EP2723844B1 - Détergents pour vaisselle avec protection de décor améliorée - Google Patents

Détergents pour vaisselle avec protection de décor améliorée Download PDF

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Publication number
EP2723844B1
EP2723844B1 EP12724981.1A EP12724981A EP2723844B1 EP 2723844 B1 EP2723844 B1 EP 2723844B1 EP 12724981 A EP12724981 A EP 12724981A EP 2723844 B1 EP2723844 B1 EP 2723844B1
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Prior art keywords
zinc
weight
automatic dishwashing
dishwashing detergent
acid
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EP12724981.1A
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German (de)
English (en)
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EP2723844A1 (fr
Inventor
Thomas Eiting
Nina Mussmann
Thorsten Bastigkeit
Konstantin Benda
Arnd Kessler
Clarissa MAISEY
Dominique SCHUL
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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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • 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
    • C11D3/168—Organometallic compounds or orgometallic complexes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3776—Heterocyclic compounds, e.g. lactam

Definitions

  • the present application describes machine dishwashing detergents and machine dishwashing methods using these dishwashing agents and the use of these dishwashing agents to reduce glass and porcelain corrosion and / or to improve the decor protection.
  • Dishwashing detergents are available to consumers in a variety of forms. In addition to the traditional liquid hand dishwashing detergents, machine dishwashing detergents in particular have become very important with the spread of household dishwashing machines. These machine dishwashing agents are typically offered to the consumer in solid form, for example as powder or as tablets, but increasingly also in liquid form.
  • One of the main goals of the manufacturers of machine cleaning agents is to improve the cleaning and rinsing performance of these agents, with a recent focus on cleaning and rinsing performance in low-temperature cleaning cycles or in cleaning cycles with reduced water consumption. In addition to the cleaning and rinsing performance of these agents, however, it is also desirable that the agents advantageously perform other functions.
  • Dishwashing problems can occur with glasses and porcelain, for example.
  • the glasses and the porcelain corrode over time after frequent dishwashing and in particular the decor on the glasses and the porcelain is worn away over time.
  • the addition of special corrosion inhibitors, such as zinc salts, can reduce glass and porcelain corrosion and remove the decor.
  • the international patent application WO 07/049250 A1 is concerned with improved dirt removal using automatic dishwashing detergents.
  • the international patent application WO 03/104370 A1 deals with glass corrosion protection through zinc salts and crystalline layered silicates.
  • the German patent application DE 10153555 A1 deals with dishwasher detergents that contain magnesium and / or zinc salts of at least one organic acid to protect against glass corrosion.
  • the German patent application DE 102008020275 A1 deals with zinc-containing cogranulate in automatic dishwashing detergents.
  • the Improved glass, porcelain and / or decorative protective properties should preferably also be achieved with low-temperature cleaning cycles, i.e. in cleaning processes with rinsing liquor temperatures of 50 ° C. or below and / or in short-lasting cleaning processes, in particular in cleaning processes with a duration of less than 60 minutes can.
  • the improved glass, porcelain and / or decorative protective properties should also preferably be present even with high alkalinity and / or in the presence of strong complexing agents.
  • the object of the invention was achieved by a dishwashing detergent which, in addition to a zinc salt, additionally contains a polymer which comprises N-containing heterocycles.
  • the polymer is a polyvinylpyrrolidone, which is in particulate form.
  • a first subject of the present invention are therefore dishwasher detergents, characterized in that they contain at least one zinc salt and at least one polymer which comprises N-containing heterocycles, the polymer with N-containing heterocycles being a polyvinylpyrrolidone, the polyvinylpyrrolidone is in particulate form, the polyvinylpyrrolidone particles preferably having an average particle diameter of 100 to 150 ⁇ m.
  • the polyvinyl pyrrolidone can be branched or linear. In a preferred embodiment, the polyvinylpyrrolidone is in a branched and crosslinked form.
  • the polyvinylpyrrolidone particles preferably have an average particle diameter of 100 to 150 ⁇ m.
  • Another object of the present invention is also a machine dishwashing process using the dishwashing agents according to the invention, in particular for protecting the treated glass and porcelain goods, especially for reducing glass and porcelain corrosion and / or for improving the decor protection.
  • the dishwashing process is preferably carried out at a liquor temperature below 60 ° C., preferably below 50 ° C.
  • the dishwashing process takes a maximum of 90 minutes, in particular a maximum of 75 minutes, particularly preferably a maximum of 60 minutes.
  • the dishwashing process takes a maximum of 50, 40 or 30 minutes.
  • Another object of the present invention is also the use of a combination of a zinc salt and a polymer which contains N-containing heterocycles to effect improved glass, porcelain and / or decor protection or to reduce glass and porcelain corrosion and / or to reduce the removal of decor or to reduce the fading of the decor, the polymer being a polyvinylpyrrolidone.
  • a dishwashing agent according to the invention is preferably used as a combination of zinc salt and polymer containing N-containing heterocycles, the polymer being a polyvinylpyrrolidone.
  • the decor is preferably on a glass or porcelain surface.
  • machine dishwashing detergents are compositions which can be used for cleaning soiled dishes in an automatic dishwashing process.
  • the machine dishwashing detergents according to the invention thus differ, for example, from the machine rinse aids which are always used in combination with machine dishwashing agents and do not have their own cleaning action.
  • the automatic dishwashing detergents according to the invention can be in solid or liquid form. In a preferred embodiment, they are in powder, granulated or compressed form.
  • the automatic dishwashing detergents according to the invention are in the form of moldings, preferably as compact, in particular as tablets.
  • they can also be in combination with other offer forms, in particular in combination with solid offer forms such as powders, granules or extrudates or in combination with liquid offer forms based on water and / or organic solvents.
  • Agents according to the invention can be packaged as single-phase or multi-phase products.
  • Machine dishwashing detergents with one, two, three or four phases are particularly preferred.
  • Machine dishwashing detergents, characterized in that they are in the form of a prefabricated metering unit with two or more phases, are particularly preferred.
  • Particularly preferred are two-phase or multi-phase tablets, for example two-layer tablets, in particular two-layer tablets with a trough and a molded body located in the trough.
  • Automatic dishwashing agents according to the invention are preferably prefabricated into dosing units. These metering units preferably comprise the amount of washing or cleaning-active substances necessary for a 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 selected with particular preference such 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 pH of a 10% solution of an automatic dishwashing agent according to the invention in distilled water is preferably between 7 and 13, particularly preferably between 8 and 12, in particular between 9 and 11.
  • the automatic dishwashing agents according to the invention in particular the prefabricated metering units, particularly preferably have a water-soluble coating.
  • Dishwashing detergents according to the invention contain at least one polymer which comprises N-containing heterocycles, the polymer being a polyvinylpyrrolidone.
  • Dishwashing agents according to the invention in particular moldings according to the invention, contain polyvinylpyrrolidone in the form of polyvinylpyrrolidone particles.
  • Polyvinylpyrrolidone particles have the additional advantage that they facilitate the disintegration of the shaped bodies and, in this respect, also serve as disintegration aids or tablet disintegrants.
  • the function of the PVP particles is therefore not limited to improved glass, porcelain and decor protection.
  • polyvinylpyrrolidone particles with an average particle diameter of 100 to 150 ⁇ m, in particular with an average particle diameter of 110 to 130 ⁇ m.
  • the term “average particle diameter” or “average diameter” is understood to mean the volume-average D 50 particle diameter, which can be determined by customary methods.
  • the volume-average D 50 particle diameter is the point in the particle size distribution at which 50% by volume of the particles have a smaller diameter and 50% by volume of the particles have a larger diameter.
  • the average particle diameters can be determined in particular with the aid of dynamic light scattering, which are usually carried out on dilute suspensions which contain, for example, 0.01 to 1% by weight of particles.
  • the PVP particles used not only have an average particle diameter of 100 to 150 ⁇ m, in particular 110 to 130 ⁇ m, but moreover the particle size of the particles used is preferably completely within the stated intervals. This is ensured by using grain size fractions with the specified particle sizes, which were obtained by a sieving process. According to the invention, it was also surprisingly found that granules which are used according to the invention for the production of the moldings and contain PVP particles can be pressed particularly well.
  • compactates with a hardness in the range from 150 to 250 N, in particular in the range from 200 to 230 N can be obtained, which are also particularly good Show trickle behavior.
  • the granules can thus preferably be pressed with a relatively low pressing force to give compacts with a relatively high hardness, which moreover preferably have very good flow behavior.
  • a lower pressing force must preferably be used to produce compacts of lower hardness than for the production of conventional compacts.
  • Another object which is particularly preferred according to the invention is therefore also a shaped body, in particular a compact, in particular a cleaning tablet, which comprises a mixture of polyvinylpyrrolidone particles with an average particle diameter of 100 to 150 ⁇ m, in particular 110 to 130 ⁇ m, and at least one Contains zinc salt and which preferably has a particularly good flow behavior.
  • the polyvinylpyrrolidone in compositions according to the invention is preferably in an amount of 0.1 to 5% by weight, particularly preferably in an amount of 0.2 to 3% by weight, especially in an amount of 0.3 to 1.8 % By weight.
  • disintegrants usually that they increase their volume when water enters, whereby on the one hand the intrinsic volume increases (swelling), but on the other hand a pressure can be generated by the release of gases, which disintegrates the tablet into smaller particles .
  • further or alternative disintegrants can also be present in dishwashing detergents according to the invention, for example carbonate / citric acid systems or carbonate in combination with other organic acids, synthetic polymers or natural polymers or modified natural substances such as cellulose and starch and their Derivatives and alginates or casein derivatives.
  • gas-developing shower systems can also be used as further or alternative disintegrants.
  • Preferred effervescent systems consist of at least two constituents which react with one another to form a gas, for example alkali metal carbonate and / or hydrogen carbonate and an acidifying agent which is suitable for releasing carbon dioxide from the alkali metal salts in aqueous solution.
  • An acidifying agent that releases carbon dioxide from the alkali salts in aqueous solution is, for example, citric acid.
  • the further disintegration aids are preferably used in amounts of 0.1 to 10% by weight, preferably 0.2 to 5% by weight and in particular 0.5 to 2% by weight, in each case based on the total weight of the Dishwashing detergent used.
  • the shaped body according to the invention contains no further disintegration aids apart from the PVP particles.
  • Dishwashing detergents according to the invention contain at least one zinc salt as a further constituent.
  • the zinc salt can be an inorganic or organic zinc salt.
  • the zinc salt to be used according to the invention preferably has 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 inorganic zinc salt is preferably selected from the group consisting of zinc bromide, zinc chloride, zinc iodide, zinc nitrate and zinc sulfate.
  • the organic zinc salt is preferably selected from the group consisting of zinc salts of monomeric or polymeric organic acids, in particular from the group of zinc acetate, zinc acetylacetonate, zinc benzoate, zinc formate, zinc lactate, zinc gluconate, zinc ricinoleate, zinc abietate, zinc valerate and zinc p-toluenesulfonate.
  • zinc acetate is used as the zinc salt.
  • the zinc salt in dishwashing detergents according to the invention is preferably in an amount of 0.01 to 3% by weight, particularly preferably in an amount of 0.05 to 2% by weight, in particular in an amount of 0.1 to 1% by weight. %, contain.
  • Preferred automatic dishwashing agents according to the invention contain at least one bleaching agent as a further constituent, oxygen bleaching agents being preferred.
  • oxygen bleaching agents being preferred.
  • sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid.
  • Bleaching agents from the group of organic bleaching agents can also be used.
  • Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide.
  • organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids.
  • Preferred automatic dishwashing agents according to the invention are characterized in that they contain an oxygen bleach, preferably sodium percarbonate, particularly preferably a coated sodium percarbonate.
  • the proportion by weight of the bleaching agent, based on the total weight of the washing or cleaning agent, is in preferred embodiments between 2 and 30% by weight, preferably between 4 and 20% by weight and in particular between 6 and 15% by weight.
  • Automatic dishwashing detergents according to the invention can furthermore contain bleach activators. Under perhydrolysis conditions, these compounds give aliphatic peroxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Multi-acylated alkylenediamines are preferred, with tetraacetylethylenediamine (TAED) having proven to be particularly suitable.
  • TAED tetraacetylethylenediamine
  • Automatic dishwashing agents characterized in that they contain a bleach activator from the group of acetylated amines, preferably tetraacetylenediamine (TAED), as the bleach activator, are preferred according to the invention.
  • TAED tetraacetylenediamine
  • the automatic dishwashing agents according to the invention preferably contain at least one bleaching catalyst.
  • bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can also be used as bleaching catalysts.
  • Complexes of manganese in oxidation state II, III, IV or V are used with particular preference, which preferably contain one or more macrocyclic ligand (s) with the donor functions N, NR, PR, O and / or S.
  • Ligands which have nitrogen donor functions are preferably used.
  • bleaching catalyst (s) in the agents according to the invention which contain 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN), 1,4,7-triazacyclononane (TACN) as macromolecular ligands ), 1,5,9-trimethyl-1,5,9-triazacyclododecane (Me-TACD), 2-methyl-1,4,7-trimethyl-1,4,7-triazacyclononane (Me / Me-TACN) and / or 2-methyl-1,4,7-triazacyclononane (Me / TACN ) contain.
  • Me-TACN 1,4,7-trimethyl-1,4,7-triazacyclononane
  • TACN 1,4,7-triazacyclononane
  • Automatic dishwashing detergents characterized in that they also contain a bleaching catalyst selected from the group of bleach-enhancing transition metal salts and transition metal complexes, preferably from the group of complexes of manganese with 1,4,7-trimethyl-1,4,7-triazacyclononane (Me 3 -TACN ) or 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (Me 4 -TACN) are preferred according to the invention, since in particular the cleaning result can be significantly improved by the aforementioned bleaching catalysts.
  • a bleaching catalyst selected from the group of bleach-enhancing transition metal salts and transition metal complexes, preferably from the group of complexes of manganese with 1,4,7-trimethyl-1,4,7-triazacyclononane (Me 3 -TACN ) or 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (Me 4 -TACN) are preferred according to the invention, since in particular the cleaning result can be significantly improved by
  • the aforementioned bleach-enhancing transition metal complexes are used in customary 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 catalyst-containing agents. In special cases, however, more bleaching catalyst can also be used.
  • Preferred automatic dishwashing agents according to the invention contain at least one anionic polymer as a further constituent.
  • Preferred anionic polymers are the copolymeric polycarboxylates and the copolymeric polysulfonates.
  • the weight fraction of the anionic polymer in the total weight of the automatic dishwashing detergent according to the invention is from 0.1 to 20% by weight, preferably from 0.5 to 18% by weight, particularly preferably from 1.0 to 15% by weight. % and in particular from 4 to 14% by weight.
  • Automatic dishwashing detergents characterized in that the copolymeric anionic polymer is selected from the group of the hydrophobically modified polycarboxylates and polysulfonates is a particularly preferred object, since the hydrophobic modification of the anionic copolymers improves the rinse aid and drying properties of these agents while at the same time reducing the formation of deposits can be achieved.
  • the copolymers can have two, three, four or more different monomer units.
  • preferred copolymeric polysulfonates contain 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, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylene malonic acid, sorbic acid, cinnamic acid or mixtures thereof.
  • unsaturated dicarboxylic acids can also be used.
  • copolymers of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid are particularly preferably used as copolymeric polycarboxylates.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.
  • Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3- Methacrylamido-2-hydroxy-propanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propen1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl sulfopropyl acrylate , Sulfomethacrylamide, sulfomethyl methacrylamide and mixtures of the acids mentioned or their water-soluble salts.
  • the sulfonic acid groups in the polymers can be wholly or partly in neutralized form, ie the acidic hydrogen atom of the sulfonic acid group in some or all of the sulfonic acid groups can be replaced by metal ions, preferably alkali metal ions and in particular by sodium ions.
  • metal ions preferably alkali metal ions and in particular by sodium ions.
  • the use of partially or fully neutralized copolymers containing sulfonic acid groups is preferred according to the invention.
  • the monomer distribution of the copolymers preferably used according to the invention is preferably 5 to 95% by weight in each case in copolymers which contain only monomers containing carboxylic acid groups and monomers containing sulfonic acid groups, particularly preferably the proportion of the monomer containing sulfonic acid groups is 50 to 90% by weight. % and the proportion of the carboxylic acid group-containing monomer 10 to 50 wt .-%, the monomers are preferably selected from the aforementioned.
  • the 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 intended use.
  • Preferred automatic dishwashing detergents are characterized in that the copolymers have molar masses from 2000 to 200,000 gmol -1 , preferably from 4000 to 25,000 gmol -1 and in particular from 5000 to 15,000 gmol -1 .
  • the copolymers in addition to the monomer containing carboxyl groups and monomer containing sulfonic acid groups, the copolymers further comprise at least one nonionic, preferably hydrophobic monomer.
  • 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 are -H, -CH 3 or -C 2 H 5 , are preferably used as nonionic monomers , X stands for an optionally available spacer group which is selected from -CH 2 -, -C (O) O- and -C (O) -NH-, and R 4 for a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or represents an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms.
  • nonionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 , 4-trimethylpentene-1, 2,4,4-trimethylpentene-2, 2,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethylhexene-1, 3,5-dimethylhexene-1,4 , 4-dimethylhexane-1, ethylcyclohexyne, 1-octene, ⁇ -olefins with 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C22
  • dishwashing detergents further comprise at least one nonionic surfactant of the general formula R 1 O (AlkO) x M (OAlk) y OR 2 , where R 1 and R 2 independently of one another are a branched or unbranched, saturated or unsaturated, optionally hydroxylated Alkyl radical having 4 to 22 carbon atoms; Alk represents a branched or unbranched alkyl radical having 2 to 4 carbon atoms; x and y independently represent values between 1 and 70; and M represents an alkyl radical from the group CH 2 , CHR 3 , CR 3 R 4 , CH 2 CHR 3 and CHR 3 CHR 4 , where R 3 and R 4 independently of one another represent a branched or unbranched, saturated or unsaturated alkyl radical with 1 are up to 18 carbon atoms.
  • R 1 and R 2 independently of one another are a branched or unbranched, saturated or unsaturated, optionally hydroxylated Alkyl radical having 4 to 22 carbon atom
  • R 1 -CH (OH) CH 2 -O (CH 2 CH 2 O) x CH 2 CHR (OCH 2 CH 2 ) y O-CH 2 CH (OH) -R 2 in are particularly preferred where R is a linear, saturated alkyl radical having 8 to 16 carbon atoms, preferably 10 to 14 carbon atoms and n and m independently of one another have values from 20 to 30.
  • Corresponding compounds can be obtained, for example, by reacting HO-CHR-CH 2 -OH alkyldiols with ethylene oxide, followed by a reaction with an alkyl epoxide to block the free OH functions to form a dihydroxy ether.
  • the weight fraction of the nonionic surfactant of the general formula R 1 O (AlkO) x M (OAlk) y OR 2 in the total weight of the automatic dishwashing detergent according to the invention is in a preferred embodiment between 0.05 and 10% by weight, preferably between 0.1 and 8% by weight, preferably between 0.5 and 5% by weight and in particular between 1 and 3% by weight.
  • Dishwashing agents according to the invention preferably further contain builders (e) and / or enzymes (e) to ensure their cleaning action.
  • automatic dishwashing agents according to the invention preferably contain one or more builders.
  • the weight fraction of the builders in the total weight of automatic dishwashing agents according to the invention is preferably 15 to 80% by weight and in particular 20 to 70% by weight.
  • the builders in particular include carbonates, phosphates, citrates, organic cobuilders and silicates.
  • alkali carbonate (s) particularly preferably sodium carbonate
  • phosphate is also preferred.
  • the alkali metal phosphates with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), are of the greatest importance in the detergent and cleaning agent industry.
  • Alkali metal phosphates is the summary name for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one uses metaphosphoric acids (HPO 3 ) n and orthophosphoric acid H 3 PO 4 in addition to higher molecular weight representatives can distinguish.
  • the phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and lime incrustations in tissues and also contribute to cleaning performance.
  • Phosphates which are particularly preferred according to the invention are pentasodium triphosphate, Na 5 P 3 O 10 (sodium tripolyphosphate) and the corresponding potassium salt pentapotassium triphosphate, K 5 P 3 O 10 (potassium tripolyphosphate).
  • the sodium potassium tripolyphosphates are also preferably used according to the invention.
  • phosphates are used as washing or cleaning-active substances in automatic dishwashing detergents in the context of the present application, they contain phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), in quantities from 5 to 60% by weight, preferably from 15 to 45% by weight and in particular from 20 to 40% by weight, in each case based on the weight of the dishwasher detergent.
  • phosphate preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate)
  • Organic cobuilders include, in particular, polycarboxylates / polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals, dextrins and organic cobuilders. These classes of substances are described below.
  • Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids being understood as meaning those carboxylic acids which carry more than one acid function.
  • these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as 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 of detergents or cleaning agents.
  • Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.
  • Automatic dishwashing agents contain citrate as one of their essential builders.
  • Automatic dishwashing detergents characterized in that they contain 2 to 40% by weight, preferably 5 to 30% by weight and in particular 7 to 20% by weight, of citrate are preferred according to the invention.
  • the citrates are preferably used in combination with carbonates and / or hydrogen carbonate.
  • Preferred machine dishwashing detergents are therefore characterized by a combination of builders consisting of phosphate and carbonate / hydrogen carbonate or of citrate and carbonate / hydrogen carbonate (cf. Tables 1a and 1b below).
  • phosphate and carbonate / hydrogen carbonate consisting of phosphate and carbonate / hydrogen carbonate or of citrate and carbonate / hydrogen carbonate (cf. Tables 1a and 1b below).
  • dishwashing agents are characterized in that the dishwashing agent contains at least two builders from the group of the phosphates, carbonates and citrates, the weight fraction of these builders, based on its total weight of the automatic dishwashing agent, preferably 5 to 80% by weight, preferably 15 is up to 75 wt .-% and in particular 30 to 70 wt .-%.
  • the combination of two or more builders from the group mentioned above has proven to be advantageous for the cleaning and rinsing performance of automatic dishwashing detergents according to the invention.
  • 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 weight of 500 to 70,000 g / mol.
  • Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates which have molar masses from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, can in turn be preferred from this group.
  • the amount of (homo) polymeric polycarboxylates in the automatic dishwashing detergent is preferably 0.5 to 20% by weight and in particular 3 to 10% by weight.
  • Automatic dishwashing agents according to the invention can contain 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, where are 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 with a modulus Na 2 O: SiO 2 of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, can also be used are preferably delayed release and have secondary washing properties.
  • the silicate content based on the total weight of the automatic dishwashing agent, is below 10 Limited by weight, preferably below 5% by weight and in particular below 2% by weight.
  • Particularly preferred automatic dishwashing agents according to the invention are silicate-free.
  • MGDA methylglycinediacetic acid
  • GLDA glutamic acid-N, N-diacetic acid
  • the agents according to the invention can contain alkali metal hydroxides.
  • These alkali carriers are preferably used in the cleaning agents only in small amounts, preferably in amounts below 10% by weight, preferably below 6% by weight, preferably below 5% by weight, particularly preferably between 0.1 and 5% by weight. and in particular between 0.5 and 5% by weight, in each case based on the total weight of the cleaning agent.
  • Alternative automatic dishwashing detergents are free from alkali metal hydroxides.
  • Agents according to the invention preferably also contain phosphonates. Hydroxyalkane and / or aminoalkane phosphonates are preferably used. Of the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance. Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. Phosphonates are present in the agents according to the invention preferably in amounts of 0.1 to 10% by weight, in particular in amounts of 0.5 to 8% by weight, in each case based on the total weight of the cleaning agent.
  • ETMP ethylenediaminetetramethylenephosphonate
  • DTPMP diethylenetriaminepentamethylenephosphonate
  • Phosphonates are present in the agents according to the invention preferably in amounts of 0.1 to 10% by weight, in particular in amounts of 0.5 to 8% by weight, in each case
  • Dishwashing agents preferably contain enzyme (s) as a further constituent.
  • enzyme include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably their mixtures.
  • these enzymes are of natural origin; Based on the natural molecules, improved variants are available for use in detergents or cleaning agents, which are accordingly preferred.
  • Detergents or cleaning agents preferably contain enzymes in total amounts of 1 ⁇ 10 -6 to 5% by weight, based on active protein. The protein concentration can be determined using known methods, for example the BCA method or the biuret method.
  • subtilisins those of the subtilisin type are preferred. Examples of this 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 can no longer be assigned to the subtilisins in the narrower sense.
  • amylases which can be used according to the invention are the ⁇ -amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae, and the further developments of the aforementioned amylases, which have been improved for use in detergents and cleaning agents. Furthermore, the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. to highlight agaradherens (DSM 9948).
  • Lipases or cutinases can also be used according to the invention, in particular because of their triglyceride-cleaving activities, but also to generate peracids in situ from suitable precursors.
  • suitable precursors include, for example, the lipases originally obtainable from Humicola lanuginosa ( Thermomyces lanuginosus ) or developed further, in particular those with the amino acid exchange D96L.
  • oxidoreductases for example oxidases, oxygenases, catalases, peroxidases, such as halo-, chloro-, bromo-, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases)
  • peroxidases such as halo-, chloro-, bromo-, lignin, glucose or manganese peroxidases, dioxygenases or laccases
  • organic, particularly preferably aromatic, compounds interacting with the enzymes are additionally added in order to increase the activity of the oxidoreductases in question (enhancers) or to ensure the flow of electrons (mediators) in the case of very different redox potentials between the oxidizing enzymes and the soiling.
  • a protein and / or enzyme can be protected against damage, such as inactivation, denaturation or decay, for example by physical influences, oxidation or proteolytic cleavage, especially during storage.
  • damage such as inactivation, denaturation or decay, for example by physical influences, oxidation or proteolytic cleavage, especially during storage.
  • the proteins and / or enzymes are obtained microbially, inhibition of proteolysis is particularly preferred, in particular if the agents also contain proteases.
  • Detergents or cleaning agents can contain stabilizers for this purpose; the provision of such agents is a preferred embodiment of the present invention.
  • Proteases and amylases that are active in washing or cleaning are generally not provided in the form of the pure protein but rather in the form of stabilized, storable and transportable preparations.
  • These prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, particularly in the case of liquid or gel form agents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or with stabilizers or other auxiliaries.
  • the enzymes can be encapsulated both for the solid and for the liquid administration form, for example by spray drying or extrusion of the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are enclosed as in a solidified gel or those of the core-shell type, in which an enzyme-containing core is coated with a protective layer impermeable to water, air and / or chemicals.
  • Additional active ingredients for example stabilizers, emulsifiers, pigments, bleaching agents or dyes, can additionally be applied in layers.
  • Capsules of this type are applied by methods known per se, for example by shaking or roll granulation or in fluid-bed processes. Such granules are advantageously low in dust, for example by applying polymeric film formers, and are stable on storage due to the coating.
  • the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations.
  • Protease and amylase preparations preferably used according to the invention contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, particularly preferably between 0.4 and 20% by weight and in particular between 0, 8 and 10% by weight of the enzyme protein.
  • automatic dishwashing agents which, based on their total weight, contain 0.1 to 12% by weight, preferably 0.2 to 10% by weight and in particular 0.5 to 8% by weight, of enzyme preparations ,
  • the automatic dishwashing detergents according to the invention can also contain further nonionic surfactants.
  • the weight fraction of the further nonionic surfactant in the total weight of the automatic dishwashing detergent according to the invention is between 0.1 and 30% by weight, preferably between 0.5 and 20% by weight, preferably between 1 and 10% by weight in particular between 2 and 6% by weight.
  • preferred further nonionic surfactants have the general formula R 1 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y [CH 2 CH (CH 3 ) O] z CH 2 CH (OH ) R 2 , in which R 1 represents a linear or branched aliphatic hydrocarbon radical with 4 to 22 carbon atoms or mixtures thereof, R 2 denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x and z for values between 0 and 40 and y is at least 15.
  • the dishwasher detergent based on its total weight, contains nonionic surfactant of the general formula R 1 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y [CH 2 CH (CH 3 ) O ] z CH 2 CH (OH) R 2 in amounts of 0.1 to 15% by weight, preferably 0.2 to 10% by weight, particularly preferably 0.5 to 8% by weight and in particular 1, 0 to 6% by weight.
  • Those end group-capped poly (oxyalkylated) nonionic surfactants which, according to the formula R 1 O [CH 2 CH 2 O] y CH 2 CH (OH) R 2 , in which R 1 is a linear or branched aliphatic hydrocarbon radical with 4 up to 22 carbon atoms or mixtures thereof, R 2 denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and y stands for a value between 15 and 120, preferably 20 to 100, in particular 20 to 80.
  • the group of these nonionic surfactants includes, for example, hydroxy mixed ethers of the general formula C 6-22 -CH (OH) CH 2 O- (EO) 20-120 -C 2-26 , for example the C 8-12 fatty alcohol (EO) 22 - 2-hydroxydecyl ether and the C 4-22 fatty alcohol (EO) 40-80 -2-hydroxyalkyl ether.
  • Automatic dishwashing detergent characterized in that a surfactant of the general formula R 1 CH (OH) CH 2 O- (CH 2 CH 2 O) 20-120 -R 2 is used as a further nonionic surfactant, R 1 and R 2 being independent from each other represent a linear or branched aliphatic hydrocarbon radical having 2 to 20 carbon atoms are particularly preferred.
  • surfactants of the formula R 1 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y CH 2 CH (OH) R 2 , in which R 1 is a linear or branched aliphatic hydrocarbon radical with 4 up to 22 carbon atoms or mixtures thereof, R 2 is a linear or branched Designated hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x stands for values between 0.5 and 4, preferably 0.5 to 1.5, and y stands for a value of at least 15.
  • surfactants of the general formula R 1 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y CH 2 CH (OH) R 2 are also preferred, in which R 1 is a linear or branched aliphatic Is a hydrocarbon radical having 4 to 22 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 a value between 1 and 40 and y is a value between 15 and 40, the alkylene units [CH 2 CH (CH 3 ) O] and [CH 2 CH 2 O] randomized, ie in the form of a statistical, random distribution.
  • the rinse aid and drying can be significantly improved compared to conventional polyalkoxylated fatty alcohols without a free hydroxyl group.
  • the stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the above-mentioned nonionic surfactants represent statistical mean values, which can be an integer or a fraction for a specific product. Due to the manufacturing process, commercial products of the formulas mentioned usually do not consist of an individual representative, but rather of mixtures, which can result in mean values and broken numbers both for the C chain lengths and for the degrees of ethoxylation or degrees of alkoxylation.
  • nonionic surfactants can be used not only as individual substances, but also as surfactant mixtures of two, three, four or more surfactants.
  • Surfactant mixtures are not mixtures of nonionic surfactants which, in their entirety, fall under one of the general formulas mentioned above, but rather mixtures which contain two, three, four or more nonionic surfactants included, which can be described by different of the aforementioned or other general formulas.
  • Nonionic surfactants which have a melting point above room temperature are particularly preferred.
  • the agents according to the invention can contain further washing or cleaning substances, preferably from the group of corrosion inhibitors, fragrances and perfume carriers.
  • the combinations of active ingredients described above are particularly suitable for cleaning dishes in automatic dishwashing processes.
  • Another subject of the present application is a method for cleaning dishes in a dishwasher, using an automatic dishwashing agent according to the invention, the automatic Dishwashing agents are preferably metered into the interior of a dishwasher during the course of a dishwashing program, before the start of the main wash cycle or in the course of the main wash cycle.
  • the agent according to the invention can be metered into the interior of the dishwasher manually, but the agent is preferably metered into the interior of the dishwasher by means of the dosing chamber of the dishwasher.
  • the automatic dishwashing detergents according to the invention show their advantageous cleaning and decorative protective properties, in particular also in low-temperature cleaning processes.
  • Preferred dishwashing methods using agents according to the invention are therefore characterized in that the dishwashing methods are carried out at a liquor temperature below 60 ° C., preferably below 50 ° C.
  • PVP particles with a particle diameter of 100-150 ⁇ m were incorporated into a commercially available dishwasher detergent tablet which contains zinc acetate. Comparative tests were now carried out in a dishwasher (Miele G 1355 SC, light 50 ° C turbo, 21 ° dH) with the tablet containing PVP particles on the one hand and the tablet without PVP particles on the other hand. An evaluation was made after going through 50 and 100 cycles. Both the glass corrosion and the decor removal of the treated glassware were assessed visually on a scale from 0 to 5, 5 being the best grade. The results are shown in the following table: Dishwashing liquid with PVP Dishwashing liquid without PVP Number of cycles glass corrosion decor glass corrosion decor 50 4.14 4.2 3.96 3.8 100 3.13 3.3 3.08 2.8

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • Oil, Petroleum & Natural Gas (AREA)
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Claims (9)

  1. Agent détergent pour le lavage de la vaisselle en machine, contenant au moins un sel de zinc et au moins un polymère contenant des hétérocycles contenant N, caractérisé en ce que le polymère contenant des hétérocycles contenant N est une polyvinylpyrrolidone, la polyvinylpyrrolidone étant présente sous forme de particules, les particules de polyvinylpyrrolidone ayant de préférence un diamètre moyen de particules de 100 à 150 µm.
  2. Agent détergent pour le lavage de la vaisselle en machine selon la revendication 1, caractérisée en ce que les particules de polyvinylpyrrolidone sont présentes dans l'agent détergent en une quantité de 0,1 à 5 % en poids, notamment en une quantité de 0,2 à 3 % en poids, en particulier en une quantité de 0,3 à 1,8 % en poids.
  3. Agent détergent pour le lavage de la vaisselle en machine selon l'une des quelconque revendications 1 à 2, caractérisé en ce que le sel de zinc est choisi dans le groupe constitué des sels de zinc inorganiques et organiques, en particulier du bromure de zinc, du chlorure de zinc, de l'iodure de zinc, du nitrate de zinc, du sulfate de zinc, de l'acétate de zinc, de l'acétylacétonate de zinc, du benzoate de zinc, du formiate de zinc, du lactate de zinc, du gluconate de zinc, du ricinoléate de zinc, de l'abiétate de zinc, du valérate de zinc et du p-toluènesulfonate de zinc, et en ce que le sel de zinc est de préférence présent en une quantité de 0,01 à 3 % en poids, de préférence en une quantité de 0,05 à 2 % en poids, en particulier en une quantité de 0,1 à 1 % en poids, dans l'agent détergent.
  4. Agent détergent pour le lavage de la vaisselle en machine selon l'une des quelconque des revendications précédentes, caractérisé en ce qu'il contient au moins un adjuvant, en particulier choisi parmi les sels de tripolyphosphate, d'acide carbonique et d'acide citrique.
  5. Agent détergent pour le lavage de la vaisselle en machine selon l'une des quelconque des revendications précédentes, caractérisé en ce qu'il contient au moins un polymère anionique choisi dans le groupe des copolymères, comprenant
    i) le(s) monomère(s) contenant des groupes acide carboxylique,
    ii) le(s) monomère(s) contenant un groupe acide sulfonique et
    iii) éventuellement le(s) monomère(s) non ionique(s),
    le polymère anionique étant de préférence présent en une quantité de 0,1 à 20 % en poids, notamment de 0,5 à 18 % en poids, de manière particulièrement préférée de 1,0 à 15 % en poids et en particulier de 4 à 14 % en poids.
  6. Agent détergent pour le lavage de la vaisselle en machine selon l'une des quelconque des revendications précédentes, caractérisé en ce qu'une solution à 10 % de l'agent dans de l'eau distillée (20 °C) présente une valeur de pH de 7 à 13, en particulier de 8 à 12, de manière particulièrement préférée de 9 à 11.
  7. Agent détergent pour le lavage de la vaisselle en machine selon l'une des quelconque des revendications précédentes, caractérisé en ce qu'il se présente sous la forme d'un corps moulé pressé, en particulier sous la forme d'un produit compacté, notamment d'une pastille.
  8. Procédé de lavage de la vaisselle en machine, caractérisé en ce que l'on utilise un agent détergent pour le lavage de la vaisselle en machine selon l'une quelconque des revendications précédentes, en particulier pour obtenir une protection améliorée du verre, de la porcelaine et/ou du décor ou pour réduire la corrosion du verre et de la porcelaine et/ou pour diminuer l'élimination du décor.
  9. Utilisation d'une combinaison d'un sel de zinc et d'un polymère contenant des hétérocycles contenant N, dans laquelle le polymère est une polyvinylpyrrolidone, pour obtenir une protection améliorée du verre, de la porcelaine et/ou du décor ou pour réduire la corrosion du verre et de la porcelaine et/ou pour diminuer l'élimination du décor.
EP12724981.1A 2011-06-21 2012-05-30 Détergents pour vaisselle avec protection de décor améliorée Active EP2723844B1 (fr)

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DE102011077865A DE102011077865A1 (de) 2011-06-21 2011-06-21 Geschirrspülmittel mit verbessertem Dekor-Schutz
PCT/EP2012/060105 WO2012175292A1 (fr) 2011-06-21 2012-05-30 Détergents pour vaisselle avec protection de décor améliorée

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007049250A1 (fr) * 2005-10-28 2007-05-03 The Procter & Gamble Company Composition contenant un sulfonate esterifie a substitution benzenique

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Publication number Priority date Publication date Assignee Title
DE10153555A1 (de) * 2001-08-17 2003-05-22 Henkel Kgaa Maschinelles Geschirrspülmittel mit Glaskorrosionsschutzeigenschaften
DE10225116A1 (de) * 2002-06-06 2003-12-24 Henkel Kgaa Maschinelles Geschirrspülmittel mit verbessertem Glaskorrosionsschutz II
DE102008020275A1 (de) * 2008-04-22 2009-10-29 Henkel Ag & Co. Kgaa Zinkhaltiger Wasch- oder Reinigungsmittelformkörper

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007049250A1 (fr) * 2005-10-28 2007-05-03 The Procter & Gamble Company Composition contenant un sulfonate esterifie a substitution benzenique

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DE102011077865A1 (de) 2012-12-27
ES2786102T3 (es) 2020-10-08
PL2723844T3 (pl) 2020-08-10
WO2012175292A1 (fr) 2012-12-27

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