm, tallow or oleyl alcohol, being preferred.
  • Alcohols accessible from synthetic sources are, for example, Guerbet alcohols or radicals methyl-branched in the 2-position or linear and methyl-branched radicals in a mixture, as are usually present in oxo alcohol radicals.
  • nonionic surfactants are preferred in which R 1 in the above formula represents an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 carbon atoms.
  • butylene oxide is particularly suitable as an alkylene oxide unit which is present in the preferred nonionic surfactants in alternation with the ethylene oxide unit.
  • R 2 and R 3 are independently selected from -CH 2 CH 2 -CH 3 and -CH(CH 3 ) 2 are also suitable.
  • nonionic surfactants which have a C 9-15 alkyl radical with 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 are particularly preferred.
  • These surfactants have the required low viscosity in aqueous solution and can be used with particular preference according to the invention.
  • R 1 -CH(OH)CH 2 O-(AO) w -(A'O) x -(A"O) y -(A"'O) z -R 2 in which R 1 and R 2 independently of one another represent a straight-chain or branched, saturated or mono- or polyunsaturated C 2-40 alkyl or alkenyl radical;
  • A, A', A" and A'" independently of one another represent a radical from the group -CH 2 CH 2 , -CH 2 CH 2 -CH 2 , -CH 2 -CH(CH 3 ), -CH 2 -CH 2 -CH 2 -CH 2 , -CH 2 -CH(CH 3 )-CH 2 -, -CH 2 -CH(CH 2 -CH 3 ); and
  • w, x, y and z represent values between 0.5 and 90, where x, y and/or z can also be 0 are preferred according to the invention.
  • Particularly preferred surfactants are those 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 having 4 to 18 carbon atoms or mixtures thereof, R 2 is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is between 0.5 and 1.5 and y is at least 15.
  • Particularly preferred are also those end-capped poly(oxyalkylated) nonionic surfactants of the formula R 1 O[CH 2 CH z O] x [CH 2 CH(R 3 )O] y CH 2 CH(OH)R 2 , in which R 1 and R 2 independently of one another represent a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R 3 is independently selected from -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , -CH(CH 3 ) 2 , but preferably represents -CH 3 , and x and y independently of one another represent values between 1 and 32, with nonionic surfactants with R 3 -CH 3 and values for x from 15 to 32 and y from 0.5 to 1.5 being very particularly preferred.
  • nonionic surfactants which can preferably be used are the end-capped poly(oxyalkylated) nonionic surfactants of the formula R 1 O[CH 2 CH(R 3 )O] x [CH 2 ] k CH(OH)[CH 2 ] j OR 2 , in which R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 3 is H or a methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5.
  • each R 3 in the above formula R 1 O[CH 2 CH(R 3 )O] x [CH 2 ] k CH(OH)[CH 2 ] j OR 2 can be different.
  • R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 C atoms being particularly preferred.
  • R 3 H, -CH 3 or -CH 2 CH 3 are particularly preferred.
  • Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
  • each R 3 in the above formula can be different if x ⁇ 2.
  • the value 3 for x has been chosen here as an example and can certainly be larger, whereby the range of variation increases with increasing x values and includes, for example, a large number of (EO) groups combined with a small number of (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 have 9 to 14 C atoms, R 3 stands for H and x assumes values from 6 to 15.
  • the stated C-chain lengths and degrees of ethoxylation or alkoxylation of the aforementioned nonionic surfactants represent statistical averages, which can be a whole or a fractional number for a specific product. Due to the manufacturing processes, commercial products of the formulas mentioned usually do not consist of an individual representative, but of mixtures, which can result in averages and, consequently, fractional numbers for both the C-chain lengths and the degrees of ethoxylation or alkoxylation.
  • non-ionic surfactants can be used not only as individual substances, but also as surfactant mixtures of two, three, four or more surfactants.
  • Surfactant mixtures do not refer to mixtures of non-ionic surfactants that as a whole fall under one of the general formulas mentioned above, but rather to mixtures that contain two, three, four or more non-ionic surfactants that can be described by different ones of the general formulas mentioned above.
  • Some example recipes for such preferred phosphate-free automatic dishwashing detergents can be found in the table below: ingredient Formulation 5 [wt.%] Formulation 6 [wt.%] Formulation7 [wt.%] Formulation 8 [wt.%] Citrate 5 to 60 10 to 55 15 to 50 15 to 50 Sodium percarbonate 1 to 20 2 to 15 4 to 10 4 to 10 Bleach catalyst 0.01 to 3 0.02 to 2 0.02 to 2 .
  • Non-ionic surfactant 1 to 10 1 to 10 2 to 8 3 to 6 Copolymer 1 0.1 to 30 0.5 to 25 1.0 to 20 1.0 to 20 MGDA 0.5 to 20 0.5 to 20 0.5 to 10 0.5 to 8 Misc Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 1 copolymer containing i) Monomers containing sulfonic acid groups ii) Monomers of the general formula R 1 (R 2 )C C(R 3 )-XR 4 , in which R 1 to R 3 independently of one another represent -H, -CH 3 or - C 2 H 5 , X represents an optionally present spacer group selected from -CH 2 -, -C(O)O- and -C(O)-NH-, and R 4 represents a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms,
  • anionic surfactants are used as a component of automatic dishwashing detergents, their content, based on the total weight of the detergent, is preferably less than 4% by weight, preferably less than 2% by weight and very particularly preferably less than 1% by weight. Automatic dishwashing detergents which do not contain anionic surfactants are particularly preferred.
  • Cationic and/or amphoteric surfactants can also be used instead of the surfactants mentioned or in combination with them.
  • Automatic dishwashing detergents in which the weight proportion of methylglycinediacetic acid b) is 0.5 to 20 wt.%, preferably 0.5 to 10 wt.% and in particular 0.5 to 8 wt.%, also have particularly good cleaning, rinsing and deposit removal results and are preferred according to the invention for this reason.
  • terpolymers particularly preferably contain carboxyl group-containing monomers.
  • preferred automatic dishwashing detergents contain other ingredients, preferably active ingredients from the group of polymers, enzymes, corrosion inhibitors, fragrances or dyes.
  • the group of washing or cleaning-active polymers includes, for example, rinse aid polymers and/or polymers that act as softeners.
  • rinse aid polymers for example, rinse aid polymers and/or polymers that act as softeners.
  • cationic, anionic and amphoteric polymers can be used in washing or cleaning agents in addition to non-ionic polymers.
  • “Cationic polymers” in the sense of the present invention are polymers which carry a positive charge in the polymer molecule. This can be achieved, for example, by (alkyl) ammonium groups or other positively charged groups present in the polymer chain.
  • Particularly preferred cationic polymers come from the groups of quaternized cellulose derivatives, polysiloxanes with quaternary groups, cationic guar derivatives, polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate, vinylpyrrolidone-methoimidazolinium chloride copolymers, quaternized polyvinyl alcohols or the polymers specified under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.
  • Amphoteric polymers in the sense of the present invention have, in addition to a positively charged group in the polymer chain, also negatively charged groups or monomer units. These groups can be, for example, carboxylic acids, sulfonic acids or phosphonic acids.
  • Particularly preferred cationic or amphoteric polymers in the context of the present application contain as monomer unit a compound of the general formula in which R 1 and R 4 independently of one another represent H or a linear or branched hydrocarbon radical having 1 to 6 carbon atoms; R 2 and R 3 independently of one another represent an alkyl, hydroxyalkyl or aminoalkyl group in which the alkyl radical is linear or branched and has between 1 and 6 carbon atoms, preferably a methyl group; x and y independently of one another represent integers between 1 and 3.
  • X represents a counterion, preferably a counterion from the group chloride, bromide, iodide, sulfate, hydrogen sulfate, methosulfate, lauryl sulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate), cumenesulfonate, xylenesulfonate, phosphate, citrate, formate, acetate or mixtures thereof.
  • Preferred radicals R 1 and R 4 in the above formula are selected from -CH 3 , -CH 2 -CH 3 , - CH 2 -CH 2 -CH 3 , -CH(CH 3 )-CH 3 , -CH 2 -OH, -CH 2 -CH 2 -OH, -CH(OH)-CH 3 , -CH 2 -CH 2 -OH, -CH 2 -CH(OH)-Ch 3 , -CH(OH)-CH 2 -CH 3 , and -(CH 2 CH 2 -O) n H.
  • R 1 HC CR 2 -C(O)-NH-(CH 2 )-N + R 3 R 4 R 5 X - in which R 1 , R 2 , R 3 , R 4 and R 5 independently of one another represent a linear or branched, saturated or unsaturated alkyl or hydroxyalkyl radical having 1 to 6 carbon atoms, preferably a linear or branched alkyl radical selected from -CH 3 , -CH 2 -CH 3 , -CH 2 -CH 2 -CH 3 , -CH(CH 3 )CH 3 , -CH 2 -OH, -CH 2 -CH 2 -OH, -CH(OH)-CH 3 , -CH 2 -CH 2 -CH 2 -OH, -CH 2 -CH(OH)-CH 3 , -CH(OH)-CH 3 , -CH(OH)-CH 2 -CH 3 , and -(CH 2 CH 2
  • amphoteric polymers mentioned above have not only cationic groups, but also anionic groups or monomer units.
  • anionic monomer units originate, for example, from the group of linear or branched, saturated or unsaturated carboxylates, linear or branched, saturated or unsaturated phosphonates, linear or branched, saturated or unsaturated sulfates or linear or branched, saturated or unsaturated sulfonates.
  • Preferred monomer units are acrylic acid, (meth)acrylic acid, (dimethyl)acrylic acid, (ethyl)acrylic acid, cyanoacrylic acid, vinylacetic acid, allylacetic acid, crotonic acid, maleic acid, fumaric acid, cinnamic acid and their derivatives, allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, or allylphosphonic acids.
  • Preferred amphoteric polymers that can be used come from the group of alkylacrylamide/acrylic acid copolymers, alkylacrylamide/methacrylic acid copolymers, alkylacrylamide/methylmethacrylic acid copolymers, alkylacrylamide/acrylic acid/alkylaminoalkyl(meth)acrylic acid copolymers, alkylacrylamide/methacrylic acid/alkylaminoalkyl(meth)acrylic acid copolymers, alkylacrylamide/methylmethacrylic acid/alkylaminoalkyl(meth)acrylic acid copolymers, alkylacrylamide/alkylmethacrylate/alkylaminoethylmethacrylate/alkylmethacrylate copolymers and copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally other ionic or nonionic monomers.
  • Preferred zwitterionic polymers 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. Also preferred are amphoteric polymers which, in addition to one or more anionic monomers, comprise methacrylamidoalkyltrialkylammonium chloride and dimethyl(diallyl)ammonium chloride as cationic monomers.
  • amphoteric polymers come from the group of methacrylamidoalkyltrialkylammonium chloride/dimethyl(diallyl)ammonium chloride/acrylic acid copolymers, methacrylamidoalkyltrialkylammonium chloride/dimethyl(diallyl)ammonium chloride/methacrylic acid copolymers and methacrylamidoalkyltrialkylammonium chloride/dimethyl(diallyl)ammonium chloride/alkyl(meth)acrylic acid copolymers and their alkali and ammonium salts.
  • amphoteric polymers from the group of methacrylamidopropyltrimethylammonium chloride/dimethyl(diallyl)ammonium chloride/acrylic acid copolymers, methacrylamidopropyltrimethylammonium chloride/dimethyl(diallyl)ammonium chloride/acrylic acid copolymers and methacrylamidopropyltrimethylammonium chloride/dimethyl(diallyl)ammonium chloride/alkyl(meth)acrylic acid copolymers and their alkali and ammonium salts.
  • Detergents or cleaning agents preferably contain the aforementioned cationic and/or amphoteric polymers in amounts of between 0.01 and 10% by weight, based in each case on the total weight of the detergent or cleaning agent.
  • Enzymes can be used to increase the washing or cleaning performance of washing or cleaning agents. These include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are in principle of natural origin; based on the natural molecules, improved variants are available for use in washing or cleaning agents, which are therefore preferred. Washing or cleaning agents preferably contain enzymes in total quantities of 1 x 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.
  • subtilisins those of the subtilisin type are preferred.
  • these are the subtilisins BPN' and Carlsberg and their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus , subtilisin DY and the enzymes thermitase, proteinase K and the proteases TW3 and TW7, which are classified as subtilases but no longer as subtilisins in the narrower sense.
  • amylases examples include the ⁇ -amylases from Bacillus licheniformis , from B. amyloliquefaciens , from B. stearothermophilus , from Aspergillus niger and A. oryzae , as well as the further developments of the aforementioned amylases that have been improved for use in washing and cleaning agents. Furthermore, the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948) are particularly suitable for this purpose.
  • Lipases or cutinases can also be used according to the invention, in particular because of their triglyceride-cleaving activities, but also to produce peracids from suitable precursors in situ .
  • these include, for example, the lipases originally obtainable from Humicola lanuginosa ( Thermomyces lanuginosus ) or further developed lipases, in particular those with the amino acid exchange D96L.
  • the cutinases that were originally isolated from Fusarium solani pisi and Humicola insolens can be used.
  • Lipases or cutinases whose starting enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii can also be used.
  • oxidoreductases for example oxidases, oxygenases, catalases, peroxidases such as halo-, chloro-, bromo-, lignin-, glucose- or manganese-peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases)
  • organic compounds, particularly aromatic ones, which interact with the enzymes are also added in order to increase the activity of the oxidoreductases in question (enhancers) or to ensure the flow of electrons in the event of very different redox potentials between the oxidizing enzymes and the soiling (mediators).
  • the enzymes can be used in any form established according to the state of the art. These include, for example, solid preparations obtained by granulation, extrusion or lyophilization or, in particular in the case of liquid or gel-like agents, solutions of the enzymes, advantageously as concentrated as possible, with little water and/or mixed with stabilizers.
  • the enzymes can be encapsulated for both the solid and liquid dosage forms, 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 if in a solidified gel or in those of the core-shell type in which an enzyme-containing core is covered with a water, air and/or chemical-impermeable protective layer.
  • additional Active ingredients such as stabilizers, emulsifiers, pigments, bleaching agents or dyes, are applied.
  • Such capsules are applied using methods known per se, for example by shaking or rolling granulation or in fluid bed processes.
  • Such granules for example by applying polymeric film formers, are advantageously low in dust and are stable in storage due to the coating.
  • a protein and/or enzyme can be protected, particularly during storage, against damage such as inactivation, denaturation or decomposition, for example due to physical influences, oxidation or proteolytic cleavage.
  • damage such as inactivation, denaturation or decomposition, for example due to physical influences, oxidation or proteolytic cleavage.
  • inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases. Washing or cleaning agents can contain stabilizers for this purpose; the provision of such agents represents a preferred embodiment of the present invention.
  • one or more enzymes and/or enzyme preparations are used in amounts of from 0.1 to 5% by weight, preferably from 0.2 to 5% by weight and in particular from 0.4 to 5% by weight, in each case based on the total enzyme-containing agent.
  • Glass corrosion inhibitors prevent the appearance of clouding, streaks and scratches, as well as the iridescence of the glass surface of machine-cleaned glasses.
  • Preferred glass corrosion inhibitors come from the group of magnesium and zinc salts and magnesium and zinc complexes.
  • the spectrum of zinc salts preferred according to the invention ranges from salts that are sparingly or insoluble in water, i.e. have a solubility below 100 mg/l, preferably below 10 mg/l, in particular below 0.01 mg/l, to those salts that have a solubility in water above 100 mg/l, preferably above 500 mg/l, particularly preferably above 1 g/l and in particular above 5 g/l (all solubilities at 20°C water temperature).
  • the first group of zinc salts includes, for example, zinc citrate, zinc oleate and zinc stearate, while the group of soluble zinc salts includes, for example, zinc formate, zinc acetate, zinc lactate and zinc gluconate.
  • At least one zinc salt of an organic carboxylic acid as a glass corrosion inhibitor, particularly preferably a zinc salt from the group zinc stearate, zinc oleate, zinc gluconate, zinc acetate, zinc lactate and zinc citrate.
  • Zinc ricinoleate, zinc abietate and zinc oxalate are also preferred.
  • the content of zinc salt in washing or cleaning agents is preferably between 0.1 and 5% by weight, preferably between 0.2 and 4% by weight and in particular between 0.4 and 3% by weight, or the content of zinc in oxidized form (calculated as Zn 2+ ) is between 0.01 and 1% by weight, preferably between 0.02 and 0.5% by weight and in particular between 0.04 and 0.5% by weight, in each case based on the total weight of the glass corrosion inhibitor-containing agent.
  • Corrosion inhibitors serve to protect the items being washed or the machine, with silver protection agents being particularly important in the field of machine dishwashing.
  • the known substances of the prior art can be used.
  • silver protection agents selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes can be used. Benzotriazole and/or alkylaminotriazole are particularly preferred.
  • 3-amino-5-alkyl-1,2,4-triazoles or their physiologically acceptable salts preference is given to using 3-amino-5-alkyl-1,2,4-triazoles or their physiologically acceptable salts, with these substances being used with particular preference in a concentration of 0.001 to 10% by weight, preferably 0.0025 to 2% by weight, particularly preferably 0.01 to 0.04% by weight.
  • disintegration aids so-called tablet disintegrants
  • Disintegration aids are preferably 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 the disintegration aid.
  • Cellulose-based disintegrants are used as preferred disintegrants, so that preferred washing or cleaning agents contain such a cellulose-based disintegrant in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight.
  • the cellulose used as a disintegrant is preferably not used in finely divided form, but is converted into a coarser form, for example granulated or compacted, before being mixed into the premixes to be pressed.
  • the particle sizes of such disintegrants are usually above 200 ⁇ m, preferably at least 90% by weight between 300 and 1600 ⁇ m and in particular at least 90% by weight between 400 and 1200 ⁇ m.
  • Preferred disintegration aids preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, are contained in the disintegration agent-containing agents in amounts of 0.5 to 10 wt.%, preferably 3 to 7 wt.% and in particular 4 to 6 wt.%, in each case based on the total weight of the disintegration agent-containing agent.
  • gas-generating effervescent systems can also preferably be used as tablet disintegration aids.
  • the gas-generating effervescent system can consist of a single substance that releases a gas when it comes into contact with water.
  • magnesium peroxide is particularly worth mentioning, which releases oxygen when it comes into contact with water.
  • preferred effervescent systems consist of at least two components that react with one another to form gas, for example alkali metal carbonate and/or hydrogen carbonate and an acidifying agent that is suitable for releasing carbon dioxide from the alkali metal salts in aqueous solution.
  • Acidifying agents that release carbon dioxide from the alkali metal salts in aqueous solution can be, for example, boric acid, alkali metal hydrogen sulfates, alkali metal dihydrogen phosphates and other inorganic salts.
  • organic acidifying agents are preferably used, with citric acid being a particularly preferred acidifying agent.
  • Acidifying agents in the effervescent system are preferably from the group of organic di-, tri- and oligocarboxylic acids or mixtures.
  • fragrance compounds e.g. synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type
  • perfume oils or fragrances can be used as perfume oils or fragrances.
  • mixtures of different fragrances are preferably used which together produce an appealing scent.
  • perfume oils can also contain natural fragrance mixtures, such as those available from plant sources, e.g. pine, citrus, jasmine, patchouli, rose or ylang-ylang oil.
  • the fragrances can be processed directly, but it can also be advantageous to apply the fragrances to carriers that ensure a long-lasting fragrance through a slower release of the fragrance.
  • Cyclodextrins for example, have proven to be suitable carrier materials, although the cyclodextrin perfume complexes can also be coated with other auxiliary substances.
  • Preferred dyes the selection of which presents no difficulty to the person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the agents and to light, as well as no pronounced substantivity towards the substrates to be treated with the dye-containing agents, such as textiles, glass, ceramics or plastic tableware, in order not to stain them.
  • the automatic dishwashing detergents according to the invention can be packaged in solid or liquid form, but can also be available, for example, as a combination of solid and liquid forms.
  • Powders, granules, extrudates or compacts, especially tablets, are particularly suitable as solid forms.
  • the liquid forms based on water and/or organic solvents can be thickened and in the form of gels.
  • Agents according to the invention can be packaged as single-phase or multi-phase products.
  • automatic dishwashing agents with one, two, three or four phases are preferred.
  • Automatic dishwashing agents characterized by being in the form of a prefabricated dosing unit with two or more phases are particularly preferred.
  • the individual phases of multiphase agents can have the same or different states of aggregation.
  • Particularly preferred are automatic dishwashing agents which have at least two different solid phases and/or at least two liquid phases and/or at least one solid and at least one liquid phase.
  • Machine dishwashing detergents according to the invention are preferably pre-packaged into dosing units. These dosing units preferably contain the amount of washing or cleaning active substances required for one cleaning cycle. Preferred dosing units have a weight between 12 and 30 g, preferably between 14 and 26 g and in particular between 15 and 22 g.
  • the volume of the aforementioned dosing units and their spatial shape are particularly preferably selected so that the pre-assembled units can be dosed via the dosing chamber of a dishwasher.
  • the volume of the dosing unit is therefore preferably between 10 and 35 ml, preferably between 12 and 30 ml and in particular between 15 and 25 ml.
  • the automatic dishwashing detergents according to the invention in particular the prefabricated dosing units, particularly preferably have a water-soluble coating.
  • the present application further relates to a method for cleaning dishes in a dishwasher using automatic dishwashing agents according to the invention, wherein the automatic dishwashing agents are preferably dosed into the interior of a dishwasher while a dishwashing program is running, before the start of the main wash cycle or during the main wash cycle.
  • the agent according to the invention can be dosed or introduced into the interior of the dishwasher manually, but the agent is preferably dosed into the interior of the dishwasher using the dosing chamber of the dishwasher. During the cleaning process, preferably no additional water softener or rinse aid is dosed into the interior of the dishwasher.
  • agents according to the invention are distinguished from conventional automatic dishwashing agents by an improved rinse effect.
  • the use of an automatic dishwashing agent according to the invention as a rinse agent in automatic dishwashing is therefore a further subject matter of the present application.
  • the composition of the dishwashing detergents used can be found in the table below: raw material V1 V2 V3 E1 phosphate 33 -- -- -- Citrate -- 23 23 23 23 MGDA -- -- 8.0 8.0 Copolymer 1 12.0 12.0 -- 12.0 HEDP 2.0 2.0 2.0 2.0 soda 28.0 28.0 28.0 Sodium percarbonate 10.0 10.0 10.0 10.0 TAE 2.4 2.4 2.4 2.4 Protease/Amylase 4.0 4.0 4.0 4.0 4.0 Non-ionic surfactant 5.0 5.0 5.0 5.0 Misc Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 Add 100 1 Copolymer containing sulfonic acid groups

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Claims (10)

  1. Produit de lavage de la vaisselle en machine sans phosphate, contenant un adjuvant, un agent de blanchiment, un tensioactif non ionique, ainsi qu'en outre
    a) Copolymère contenant
    i) des monomères contenant des groupes acide sulfonique
    ii) des monomères de formule générale R1(R2)C=C(R3)-X-R4, dans laquelle R1 à R3 représentent indépendamment les uns des autres -H, -CH3 ou -C2H5, X représente un groupe espaceur éventuellement présent, qui est choisi parmi -CH2-, C(O)O- et C(O)-NH-, et R4 représente un radical alkyle saturé à chaîne droite ou ramifiée ayant de 2 à 22 atomes de carbone ou un radical insaturé, de préférence aromatique, ayant de 6 à 22 atomes de carbone,
    b) l'acide méthylglycine diacétique.
  2. Détergent pour lave-vaisselle automatique selon la revendication 1, caractérisé en ce que la proportion en poids du copolymère a) est de 4 à 18 % en poids, de préférence de 6 à 15 et en particulier de 6 à 12 % en poids.
  3. Détergent pour lave-vaisselle automatique selon l'une quelconque des revendications précédentes, caractérisé en ce que la proportion en poids d'acide méthylglycine diacétique b) est de 0,5 à 20 % en poids, de préférence de 0,5 à 10 % en poids et en particulier de 0,5 à 8 % en poids.
  4. Détergent pour lave-vaisselle automatique selon l'une quelconque des revendications précédentes, caractérisé en ce qu'il contient de 5 à 60 % en poids, de préférence de 10 à 50 % en poids et en particulier de 15 à 40 % en poids de citrate.
  5. Détergent pour lave-vaisselle automatique selon l'une quelconque des revendications précédentes, caractérisé en ce qu'il contient de 1 à 20 % en poids, de préférence de 2 à 15 % en poids et en particulier de 4 à 12 % en poids de percarbonate de sodium.
  6. Détergent pour lave-vaisselle automatique selon l'une quelconque des revendications précédentes, caractérisé en ce qu'il contient le tensioactif non ionique dans des quantités de 1 à 10 % en poids, de préférence de 2 à 8 % en poids et en particulier de 3 à 6 % en poids.
  7. Détergent pour lave-vaisselle automatique selon l'une quelconque des revendications précédentes, contenant
    a) 6 à 15 % en poids de copolymère comprenant
    i) des monomères contenant des groupes acide sulfonique
    ii) des monomères de formule générale R1(R2)C=C(R3)-X-R4, dans laquelle R1 à R3 représentent indépendamment -H, -CH3 ou -C2H5, X représente un groupe espaceur éventuellement présent, qui est choisi parmi -CH2-, C(O)O- et C(O)-NH-, et R4 représente un radical alkyle saturé à chaîne droite ou ramifiée ayant de 2 à 22 atomes de carbone ou un radical insaturé, de préférence aromatique, ayant de 6 à 22 atomes de carbone.
    b) 0,5 à 10 % en poids d'acide méthylglycinediacétique
    c) 10 à 50 % en poids de citrate
    d) 2 à 15 % en poids de percarbonate de sodium
    e) 2 à 8 % en poids d'agent de surface non ionique
  8. Détergent pour lave-vaisselle automatique selon l'une quelconque des revendications précédentes, contenant
    a) 6 à 15 % en poids de copolymère comprenant
    i) des monomères contenant des groupes acide sulfonique
    ii) des monomères de formule générale R1(R2)C=C(R3)-X-R4, dans laquelle R1 à R3 représentent indépendamment -H, -CH3 ou -C2H5, X représente un groupe espaceur éventuellement présent, qui est choisi parmi -CH2-, C(O)O- et C(O)-NH-, et R4 représente un radical alkyle saturé à chaîne droite ou ramifiée ayant de 2 à 22 atomes de carbone ou un radical insaturé, de préférence aromatique, ayant de 6 à 22 atomes de carbone.
    b) 0,5 à 10 % en poids d'acide méthylglycinediacétique
    c) 10 à 50 % en poids de citrate
    d) 2 à 15 % en poids de percarbonate de sodium
    e) 2 à 8 % en poids d'agent de surface non ionique
    f) 1,0 à 6 % en poids d'enzyme.
  9. Procédé de lavage de la vaisselle dans un lave-vaisselle, utilisant des produits de lavage de la vaisselle en machine selon l'une quelconque des revendications 1 à 8.
  10. Procédé selon la revendication 9, caractérisé en ce que, au cours du procédé de nettoyage, aucun adoucisseur d'eau supplémentaire ni aucun produit de rinçage supplémentaire n'est dosé dans l'espace intérieur du lave-vaisselle.
EP07847823.7A 2007-02-06 2007-12-05 Composition detergente Active EP2118255B2 (fr)

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PCT/EP2007/063326 WO2008095560A1 (fr) 2007-02-06 2007-12-05 Détergents

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PL2118255T3 (pl) 2014-07-31
DE102007006628A1 (de) 2008-08-07
EP2118255A1 (fr) 2009-11-18
EP2118255B1 (fr) 2014-01-22
US9752100B2 (en) 2017-09-05
PL2118255T5 (pl) 2024-07-29
ES2448515T3 (es) 2014-03-14
WO2008095560A1 (fr) 2008-08-14

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