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EP1417291B1 - Produits de lavage pour lave-vaisselle garantissant une protection amelioree contre la corrosion du verre - Google Patents

Produits de lavage pour lave-vaisselle garantissant une protection amelioree contre la corrosion du verre Download PDF

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Publication number
EP1417291B1
EP1417291B1 EP02767346A EP02767346A EP1417291B1 EP 1417291 B1 EP1417291 B1 EP 1417291B1 EP 02767346 A EP02767346 A EP 02767346A EP 02767346 A EP02767346 A EP 02767346A EP 1417291 B1 EP1417291 B1 EP 1417291B1
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EP
European Patent Office
Prior art keywords
acid
weight
zinc
automatic dishwashing
dishwashing agent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Revoked
Application number
EP02767346A
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German (de)
English (en)
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EP1417291A2 (fr
Inventor
Arnd Kessler
Rainer Sorg
Melanie Baumann
Wolfgang Wick
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority claimed from DE2001140535 external-priority patent/DE10140535B4/de
Priority claimed from DE2001153555 external-priority patent/DE10153555A1/de
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP1417291A2 publication Critical patent/EP1417291A2/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0073—Anticorrosion 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/265—Carboxylic acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3245—Aminoacids

Definitions

  • the present invention is in the field of automatic dishwashing detergents. More particularly, the present invention relates to automatic dishwashing compositions containing magnesium and / or zinc salts.
  • the so-called lower alkaline cleaners required for automatic dishwashing frequently contain mixtures of sodium disilicate and soda as alkali carriers, builders such as citric acid, for example in conjunction with polycarboxylates, and preferably low-foaming nonionic surfactants. Furthermore, bleaching agents, bleach activators, silver and corrosion inhibitors and, to enhance the cleaning power, enzymes may be included.
  • the dishes set in baskets are cleaned by intensive contact with the aqueous detergent solution at about 65 ° C and pH values between 9 and 11 and then rinsed clear.
  • dishwasher detergents containing phosphate which contain a powdery to granular additive which contains as essential constituents a crystalline layered silicate of general formula NaMSi x O 2x + 1 ⁇ y H 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 22 and y is a number from 0 to 33, and have (co) polymeric polycarboxylic acid and in addition to glass or decor-preserving effects also have excellent cleaning performance.
  • the European patent application EP 0 383 482 (Procter & Gamble) finally describes automatic dishwasher detergents containing insoluble zinc salts, which are distinguished by improved glass corrosion protection.
  • the insoluble zinc salts must have a particle size below 1.7 millimeters to achieve such an effect.
  • the international patent application WO 00/39259 discloses water-soluble glasses according to DIN ISO 719, which contain at least one glass corrosion-inhibiting active ingredient whose weight fraction of the glass is not more than 85 wt .-% and which is released under the conditions of cleaning and / or rinsing from this glass.
  • an object of the present invention to provide a machine dishwashing detergent which does not corrosively change the surfaces of glassware, even after repeated use, in particular does not cause turbidity, streaks or scratches, nor iridescence of the glass surfaces.
  • an automatic dishwashing detergent additive should be provided which is suitable as a component of any type of dishwashing detergent, for example as a component of powder, tablet, liquid formulations, cleaning foams or depot products, without any limitations on the formulations of these forms.
  • the spectrum of the inventively preferred zinc salts of organic acids ranging from salts which are difficult or insoluble in water, ie a solubility below 100 mg / L, preferably below 10 mg / L, in particular have no solubility, to such salts which have a solubility in water above 100 mg / L, preferably above 500 mg / L, more preferably above 1 g / L and in particular above 5 g / L (all solubilities at 20 ° C water temperature).
  • the first group of zinc salts includes, for example, zinc oleate and zinc stearate
  • the group of soluble zinc salts includes, for example, zinc formate, zinc acetate and zinc gluconate:
  • compositions according to the invention comprise at least one zinc salt but no magnesium salt of an organic acid, which is preferably at least one zinc salt of an organic carboxylic acid, more preferably a zinc salt selected from zinc stearate, zinc oleate, zinc gluconate, Zinc acetate and / or zinc lactate.
  • An agent preferred in the context of the present invention contains zinc salt in amounts of from 0.1 to 5% by weight, preferably from 0.2 to 4% by weight and in particular from 0.4 to 3% by weight, or zinc in oxidized form in amounts of 0.01 to 1 wt .-%, preferably from 0.02 to 0.5 wt .-% and in particular from 0.04 to 0.2 wt .-%, each based on the total weight of automatic dishwashing detergent.
  • machine dishwashing detergents in the context of the present invention can therefore be provided both in solid and in liquid form.
  • Solid forms of the machine dishwashing detergent according to the invention are, for example, fine to coarse-grained powders, as obtained, for example, by spray-drying or granulation, compacted mixtures of roll compacting, but also solidified melts or shaped articles obtained by extrusion or tableting.
  • moldings of this kind can have virtually all useful designs, for example in the form of a tablet, in bar or bar form, a cube, a cuboid and corresponding spatial element with flat side surfaces and, in particular, cylindrical configurations with a circular or oval cross-section ,
  • This last embodiment covers the presentation form of the actual tablet to compact cylinder pieces with a height-to-diameter ratio above 1.
  • Preferred tabletted or extruded means in the present invention, two or more phases, for example, by their composition, their Share of the total volume of the molding and / or can distinguish their visual appearance.
  • inventive magnesium and / or zinc salts of organic acids into the automatic dishwashing compositions according to the invention does not entail any restriction with respect to the forms of preparation or the formulations of these compositions.
  • Machine dishwashing detergents in the context of the present invention can therefore be provided both in solid and in liquid form.
  • automatic dishwashing agents which contain the described magnesium and / or zinc salts for glass corrosion protection, these salts being formulated in such a way that they can be safely and reliably added to a dishwasher detergent even in small quantities and continue to be present in do not demix a fully prepared powdered or granular automatic dishwashing detergent.
  • a further preferred subject of this application is therefore an automatic dishwasher detergent according to the invention, characterized in that one or more magnesium and / or zinc salt (s) is present in particulate form and in the form with one or more further active and / or builder substances.
  • Solid forms of the machine dishwashing detergent according to the invention contain, for example, fine to coarse-grained powders, as obtained, for example, by spray-drying or granulation.
  • Such powders can be marketed as a commercial product or used as a premix for compaction, for example for tableting, and generally have a particle size in the range from 0.1 to 10 mm.
  • it is preferred that these compounds have a particle size comparable to the powders.
  • a preferred subject of the present application is therefore a machine dishwashing detergent, characterized in that the particle size of the one or more Active and / or builders formulated magnesium and / or zinc salts 0.1 and 10 mm, preferably 0.2 and 8 mm and in particular 0.5 and 5 mm, with preferred particulate compounds to avoid demixing additionally a density of 0 , 1 to 2.0 g / cm 3 , preferably from 0.2 to 1.6 g / cm 3 and in particular from 0.4 to 1.2 g / cm 3 .
  • Dishwashing detergents which are preferred according to the invention are characterized in particular by the fact that the particles of the magnesium and / or zinc salts compounded with one or more active and / or builder substances contain from 0.1 to 80% by weight of this magnesium and / or zinc salt (s). -%, particularly preferably from 0.2 to 70% by weight and particularly preferably from 0.5 to 60 wt .-%, each based on the total weight of the assembled magnesium and / or zinc salts.
  • the abovementioned particulate compounds are obtained according to the invention preferably by spray drying and / or granulation and / or extrusion and / or roller compaction and / or tabletting and / or solidification and / or crystallization, but in particular by spray drying and / or granulation.
  • the particulate present, with one or more active and / or builders formulated magnesium and / or zinc salts may be provided to protect environmental influences and thus to improve their storage stability or to influence the dissolution behavior with a coating (coating).
  • Preferred subject matter of the present invention are automatic dishwashing detergents, characterized in that the magnesium and / or zinc salts compounded with one or more active and / or builder substances additionally have a coating.
  • the dissolution behavior of magnesium and / or zinc salts prepared according to the invention can also be influenced by the abovementioned compaction methods.
  • aids such as binders
  • the choice of / the co-assembled active and / or builders of great importance in addition to the amount of pressure used and the use of aids, such as binders, in particular the choice of / the co-assembled active and / or builders of great importance.
  • compacted silicates, in particular disilicates, and / or polycarboxylates and / or mixtures of different polycarboxylates are suitable as "depot substances" for the magnesium and magnesium according to the invention because of their delayed solution / dispersion or due to gelling of these substances or substance mixtures in aqueous liquor / or zinc salts.
  • an agent containing the zinc and / or magnesium salts of an organic acid preferably an organic carboxylic acid
  • a commercially available cleaning agent for example in the form of a special glass protection agent.
  • Such a dosage can take place both before the beginning of each rinsing program and in the form of a depot product which causes a continuous release of the zinc and / or magnesium salts of organic acid according to the invention over several rinsing cycles.
  • preferred automatic dishwashing agents In addition to the builders (builders, cobuilders) and the zinc and / or magnesium salts of organic acids, preferred automatic dishwashing agents according to the invention also contain one or more substances from the group of surfactants, bleaches, bleach activators, enzymes, dyes, fragrances, corrosion inhibitors, polymers, or a another common ingredient of detergents and cleaners. These ingredients are described below.
  • all builders commonly used in detergents and cleaners in particular silicates, carbonates, organic cobuilders and also the phosphates, may be incorporated into the detergents and cleaners.
  • Suitable crystalline layered sodium silicates have the general formula NaMSi x O 2x + 1 .H 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4 are.
  • Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O s ⁇ yH 2 O are preferred.
  • both the monoalkali metal salts and the dialkali metal salts of carbonic acid as well as sesquicarbonates can be contained in the compositions.
  • Preferred alkali metal ions are sodium and / or potassium ions.
  • Compounds of, for example, carbonate, silicate and optionally other auxiliaries such as, for example, anionic surfactants or other, in particular organic builders, may be present as a separate component in the finished compositions.
  • the alkali metal phosphates with a particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest importance in the washing and cleaning agent industry.
  • Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO 3 ) n and orthophosphoric H 3 PO 4 in addition to higher molecular weight representatives.
  • the phosphates combine several advantages: they act as alkali carriers, prevent limescale deposits on machine parts or limescale deposits on the items to be washed and also contribute to the cleaning performance.
  • pentasodium triphosphate Na 5 P 3 O 10 (sodium tripolyphosphate)
  • pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.).
  • Pentakaliumtriphosphat, K 5 P 3 O 10 potassium tripolyphosphate
  • the potassium polyphosphates are widely used in the washing and cleaning industry.
  • sodium potassium tripolyphosphates which can also be used in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH: (NaPO 3 ) 3 + 2 KOH ⁇ Na 3 K 2 P 3 O 10 + H 2 O
  • Automatic dishwashing detergents preferred in the context of the present invention contain no sodium and / or potassium hydroxide.
  • a waiver of sodium and / or potassium hydroxide as an alkali source has proved to be particularly advantageous if zinc gluconate, zinc formate and zinc acetate are used as zinc salts.
  • organic cobuilders in the detergent in the context of the present invention in particular polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates can be used. These classes of substances are described below.
  • Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, methylglycinediacetic acid, sugar acids and mixtures thereof.
  • the acids themselves can also be used.
  • the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners.
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
  • polymeric polycarboxylates for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol.
  • the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.
  • Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of from 1000 to 20 000 g / mol. Because of their superior solubility, this group may in turn, the short-chain polyacrylates, the molar masses of 1000 to 10,000 g / mol, and more preferably from 1200 to 4000 g / mol, have to be preferred.
  • Both polyacrylates and copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally further ionic or nonionogenic monomers are particularly preferably used in the compositions according to the invention.
  • the sulfonic acid-containing copolymers will be described in detail below.
  • the invention is characterized by an improved "cleanability" of the treated substrates in subsequent cleaning operations and by a significant reduction in the drying time compared to comparable agents without the use of sulfonic acid-containing polymers.
  • Drying time in the context of the teaching according to the invention is generally understood to mean the meaning of the word, ie the time that elapses until a dish surface treated in a dishwasher has dried, but in particular the time that elapses, up to 90% with a cleaning or Rinse aid is dried in concentrated or diluted form treated surface.
  • R 1 (R 2 ) C C (R 3 ) COOH (VI)
  • R 1 to R 3 independently of one another are -H-CH 3 , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH 2 , -OH or - COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or - COOR 4 , wherein R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.
  • R 5 (R 6 ) C C (R 7 ) -X-SO 3 H (VII)
  • H 2 C CH-X-SO 3 H (VIIa)
  • H 2 C C (CH 3 ) -X-SO 3 H (VIIb)
  • HO 3 SX- (R 6 ) C C (R 7 ) -X-SO 3 H (VIIc)
  • R 6 and R 7 are independently selected from -H, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH (CH 3 ) 2
  • Suitable further ionic or nonionic monomers are, in particular, ethylenically unsaturated compounds.
  • the content of the polymers used according to the invention to monomers of group iii) is preferably less than 20% by weight, based on the polymer.
  • Particularly preferred polymers to be used consist only of monomers of groups i) and ii).
  • copolymers present in the compositions according to the invention may contain the monomers from groups i) and ii) and optionally iii) in varying amounts, all representatives from group i) with all representatives from group ii) and all representatives from group iii ) can be combined.
  • Particularly preferred polymers have certain structural units, which are described below.
  • maleic acid can also be used as a particularly preferred monomer from group i).
  • machine dishwashing detergents which comprise one or more copolymers as ingredient b), the structural units of the formulas VIII and / or IX and / or X and / or XI and / or XI and / or XIII - [CH 2 -CHCOOH] m - [CH 2 -CHC (O) -Y-SO 3 H] p - (VIII) - [CH 2 -C (CH 3 ) COOH] m - [CH 2 -CHC (O) -Y-SO 3 H] p - (IX), - [CH 2 -CHCOOH] m - [CH 2 -C (CH 3 ) C (O) -Y-SO 3 H] p - (X), - [CH 2 -C (CH 3 ) COOH] m - [CH 2 -C (CH 3 ) C (O) -Y-SO 3 H] p - (XI), - [CH 2 -C (CH
  • the sulfonic acid groups may be wholly or partially in neutralized form, i. in that the acidic hydrogen atom of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions.
  • metal ions preferably alkali metal ions and in particular for sodium ions.
  • Corresponding agents which are characterized in that the sulfonic acid groups are partially or fully neutralized in the copolymer, are preferred according to the invention.
  • the monomer distribution of the copolymers used in the agents according to the invention in the case of copolymers which contain only monomers from groups i) and ii) is preferably in each case from 5 to 95% by weight i) or ii), particularly preferably from 50 to 90% by weight. % Of monomer from group i) and from 10 to 50% by weight of monomer from group ii), in each case based on the polymer.
  • terpolymers particular preference is given to those containing from 20 to 85% by weight of monomer from group i), from 10 to 60% by weight of monomer from group ii) and from 5 to 30% by weight of monomer from group iii) ,
  • the molecular weight of the polymers used in the agents according to the invention can be varied in order to adapt the properties of the polymers to the desired use.
  • Preferred automatic dishwashing agents are characterized in that the copolymers have molar masses of from 2000 to 200,000 gmol -1 , preferably from 4000 to 25,000 gmol -1 and in particular from 5000 to 15,000 gmol -1 .
  • the content of one or more copolymers in the compositions according to the invention may vary depending on the intended use and the desired product performance, preferred automatic dishwashing compositions according to the invention being characterized in that they contain the copolymer (s) in amounts of from 0.25 to 50% by weight. %, preferably from 0.5 to 35 wt .-%, particularly preferably from 0.75 to 20 wt .-% and in particular from 1 to 15 wt .-%.
  • polyacrylates As already mentioned above, in the agents according to the invention it is particularly preferable to use both polyacrylates and the above-described copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally further ionic or nonionogenic monomers.
  • the polyacrylates were described in detail above. Particularly preferred are combinations of the above-described sulfonic acid-containing copolymers with low molecular weight polyacrylates, for example in the range between 1000 and 4000 daltons.
  • Such polyacrylates are commercially available under the trade name Sokalan ® PA15 and Sokalan ® PA25 (BASF).
  • preferred automatic dishwashing detergents therefore comprise one or more zinc salts, preferably from the group consisting of zinc stearate, zinc oleate, zinc citrate, zinc gluconate, zinc lactate and / or zinc acetate, as well as one or more sulfonic acid groups.
  • the preferred weight ratio of zinc salt (calculated on Zn 2+ ) to sulfonic acid group-containing copolymer in such a preferred automatic dishwashing detergent is between 20: 1 and 1: 500, in particular between 1: 1 and 1: 400 and particularly preferably between 1:10 and 1: 250th
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their molecular weight relative to free acids is generally from 2000 to 100,000 g / mol, preferably from 20,000 to 90,000 g / mol and in particular from 30,000 to 80,000 g / mol.
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution.
  • the content of (co) polymeric polycarboxylates in the compositions is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.
  • the polymers may also contain allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.
  • biodegradable polymers of more than two different monomer units for example those which contain as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives ,
  • phosphonates are, in particular, hydroxyalkane or aminoalkanephosphonates.
  • hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B.
  • the builder used here is preferably HEDP from the class of phosphonates.
  • the aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
  • agents according to the invention are characterized in that they comprise builders, preferably from the group of silicates, carbonates, organic cobuilders and / or phosphates, in amounts of from 0.1 to 99.5% by weight, preferably from 1 to 95% Wt .-%, particularly preferably from 5 to 90 wt .-% and in particular from 10 to 80 wt .-%, each based on the composition.
  • preferred cleaners comprise one or more surfactants from the groups of anionic, nonionic, cationic and / or amphoteric surfactants.
  • nonionic surfactants are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
  • EO ethylene oxide
  • alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohols with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols containing 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12-14 alcohol with 3 EO and C12-18 alcohol containing 5 EO.
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain.
  • nonionic surfactants in detergents and cleaners for automatic dishwashing come as surfactants in general all surfactants in question.
  • the nonionic surfactants described above and, above all, the low-foaming nonionic surfactants are preferred for this purpose.
  • Particularly preferred are the alkoxylated alcohols, especially the ethoxylated and / or propoxylated alcohols.
  • the person skilled in the art generally understands, under alkoxylated alcohols, the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferably in the context of the present invention, the longer-chain alcohols (C 10 to C 18 , preferably between C 12 and C 16 , such as, for example, C 11 -, C 12 -, C 13 -, C 14 -, C 15 -, C 18 -, C 17 - and C 18 -alcohols).
  • C 10 to C 18 preferably between C 12 and C 16 , such as, for example, C 11 -, C 12 -, C 13 -, C 14 -, C 15 -, C 18 -, C 17 - and C 18 -alcohols.
  • n moles of ethylene oxide and one mole of alcohol give rise to a complex mixture of addition products different depending on the reaction conditions Ethoxylation.
  • a further embodiment consists in the use of mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide. Also, if desired, by a final etherification with short-chain alkyl groups, such as preferably the butyl group, the substance class of "closed" alcohol ethoxylates reach, which can also be used in the context of the invention. Very particularly preferred for the purposes of the present invention are highly ethoxylated fatty alcohols or mixtures thereof with end-capped fatty alcohol ethoxylates.
  • nonionic surfactants have been low foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units.
  • surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows.
  • machine dishwashing agents which contain, as nonionic surfactant (s), surfactants of the general formula XVI in which R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 alkyl or alkenyl radical; each group R 2 or R 3 is independently selected from -CH 3 ; -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , -CH (CH 3 ), and the indices w, x, y, z independently represent integers from 1 to 6.
  • nonionic surfactant s
  • R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 alkyl or alkenyl radical
  • each group R 2 or R 3 is independently selected from -CH 3 ; -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , -CH (CH 3 )
  • the indices w, x, y, z independently represent integers from 1 to 6.
  • the preferred nonionic surfactants of formula XVI 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 XVI may 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 usually undisplayed, wherein the linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example from coconut, palm, tallow or Oleyl alcohol, are preferred.
  • Alcohols accessible from synthetic sources are, for example, the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position in the mixture, as they are usually present in oxo alcohol radicals.
  • R 1 in formula XVI is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 carbon atoms.
  • alkylene oxide unit which is contained in the preferred nonionic surfactants in alternation with the ethylene oxide unit, in particular butylene oxide is considered in addition to propylene oxide.
  • R 2 or R 3 are independently selected from - CH 2 CH 2 -CH 3 or -CH (CH 3 ) 2 are suitable.
  • Preferred automatic dishwashing detergents are characterized in that R 2 and R 3 are a radical -CH 3, w and x independently of one another for values of 3 or 4 and y and z are independently values of 1 or second
  • nonionic surfactants which have a C 9-15 -alkyl radical having 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed by 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units.
  • the automatic dishwasher detergents according to the invention contain a nonionic surfactant which has a melting point above room temperature.
  • preferred agents are characterized by containing nonionic surfactant (s) having a melting point above 20 ° C, preferably above 25 ° C, more preferably between 25 and 60 ° C, and most preferably between 26.6 and 43, 3 ° C, included.
  • Suitable nonionic surfactants in addition to the nonionic surfactants according to the invention which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which may be solid or highly viscous at room temperature. If high-viscosity nonionic surfactants are used at room temperature, it is preferred that they have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Nonionic surfactants which have waxy consistency at room temperature are also preferred.
  • Preferred nonionic surfactants to be used at room temperature are from the groups of the alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols, and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants.
  • Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.
  • the nonionic surfactant having a melting point above room temperature is an ethoxylated nonionic surfactant consisting of the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms, preferably at least 12 mol, more preferably at least 15 mol, especially at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol emerged.
  • a particularly preferred room temperature solid nonionic surfactant is obtained from a straight chain fatty alcohol having 16 to 20 carbon atoms (C 16-20 alcohol), preferably a C 16 alcohol and at least 12 moles, preferably at least 15 moles and especially at least 20 moles of ethylene oxide , Of these, the so-called “narrow range ethoxylates" (see above) are particularly preferred.
  • particularly preferred agents according to the invention contain ethoxylated nonionic surfactant (s) consisting of C 6-20 monohydroxyalkanols or C 6-20 alkylphenols or C 16-20 fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 moles of ethylene oxide per mole of alcohol was recovered (n).
  • ethoxylated nonionic surfactant consisting of C 6-20 monohydroxyalkanols or C 6-20 alkylphenols or C 16-20 fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 moles of ethylene oxide per mole of alcohol was recovered (n).
  • the nonionic surfactant preferably additionally has propylene oxide units in the molecule.
  • such PO units make up to 25 wt .-%, more preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant from.
  • Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units.
  • the alcohol or alkylphenol part of such nonionic surfactant molecules preferably constitutes more than 30% by weight, more preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight of such nonionic surfactants.
  • Preferred automatic dishwashing detergents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule contain up to 25% by weight, preferably up to 20% by weight and in particular up to 15% by weight of the total molecular weight of the nonionic surfactant.
  • More particularly preferred nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight. % of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.
  • Nonionic surfactants that may be used with particular preference are available, for example under the name Poly Tergent ® SLF-18 from Olin Chemicals.
  • a further preferred machine dishwashing detergent according to the invention contains nonionic 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 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 a value of at least 15.
  • nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 in which R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5.
  • each R 3 in the above formula may be different.
  • R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred.
  • R 3 H, -CH 3 or -CH 2 CH 3 are particularly preferred.
  • Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
  • each R 3 in the above formula may be different if x ⁇ 2.
  • the alkylene oxide unit in the square bracket can be varied.
  • the value 3 for x has been selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,
  • R 1 , R 2 and R 3 are as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18.
  • Particularly preferred are surfactants in which the radicals R 1 and R 2 has 9 to 14 C atoms, R 3 is H and x assumes values of 6 to 15.
  • dishwashing agents according to the invention are preferred, the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 in which R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, x is n-butyl, 2-butyl or 2-methyl-2-butyl, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5, surfactants of the type R 1 O [CH 2 CH (R 3 ) O] x CH 2 CH (OH) CH 2 OR 2 in which x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, are particularly preferred.
  • R 1 and R 2 are linear or
  • Anionic, cationic and / or amphoteric surfactants may also be used in conjunction with the surfactants mentioned, these having only minor importance because of their foaming behavior in dishwasher detergents and usually only in amounts below 10% by weight, in most cases even below 5% by weight .-%, for example, from 0.01 to 2.5 wt .-%, each based on the agent used.
  • the agents according to the invention can thus also contain anionic, cationic and / or amphoteric surfactants as surfactant component.
  • the automatic dishwashing agents comprise surfactant (s), preferably nonionic surfactant (s), in amounts of from 0.5 to 10% by weight, preferably from 0.75 to 7.5 wt .-% and in particular from 1.0 to 5 wt .-%, each based on the total agent.
  • surfactant preferably nonionic surfactant (s)
  • s nonionic surfactant
  • Bleaching agents and bleach activators are important constituents of detergents and cleaners, and a washing and cleaning agent may in the context of the present invention contain one or more substances from the groups mentioned.
  • sodium percarbonate has particular significance.
  • Further useful bleaching agents are, for example, sodium perborate tetrahydrate and the sodium perborate monohydrate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -forming peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazeiainic acid, phthalominoperacid or diperdodecanedioic acid.
  • Dishwashing detergents may also contain bleaches from the group of organic bleaches.
  • Typical organic bleaching agents which can be used as ingredients in the present invention are the diacyl peroxides, e.g. Dibenzoyl.
  • Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids.
  • Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimidoperoxycaproic acid [Phthaloiminoperoxyhexanoic acid (PAP )], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, 2-decy
  • Advantageous agents in the context of the present invention contain one or more bleaching agents, preferably from the group of the oxygen or halogen bleaches, in particular the chlorine bleach, with particular preference of sodium percarbonate and / or sodium perborate monohydrate, in amounts of 0.5 to 40 wt .-%, preferably from 1 to 30 wt .-%, particularly preferably from 2.5 to 25 wt .-% and in particular from 5 to 20 wt .-%, each based on the total agent.
  • one or more bleaching agents preferably from the group of the oxygen or halogen bleaches, in particular the chlorine bleach, with particular preference of sodium percarbonate and / or sodium perborate monohydrate, in amounts of 0.5 to 40 wt .-%, preferably from 1 to 30 wt .-%, particularly preferably from 2.5 to 25 wt .-% and in particular from 5 to 20 wt .-%, each based on the total agent.
  • cleaning agents in the context of the present invention may be bleach activators contain.
  • bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy- 2,5-dihydrofuran.
  • TAED tetraacet
  • bleach catalysts can also be incorporated into the detergents according to the present invention.
  • These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.
  • agents which comprise one or more substances from the group of bleach activators, in particular from the groups of the polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), the acylated phenolsulfonates, in particular Nonanoyl or Isononanoyloxybenzolsulfonat (n- or iso-NOBS) and n-methyl-morpholinium acetonitrile-methyl sulfate (MMA), in amounts of 0.1 to 20 wt .-%, preferably from 0.5 to 15 wt. % and in particular from 1 to 10 wt .-%, each based on the total agent included.
  • TAED tetraacetylethylenediamine
  • N-acylimides in particular N-nonanoylsuccinimide (NOSI)
  • Particularly suitable enzymes are those from the classes of hydrolases such as the proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases in the wash contribute to the removal of stains such as proteinaceous, greasy or starchy stains and graying. In addition, cellulases and other glycosyl hydrolases may contribute to color retention and to enhancing the softness of the fabric by removing pilling and microfibrils. It is also possible to use oxidoreductases for bleaching or inhibiting color transfer.
  • subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used.
  • enzyme mixtures for example from protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest.
  • lipolytic enzymes are the known cutinases.
  • Peroxidases or oxidases have also proved suitable in some cases.
  • Suitable amylases include, in particular, alpha-amylases, iso-amylases, pullulanases and pectinases.
  • As cellulases are preferably cellobiohydrolases, endoglucanases and - glucosidases, which are also called cellobiases, or mixtures thereof used. Since different cellulase types differ by their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.
  • the enzymes may be adsorbed to carriers or embedded in encapsulants to coat them against premature degradation.
  • Preferred agents according to the invention contain enzymes, preferably in the form of liquid and / or solid enzyme preparations, in amounts of from 0.1 to 10% by weight, preferably from 0.5 to 8% by weight and in particular from 1 to 5% by weight. , in each case based on the total mean.

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Claims (16)

  1. Agent pour le lavage mécanique de la vaisselle, contenant des builders et de manière facultative d'autres constituants d'agents de nettoyage, caractérisé en ce qu'il contient :
    a) un ou plusieurs sels de magnésium et/ou de zinc d'au moins un acide monocarboxylique non ramifié ou ramifié, saturé ou insaturé, à l'exception du ricinoléate de zinc et de l'abiétate de zinc ;
    b) à concurrence de 0,1 à 70 % en poids, des copolymères
    i) d'acides carboxyliques insaturés
    ii) de monomères contenant des groupes d'acides sulfoniques.
  2. Agent pour le lavage mécanique de la vaisselle selon la revendication 1, caractérisé en ce que lesdits un ou plusieurs acides monocarboxyliques non ramifiés, saturés ou insaturés sont choisis parmi le groupe comprenant : l'acide méthanoïque (acide formique), l'acide éthanoïque (acide acétique), l'acide propanoïque (acide propionique), l'acide pentanoïque (acide valérique), l'acide hexanoïque (acide caproïque), l'acide heptanoïque (acide oenanthique), l'acide octanoïque (acide caprylique), l'acide nonanoïque (acide pélargonique), l'acide décanoïque (acide caprique), l'acide undécanoïque, l'acide dodécanoïque (acide laurique), l'acide tridécanoïque, l'acide tétradécanoïque (acide myristique), l'acide pentadécanoïque, l'acide hexadécanoïque (acide palmitique), l'acide heptadécanoïque (acide margarinique), l'acide octadécanoïque (acide stéarique), l'acide eicosanoïque (acide arachidonique), l'acide docosanoïque (acide béhénique), l'acide tétracosanoïque (acide lignocérique), l'acide hexacosanoïque (acide cérotinique), l'acide triacotanoïque (acide mélissique), l'acide 9c-hexadécénoïque (acide palmitoléique), l'acide 6c-octadécénoïque (acide pétrosélinique), l'acide 6t-octadécénoïque (acide pétrosélaïdique), l'acide 9c-octadécénoïque (acide oléique), l'acide 9t-octadécénoïque (acide élaïdique), l'acide 9c,12c-octadécadiénoïque (acide linoléique), l'acide 9t,12t-octadécadiénoïque (acide linolaïdique) et l'acide 9c,12c,15c-octadécatriénoïque (acide linolénique).
  3. Agent pour le lavage mécanique de la vaisselle selon la revendication 1, caractérisé en ce que lesdits un ou plusieurs acides monocarboxyliques ramifiés, saturés ou insaturés sont choisis parmi le groupe comprenant : l'acide 2-méthylpentanoïque, l'acide 2-éthylhexanoïque, l'acide 2-propylheptanoïque, l'acide 2-butyloctanoïque, l'acide 2-pentylnonanoïque, l'acide 2-hexyldécanoïque, l'acide 2-heptylundécanoïque, l'acide 2-octyldodécanoïque, l'acide 2-nonyltridécanoïque, l'acide 2-décyltétradécanoïque, l'acide 2-undécylpentadécanoïque, l'acide 2-dodécylhexadécanoïque, l'acide 2-tridécylheptadécanoïque, l'acide 2-tétradécyloctadécanoïque, l'acide 2-pentadécylnonadécanoïque, l'acide 2-hexadécyléicosanoïque et l'acide 2-heptadécylhénéicosanoïque.
  4. Agent pour le lavage mécanique de la vaisselle selon l'une quelconque des revendications 1 à 3, caractérisé en ce qu'il contient, à titre de sel de zinc, l'oléate de zinc, le stéarate de zinc, le gluconate de zinc, l'acétate de zinc et/ou le lactate de zinc.
  5. Agent pour le lavage mécanique de la vaisselle selon l'une quelconque des revendications 1 à 4, caractérisé en ce qu'il contient au moins un sel de zinc dans des quantités de 0,1 à 5 % en poids, de préférence de 0,2 à 4 % en poids et en particulier de 0,4 à 3 % en poids, chaque fois rapportés au poids total de l'agent pour le lavage mécanique de la vaisselle.
  6. Agent pour le lavage mécanique de la vaisselle selon la revendication 4 ou 5, caractérisé en ce qu'il contient au moins un sel de zinc, l'agent pour le lavage mécanique de la vaisselle contenant du zinc sous forme oxydée dans des quantités de 0,01 à 1 % en poids, de préférence de 0,02 à 0,5 % en poids et en particulier de 0,04 à 0,2 % en poids, chaque fois rapportés au poids total de l'agent pour le lavage mécanique de la vaisselle.
  7. Agent pour le lavage mécanique de la vaisselle selon l'une quelconque des revendications 1 à 6, caractérisé en ce qu'il contient un ou plusieurs agents tensioactifs, de préférence un ou plusieurs agents tensioactifs non ioniques dans des quantités de 0,5 à 10 % en poids, de préférence de 0,75 à 7,5 % en poids et en particulier de 1,0 à 5 % en poids, chaque fois rapportés à l'agent dans sa totalité.
  8. Agent pour le lavage mécanique de la vaisselle selon l'une quelconque des revendications 1 à 7, caractérisé en ce qu'un ou plusieurs sels de magnésium et/ou de zinc est/sont présent(s) sous forme particulaire et est/sont présents sous une forme confectionnée avec une ou plusieurs autres substances actives et/ou builders.
  9. Agent pour le lavage mécanique de la vaisselle selon la revendication 8, caractérisé en ce que la granulométrie des sels de magnésium et/ou de zinc confectionnés avec une ou plusieurs substances actives et/ou builders s'élève de 0,1 à 10 mm, de préférence de 0,2 à 8 mm et en particulier de 0,5 à 5 mm.
  10. Agent pour le lavage mécanique de la vaisselle selon l'une quelconque des revendications 8 ou 9, caractérisé en ce qu'on obtient les compounds particulaires via un séchage par pulvérisation et/ou par transformation en granulés et/ou par extrusion et/ou par compression au rouleau et/ou par transformation en comprimés et/ou par solidification, mais en particulier via un séchage par pulvérisation et/ou par transformation en granulés.
  11. Agent pour le lavage mécanique de la vaisselle selon l'une quelconque des revendications 8 à 10, caractérisé en ce que les compounds particulaires présentent une densité de 0,1 à 2,0 g/cm3, de préférence de 0,2 à 1,6 g/cm3 et en particulier de 0,4 à 1,2 g/cm3.
  12. Agent pour le lavage mécanique de la vaisselle selon l'une quelconque des revendications 8 à 11, caractérisé en ce que les particules des sels de magnésium et/ou de zinc confectionnés avec une ou plusieurs substances actives et/ou builders possèdent une fraction pondérale de ces sels de magnésium et/ou de zinc s'élevant de 0,1 à 80 % en poids, de manière particulièrement préférée de 0,2 à 70 % en poids et en particulier de manière préférentielle de 0,5 à 60 % en poids, chaque fois rapportés au poids total des sels de magnésium et/ou de zinc confectionnés.
  13. Agent pour le lavage mécanique de la vaisselle selon l'une quelconque des revendications 8 à 12, caractérisé en ce que les sels de magnésium et/ou de zinc confectionnés avec une ou plusieurs substances actives et/ou builders contiennent des substances actives et/ou builders choisies parmi le groupe comprenant les phosphates, les carbonates, les hydrogénocarbonates, les sulfates, les silicates, les citrates, l'acide citrique, les acétates, de préférence dans des quantités de 20 à 99 % en poids, de préférence de 30 à 98 % en poids et de manière particulièrement préférée de 40 à 95 % en poids, chaque fois rapportés au poids total des sels de magnésium et/ou de zinc confectionnés.
  14. Agent pour le lavage mécanique de la vaisselle selon l'une quelconque des revendications 8 à 13, caractérisé en ce que les sels de magnésium et/ou de zinc confectionnés avec une ou plusieurs substances actives et/ou builders contiennent une ou plusieurs substances actives et/ou builders choisies parmi le groupe des agents tensioactifs, de préférence des agents tensioactifs non ioniques et/ou des carboxylates polymères, en particulier des polysulfocarboxylates.
  15. Agent pour le lavage mécanique de la vaisselle selon l'une quelconque des revendications 8 à 14, caractérisé en ce que les sels de magnésium et/ou de zinc confectionnés avec une ou plusieurs substances actives et/ou builders présentent en outre une enduction.
  16. Procédé de lavage mécanique de la vaisselle dans lequel on met en oeuvre un agent pour le lavage mécanique de la vaisselle selon l'une quelconque des revendications 1 à 15.
EP02767346A 2001-08-17 2002-08-08 Produits de lavage pour lave-vaisselle garantissant une protection amelioree contre la corrosion du verre Revoked EP1417291B1 (fr)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
DE2001140535 DE10140535B4 (de) 2001-08-17 2001-08-17 Maschinelles Geschirrspülmittel mit verbessertem Glaskorrosionsschutz
DE10140535 2001-08-17
DE10153555 2001-10-30
DE2001153555 DE10153555A1 (de) 2001-08-17 2001-10-30 Maschinelles Geschirrspülmittel mit Glaskorrosionsschutzeigenschaften
DE2001162145 DE10162145A1 (de) 2001-08-17 2001-12-18 Partikuläres maschinelles Geschirrspülmittel mit Glaskorrosionsschutzeigenschaften
DE10162145 2001-12-18
PCT/EP2002/008864 WO2003016444A2 (fr) 2001-08-17 2002-08-08 Produits de lavage pour lave-vaisselle garantissant une protection amelioree contre la corrosion du verre

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EP1417291A2 EP1417291A2 (fr) 2004-05-12
EP1417291B1 true EP1417291B1 (fr) 2010-04-07

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EP02767346A Revoked EP1417291B1 (fr) 2001-08-17 2002-08-08 Produits de lavage pour lave-vaisselle garantissant une protection amelioree contre la corrosion du verre

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US (1) US7153816B2 (fr)
EP (1) EP1417291B1 (fr)
AT (1) ATE463555T1 (fr)
AU (1) AU2002331215A1 (fr)
DE (1) DE50214339D1 (fr)
HU (1) HUP0401286A3 (fr)
PL (1) PL202632B1 (fr)
WO (1) WO2003016444A2 (fr)

Families Citing this family (48)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10153553A1 (de) * 2001-07-07 2003-06-12 Henkel Kgaa Nichtwäßrige "3in1"-Geschirrspülmittel II
DE10225116A1 (de) * 2002-06-06 2003-12-24 Henkel Kgaa Maschinelles Geschirrspülmittel mit verbessertem Glaskorrosionsschutz II
GB2392451A (en) * 2002-08-31 2004-03-03 Reckitt Benckiser Inc Liquid detergent compositions
DE10313455A1 (de) * 2003-03-25 2004-10-14 Henkel Kgaa Wasch- und Reinigungsmittel
DE10334047A1 (de) * 2003-07-25 2005-02-24 Clariant Gmbh Adsorbat aus Schichtsilicat und seine Verwendung
JP4410255B2 (ja) * 2003-10-16 2010-02-03 ザ プロクター アンド ギャンブル カンパニー ガラス製品の表面を腐食防止剤を使用して処理するための方法
US20050119154A1 (en) * 2003-10-16 2005-06-02 The Procter & Gamble Company Methods for protecting glassware from surface corrosion in automatic dishwashing appliances
US7241726B2 (en) * 2003-10-16 2007-07-10 The Procter & Gamble Company Complete-cycle methods for protecting glassware from surface corrosion in automatic dishwashing appliances
DE102004044411A1 (de) * 2004-09-14 2006-03-30 Basf Ag Reinigungsformulierungen für die maschinelle Geschirrreinigung enthaltend hydrophob modifizierte Polycarboxylate
MX2007013748A (es) * 2005-05-04 2008-01-28 Johnson Diversey Inc Sistema de lavado de loza que contiene bajos niveles de tensoactivo.
DE102005025332A1 (de) * 2005-05-31 2006-12-07 Henkel Kgaa Tensidcompound
DE102006028750A1 (de) * 2006-06-20 2007-12-27 Henkel Kgaa Reinigungsverfahren
WO2007025665A2 (fr) * 2005-09-02 2007-03-08 Henkel Kommanditgesellschaft Auf Aktien Agents de lavage
DE102005062648A1 (de) * 2005-12-23 2007-06-28 Henkel Kgaa Duftstofffixierung aus Wasch- und Reinigungsmitteln an harten und weichen Oberflächen
US8093200B2 (en) * 2007-02-15 2012-01-10 Ecolab Usa Inc. Fast dissolving solid detergent
ES2393813T3 (es) * 2007-04-04 2012-12-28 Henkel Ag & Co. Kgaa Detergente o agente de lavado que contiene un medio de blanqueo
EP2145032B1 (fr) 2007-05-04 2016-12-07 Ecolab Inc. Compositions comprenant des ions de dureté et du gluconate, et procédé les employant pour limiter la corrosion et le mordançage
US7828905B2 (en) * 2007-05-04 2010-11-09 Ecolab Inc. Cleaning compositions containing water soluble magnesium compounds and methods of using them
US20090082245A1 (en) * 2007-05-04 2009-03-26 Ecolab Inc. Method for formulating a branded cleaning product
US20090099054A1 (en) * 2007-05-04 2009-04-16 Ecolab Inc. Method for formulating a reduced phosphorus branded cleaning product or cleaning system
EP1997874A1 (fr) * 2007-05-25 2008-12-03 JohnsonDiversey, Inc. Système de nettoyage d'articles contenant du polysaccharide
EP2014757A1 (fr) * 2007-07-05 2009-01-14 JohnsonDiversey, Inc. Produit de rinçage
US20090032063A1 (en) * 2007-07-30 2009-02-05 Haas Geoffrey R Solid cleaning composition and method of use
US8450261B2 (en) * 2007-11-09 2013-05-28 The Procter & Gamble Company Cleaning compositions with monocarboxylic acid monomers dicarboxylic monomers, and monomers comprising sulfonic acid groups
CA2720346C (fr) * 2008-03-31 2015-05-05 The Procter & Gamble Company Composition automatique pour laver la vaisselle contenant un copolymere sulfone
DE102008020274A1 (de) 2008-04-22 2009-10-29 Henkel Ag & Co. Kgaa Verfahren zur Herstellung zinkhaltiger Wasch-oder Reinigungsmittelformkörper
DE102008020275A1 (de) 2008-04-22 2009-10-29 Henkel Ag & Co. Kgaa Zinkhaltiger Wasch- oder Reinigungsmittelformkörper
JP2012510342A (ja) * 2008-12-02 2012-05-10 ディバーシー・インコーポレーテッド カチオン性澱粉を含有する器物洗浄システム
MY158742A (en) * 2008-12-19 2016-11-15 Sanyo Chemical Ind Ltd Cleaning agent for electronic materials
DE102009027164A1 (de) * 2009-06-24 2010-12-30 Henkel Ag & Co. Kgaa Maschinelles Geschirrspülmittel
US20110021410A1 (en) * 2009-07-27 2011-01-27 Ecolab Usa Inc. Novel formulation of a ware washing solid controlling hardness
US8883035B2 (en) * 2009-07-27 2014-11-11 Ecolab Usa Inc. Formulation of a ware washing solid controlling hardness
CA2913731C (fr) 2013-06-04 2021-05-25 Monosol Llc Solutions d'etancheification de films solubles dans l'eau, procedes associes et articles associes
US9127235B2 (en) 2013-10-09 2015-09-08 Ecolab Usa Inc. Alkaline detergent composition containing a carboxylic acid/polyalkylene oxide copolymer for hard water scale control
US9487738B2 (en) 2013-10-09 2016-11-08 Ecolab Usa Inc. Solidification matrix comprising a carboxylic acid terpolymer
CA2928577C (fr) 2013-10-24 2018-11-27 Tobias Neil FOSTER Compositions et procedes pour eliminer les salissures sur des surfaces
EP3075832B1 (fr) 2015-03-30 2021-04-14 Dalli-Werke GmbH & Co. KG Composés d'acide aminé de manganèse dans des compositions de nettoyage
US10131620B2 (en) 2015-10-20 2018-11-20 Chang Chun Plastics Co., Ltd. Process for producing dimethyl carbonate
US9656943B2 (en) 2015-10-20 2017-05-23 Chang Chun Plastics Co. Ltd. Process for producing dimethyl carbonate
AU2017221146B2 (en) * 2016-02-19 2019-06-06 Rohm And Haas Company Low dust animal litter
DE102016212248A1 (de) * 2016-07-05 2018-01-11 Henkel Ag & Co. Kgaa Geschirrspülmittel enthaltend Zuckersäure und Aminocarbonsäure
DE102017223121A1 (de) * 2017-12-18 2019-06-19 Henkel Ag & Co. Kgaa Maschinelles Geschirrspülmittel mit verbesserter Klarspül- und Reinigungsleistung, Verfahren unter Einsatz dieses Mittels sowie Verwendung des Mittels
CN108117940A (zh) * 2018-01-02 2018-06-05 董春艳 一种不干胶清洗剂及其使用方法
DE102018205971A1 (de) 2018-04-19 2019-10-24 Henkel Ag & Co. Kgaa Korrosionsschutz für Glaswaren in einer Geschirrspülmaschine
US20210238502A1 (en) 2018-05-23 2021-08-05 Dow Global Technologies Llc Anhydrous autodish formulation
CN108998257A (zh) * 2018-06-15 2018-12-14 河北晨晨环境科技股份有限公司 全能清洗剂及其制备方法
CN111117794A (zh) * 2019-12-30 2020-05-08 杨粞淋 一种洗碗机复合洗涤剂的制备工艺
CN114058450B (zh) * 2021-12-03 2024-01-26 广州立白企业集团有限公司 一种稳定的颗粒型洗涤剂组合物及其制备方法

Family Cites Families (44)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1302543A (fr) 1969-06-17 1973-01-10
US3677820A (en) 1970-05-28 1972-07-18 Whirlpool Co Method to prevent glassware etching in a dishwasher
US3672820A (en) * 1970-12-07 1972-06-27 Ellis Corp Loading structure and method for laundry machines
DE2264230C3 (de) * 1972-12-30 1981-04-16 Henkel KGaA, 4000 Düsseldorf Schnellösliche, bleichend und desinfizierend wirkende Tablette
ATE16403T1 (de) * 1981-07-17 1985-11-15 Procter & Gamble Spuelhilfsmittel-zusammensetzung.
US4752409A (en) * 1985-06-14 1988-06-21 Colgate-Palmolive Company Thixotropic clay aqueous suspensions
US5413727A (en) 1985-06-14 1995-05-09 Colgate Palmolive Co. Thixotropic aqueous compositions containing long chain saturated fatty acid stabilizers
DE3743739A1 (de) 1987-12-23 1989-07-06 Basf Ag Wasserloesliche polymerisate enthaltende geschirrspuelmittel
US4917812A (en) * 1989-02-13 1990-04-17 The Procter & Gamble Company Granular automatic dishwasher detergent composition providing glassware protection containing insoluble zinc compound
US4933101A (en) * 1989-02-13 1990-06-12 The Procter & Gamble Company Liquid automatic dishwashing compositions compounds providing glassware protection
EP0439878A1 (fr) 1990-01-30 1991-08-07 Union Camp Corporation Détergent sous forme de gel clair pour machines à laver la vaisselle
IL97427A0 (en) 1990-03-13 1992-06-21 Colgate Palmolive Co Linear viscoelastic aqueous liquid detergent compositions,especially for automatic dishwashers,of improved high temperature stability
US5082578A (en) 1990-12-11 1992-01-21 Lever Brothers Company, Division Of Conopco, Inc. Fabric care compositions containing a polymeric fluorescent whitening agent
US5229027A (en) * 1991-03-20 1993-07-20 Colgate-Palmolive Company Aqueous liquid automatic dishwashing detergent composition comprising hypochlorite bleach and an iodate or iodide hypochlorite bleach stabilizer
AU655274B2 (en) * 1991-05-31 1994-12-15 Colgate-Palmolive Company, The Nonaqueous liquid, phosphate-free, improved automatic dishwashing composition containing enzymes
DK0530635T3 (da) 1991-08-29 1997-09-29 Benckiser Gmbh Joh A Neutralt middel til maskinopvask
US5308532A (en) 1992-03-10 1994-05-03 Rohm And Haas Company Aminoacryloyl-containing terpolymers
BR9306243A (pt) 1992-04-13 1998-06-23 Procter & Gamble Composiçao para lavagem automática de louça líquida tixotropica com enzima
US5691292A (en) 1992-04-13 1997-11-25 The Procter & Gamble Company Thixotropic liquid automatic dishwashing composition with enzyme
AU667600B2 (en) 1993-02-08 1996-03-28 Colgate-Palmolive Company, The Nonaqueous gelled automatic dishwashing composition containing enzymes
DE4417919A1 (de) 1994-05-24 1995-11-30 Henkel Kgaa Klarspülmittel mit biologisch abbaubaren Polymeren
DE4437486A1 (de) 1994-10-20 1996-04-25 Henkel Kgaa Kristalline Schichtsilikate in maschinellen Geschirrspülmitteln
US5516432A (en) 1994-11-21 1996-05-14 Rohm And Haas Company Method for prevention of scale formation in aqueous systems
DE19516957C2 (de) 1995-05-12 2000-07-13 Stockhausen Chem Fab Gmbh Wasserlösliche Copolymere und Verfahren zu ihrer Herstellung und ihre Verwendung
WO1998016613A1 (fr) 1996-10-17 1998-04-23 The Procter & Gamble Company Procede pour laver les textiles au moyen d'une composition detergente contenant un copolymere triple
US6210600B1 (en) 1996-12-23 2001-04-03 Lever Brothers Company, Division Of Conopco, Inc. Rinse aid compositions containing scale inhibiting polymers
JP4104704B2 (ja) 1997-10-01 2008-06-18 シスメックス株式会社 自動分析装置用洗浄剤
DE19819187A1 (de) 1998-04-30 1999-11-11 Henkel Kgaa Festes maschinelles Geschirrspülmittel mit Phosphat und kristallinen schichtförmigen Silikaten
DE19822939A1 (de) 1998-05-22 1999-11-25 Henkel Kgaa Nichtwäßrige viskose Geschirreinigungsmittel
DE19860670A1 (de) 1998-12-29 2000-08-10 Benckiser Nv Wasserlösliches Glas als Korrosionsschutz in einer Geschirrspülmaschine
US6448210B1 (en) * 1999-03-19 2002-09-10 Johnsondiversey, Inc. Liquid automatic dishwashing composition with glassware protection
DE19926378A1 (de) 1999-06-10 2000-12-14 Henkel Kgaa Maschinelle Geschirrspülmittel mit speziellen Phosphaten
AU5405300A (en) * 1999-06-25 2001-01-31 Henkel Kommanditgesellschaft Auf Aktien Packaging for a portion of an active substance
US6153913A (en) 1999-06-30 2000-11-28 United Microelectronics Corp. Electrostatic discharge protection circuit
AU5815000A (en) 1999-07-26 2001-02-13 Henkel Kommanditgesellschaft Auf Aktien Use of polyvinyl alcohols as detergent additives capable of removing soiling
CA2404579C (fr) 2000-03-29 2009-08-11 National Starch And Chemical Investment Holding Corporation Polymeres inhibant la formation de depots de carbonate et de phosphate de calcium dans des lave-vaisselle
DE20019913U1 (de) 2000-07-07 2001-03-29 Henkel KGaA, 40589 Düsseldorf Klarspülmittel II
GB0021113D0 (en) 2000-08-25 2000-10-11 Reckitt & Colmann Prod Ltd Improvements in or relating to containers
US6521576B1 (en) 2000-09-08 2003-02-18 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Polycarboxylic acid containing three-in-one dishwashing composition
MXPA03004624A (es) 2000-11-27 2003-09-05 Procter & Gamble Productos detergentes, metodos de uso de los mismos y fabricacion de los mismos.
DE10060533A1 (de) * 2000-12-06 2002-06-20 Henkel Kgaa Maschinelle Geschirrspülmittel und Klarspüler mit Geruchsabsorber
US6492312B1 (en) 2001-03-16 2002-12-10 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Water soluble sachet with a dishwashing enhancing particle
US6475977B1 (en) 2001-03-16 2002-11-05 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Water soluble sachet with a dishwasher composition
DE10153554A1 (de) 2001-07-07 2003-05-15 Henkel Kgaa Wäßrige "3in1"-Geschirrspülmittel II

Also Published As

Publication number Publication date
WO2003016444A2 (fr) 2003-02-27
HUP0401286A3 (en) 2009-06-29
EP1417291A2 (fr) 2004-05-12
AU2002331215A1 (en) 2003-03-03
US20050075258A1 (en) 2005-04-07
DE50214339D1 (de) 2010-05-20
PL202632B1 (pl) 2009-07-31
PL367794A1 (en) 2005-03-07
ATE463555T1 (de) 2010-04-15
US7153816B2 (en) 2006-12-26
WO2003016444A3 (fr) 2003-11-06
HUP0401286A2 (hu) 2004-12-28

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