EP2129761B1 - Détergents - Google Patents

Détergents Download PDF

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Publication number
EP2129761B1
EP2129761B1 EP08735746.3A EP08735746A EP2129761B1 EP 2129761 B1 EP2129761 B1 EP 2129761B1 EP 08735746 A EP08735746 A EP 08735746A EP 2129761 B1 EP2129761 B1 EP 2129761B1
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EP
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Prior art keywords
group
carbon atoms
branched
linear
saturated
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EP08735746.3A
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German (de)
English (en)
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EP2129761A1 (fr
Inventor
Nadine Warkotsch
Arnd Kessler
Johannes Zipfel
Marc-Steffen Schiedel
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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 DE102007016389A external-priority patent/DE102007016389A1/de
Priority claimed from DE102007023875A external-priority patent/DE102007023875A1/de
Priority claimed from DE200710038482 external-priority patent/DE102007038482A1/de
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to EP12166941.0A priority Critical patent/EP2487232B1/fr
Publication of EP2129761A1 publication Critical patent/EP2129761A1/fr
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Publication of EP2129761B1 publication Critical patent/EP2129761B1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3788—Graft polymers
    • 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
    • C11D3/2096—Heterocyclic compounds
    • 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
    • C11D3/22—Carbohydrates or derivatives 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
    • C11D3/28—Heterocyclic compounds containing nitrogen in the ring
    • 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
    • C11D3/32—Amides; Substituted amides
    • 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
    • C11D3/34—Organic compounds containing sulfur
    • 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
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/3454—Organic compounds containing sulfur containing sulfone groups, e.g. vinyl sulfones
    • 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
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/349—Organic compounds containing sulfur additionally containing nitrogen atoms, e.g. nitro, nitroso, amino, imino, nitrilo, nitrile groups containing compounds or their derivatives or thio urea
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/364—Organic compounds containing phosphorus containing nitrogen
    • 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
    • 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
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • 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
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • C11D3/3742—Nitrogen containing silicones
    • C11D2111/14—

Definitions

  • the present patent application relates to detergents for the automatic cleaning of dishes.
  • Machine-washed dishes are often subject to more stringent requirements today than manually-washed dishes. So the dishes after machine cleaning should not only be completely free from food debris but also, for example, have no whitish, based on water hardness or other mineral salts stains that come from lack of wetting agent from dried water droplets.
  • the patent application DE 100 50 622 A1 relates to automatic dishwashing detergents containing from 1 to 94.9% by weight of builders, from 5 to 30% by weight of nonionic surfactants and from 0.1 to 70% by weight of copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally further ionic or nonionic monomers contain
  • Compounds of the general formula (I) can be obtained by reacting diisocyanates, bis-chloroformic acid esters or amides or phosgene with thiols, alcohols or amines containing the structural element Y.
  • these starting compounds having the structural element Y have at least 2 of the said functional groups.
  • Suitable end groups are compounds which otherwise correspond to the structural element Y but are only monofunctional.
  • the polycarbonate, polyurethane and / or polyurea-polyorganosiloxane compound preferably has the structural element of the formula (I) several times in succession, the multiply occurring in each case corresponding radicals A or Y or Z or R 1 or R 2 or R 3 may be the same or different.
  • acid addition compound means a salt-like compound which can be obtained by protonation of basic groups in the molecule, such as in particular the optionally present amino groups, for example by reaction with inorganic or organic acids.
  • the acid addition compounds may be used as such or may optionally form under conditions of use of the compounds defined above.
  • the polycarbonate, polyurethane and / or polyurea-polyorganosiloxane compounds preferably contain on average at least two, in particular at least three, of said polyorganosiloxane structural elements.
  • R 4 is preferably a straight-chain or cyclic or branched, saturated or unsaturated or aromatic C 1 - to C 20 -, in particular C 1 -C 9 hydrocarbon radical, particularly preferably methyl or phenyl, and p is preferably 1 to 199, particularly preferably 1 to 99. In a preferred embodiment, all radicals R 4 are the same.
  • Preferred polycarbonate, polyurethane and / or polyurea polyorganosiloxane compounds used according to the invention are linear, ie all Y units in the structural element of the formula (I) are in each case divalent radicals.
  • branched compounds are also included in which at least one of the radicals Y is trivalent or polyvalent is tetravalent, so that branched structures with linear repeating structures of structural elements of formula (I) form.
  • R 2 and R 3 are preferably methyl groups.
  • a further embodiment relates to the multiple regular occurrence of -O-groupings in at least one of the units Y, R 1 , R 2 and / or R 3 according to the structural element of the formula (I), preferably in the form of oligoethoxy and / or oligopropoxy groups their degrees of oligomerization are preferably in the range of 2 to 60.
  • At least one of the units Y, R 1 , R 2 and / or R 3 according to the structural element of the formula (I) contains oligoethylenimine groups whose degrees of oligomerization are in particular in the range from 10 to 15 000.
  • compositions according to the invention preferably contain from 0.01% by weight to 5% by weight, in particular from 0.5% by weight to 3% by weight, of such active ingredient described here (the polycarbonate, polyurethane and / or polyurea polyorganosiloxane -Connection).
  • compositions according to the invention can moreover contain all ingredients conventionally contained in such compositions, in particular builder (s), bleach and surfactant (s), provided that they do not unduly interact negatively with the active substance essential to the invention during storage and / or application of the composition.
  • builder s
  • bleach s
  • surfactant s
  • Preferred automatic dishwasher detergents according to the invention have a weight fraction of nonionic surfactant of from 1% by weight to 10% by weight, preferably from 2% by weight to 8% by weight and in particular from 2% by weight to 6% by weight.
  • the stated C chain lengths and degrees of alkoxylation or degrees of ethoxylation of the stated nonionic surfactants represent statistical averages which may be an integer or a fractional number for a specific product. Due to the manufacturing process, commercial products of the formulas mentioned are usually not made of an individual representative, but of mixtures, resulting in both the C chain lengths as also give average values for the degrees of ethoxylation or degrees of alkoxylation and, consequently, fractional numbers.
  • nonionic surfactants can be used not only as individual substances but also as surfactant mixtures of two, three, four or more surfactants. Mixtures of surfactants are not mixtures of nonionic surfactants which fall in their entirety under one of the abovementioned general formulas, but rather mixtures which contain two, three, four or more nonionic surfactants which can be described by different general formulas ,
  • automatic dishwasher detergents preferred according to the invention contain one or more builders.
  • the builders include in particular phosphates, silicates, carbonates and organic cobuilders.
  • organic co-builders are polycarboxylates / polycarboxylic acids, polymeric carboxylates, aspartic acid, polyacetals, dextrins and other organic cobuilders. 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 the free acid and / or their sodium salts.
  • these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, and mixtures of these.
  • the free acids also typically 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.
  • One embodiment of preferred automatic dishwashing detergents according to the invention contains citrate as one of its essential builders.
  • Automatic dishwashing agents according to the invention which contain 5 to 60% by weight, preferably 10 to 50% by weight and in particular 15 to 45% by weight, of citrate are preferred according to the invention.
  • automatic dishwashing agents contain as builder crystalline layered silicates of the general formula NaMSi x O 2x + 1 .yH 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4 where particularly preferred values for x are 2, 3 or 4 and y is a number from 0 to 33, preferably from 0 to 20. It is also possible to use amorphous sodium silicates with a Na 2 O: SiO 2 module 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, which are preferably delayed release and have secondary washing properties.
  • Machine dishwashing detergents preferred in the context of the present invention comprise from 2 to 15% by weight, preferably from 3 to 12% by weight and in particular from 4 to 8% by weight, of silicate (s).
  • alkali metal phosphates in particular trisodium polyphosphate, can also be used as builders.
  • Alkaliphosphat is the summary term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO 3 ) n and orthophosphoric H 3 PO 4 in addition to high molecular weight representatives.
  • the phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance.
  • Sodium dihydrogen phosphate, NaH 2 PO 4 exists as a dihydrate (density 1.91 gcm -3 , melting point 60 ° C) and as a monohydrate (density 2.04 gcm -3 ). Both salts are white powders which are very soluble in water and which lose their water of crystallization when heated and at 200 ° C into the weak acid diphosphate (disodium hydrogen diphosphate, Na 2 H 2 P 2 O 7 ), at higher temperature in sodium trimetaphosphate (Na 3 P 3 O 9 ) and pass on Madrell's salt.
  • NaH 2 PO 4 is acidic; It arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed.
  • Potassium dihydrogen phosphate (potassium phosphate primary or monobasic phosphate, potassium biphosphate, KDP), KH 2 PO 4 , is a white salt of density 2.33 gcm -3 , has a melting point of 253 ° C (decomposition to form (KPO 3 ) x , potassium polyphosphate) and is easily soluble in water.
  • Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HPO 4 , is a colorless, very slightly water-soluble crystalline salt.
  • Disodium hydrogen phosphate is prepared by neutralization of phosphoric acid with soda solution using phenolphthalein as an indicator.
  • Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K 2 HPO 4 , is an amorphous, white salt that is readily soluble in water.
  • Trisodium phosphate, tertiary sodium phosphate, Na 3 PO 4 are colorless crystals which have a density of 1.62 gcm -3 as dodecahydrate and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P 2 O 5 ) has a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P 2 O 5 ) have a density of 2.536 gcm -3 .
  • Trisodium phosphate is readily soluble in water under alkaline reaction and is prepared by evaporating a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH.
  • Tripotassium phosphate (tertiary or tribasic potassium phosphate), K 3 PO 4 , is a white, deliquescent, granular powder of density 2.56 gcm -3 , has a melting point of 1340 ° C and is readily soluble in water with an alkaline reaction. It arises, for example, when heating Thomasschlacke with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over the corresponding sodium compounds in the detergent industry.
  • Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 O 7 , exists in anhydrous form (density 2.534 gcm -3 , melting point 988 ° C, also indicated 880 ° C) and as decahydrate (density 1.815-1.836 gcm -3 , melting point 94 ° C. under water loss).
  • Na 4 P 2 O 7 is formed on heating of disodium phosphate to> 200 ° C or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying.
  • the decahydrate complexes heavy metal salts and hardness agents and therefore reduces the hardness of the water.
  • Potassium diphosphate (potassium pyrophosphate), K 4 P 2 O 7 , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm -3 , which is soluble in water, the pH being 1% Solution at 25 ° C is 10.4. Condensation of NaH 2 PO 4 or KH 2 PO 4 results in higher mol.
  • Sodium and potassium phosphates in which one can distinguish cyclic representatives, the sodium or Kaliummetaphosphate and chain types, the sodium or potassium polyphosphates.
  • Pentakaliumtriphosphat, K 5 P 3 O 10 (potassium tripolyphosphate), for example, in the form of a 50 wt .-% solution (> 23% P 2 O 5 , 25% K 2 O) in the trade.
  • 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
  • An inventive composition contains in a preferred embodiment, up to 60 wt .-%, in particular 35 wt .-% to 50 wt .-% phosphate. In further preferred embodiments, it contains from 5% to 60%, preferably from 10% to 50% and more preferably from 15% to 45% by weight citrate and is phosphate free or contains 15% Wt .-% to 25 wt .-% phosphate.
  • Suitable builders are polymeric polycarboxylates, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass 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 of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.
  • 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 relative molecular weight, based on free acids, is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution.
  • the content of the automatic dishwashing agents in (co) polymeric polycarboxylates is preferably from 0.5 to 20% by weight and in particular from 3 to 10% by weight.
  • Preferred automatic dishwashing agents according to the invention also contain one or more bleaching agents.
  • bleaching agents include 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 peracid salts or Peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • bleaching agents from the group of organic bleaching agents can also be used.
  • Typical organic bleaching agents 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.
  • Machine dishwashing detergents which contain from 1 to 20% by weight, preferably from 2 to 15% by weight and in particular from 4 to 12% by weight, of sodium percarbonate are preferred according to the invention.
  • chlorine or bromine-releasing substances can also be used as the bleaching agent.
  • suitable chlorine or bromine releasing materials are, for example, heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium.
  • DICA dichloroisocyanuric acid
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.
  • the automatic dishwasher detergents according to the invention may additionally contain bleach activators.
  • 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.
  • Preference is given to polyacylated alkylenediamines, with tetraacetylethylenediamine (TAED) having proven particularly suitable.
  • TAED tetraacetylethylenediamine
  • Bleach activators in particular TAED, are preferably used in amounts of up to 10% by weight, in particular 0.1% by weight to 8% by weight, especially 2 to 8% by weight and more preferably 2 to 6% by weight, in each case based on the total weight of the bleach activator-containing agents used.
  • bleach catalysts can also be used. These substances are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo-salene complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can be used as bleach catalysts.
  • complexes of manganese in the oxidation state II, III or IV which preferably contain one or more macrocyclic ligands with the donor functions N, NR, PR, O and / or S.
  • ligands are used which have nitrogen donor functions.
  • bleach catalyst (s) in the compositions of the invention, which as macromolecular ligands 1,4,7-trimethyl-1,4,7-triazacyclononan (Me-TACN), 1,4,7-triazacyclononane (TACN ), 1,5,9-trimethyl-1,5,9-triazacyclododecane (Me-TACD), 2-methyl-1,4,7-trimethyl-1,4,7-triazacyclononane (Me / Me-TACN) and or 2-methyl-1,4,7-triazacyclononane (Me / TACN).
  • Me-TACN 1,4,7-trimethyl-1,4,7-triazacyclononan
  • TACN 1,4,7-triazacyclononane
  • TACD 1,5,9-trimethyl-1,5,9-triazacyclododecane
  • Me-TACD 2-methyl-1,4,7-trimethyl-1,4,7-triazacyclononane
  • 2-methyl-1,4,7-triazacyclononane
  • Automatic dishwashing detergent containing a bleach catalyst selected from the group of bleach-enhancing transition metal salts and transition metal complexes, preferably from the group of complexes of manganese with 1,4,7-trimethyl-1,4,7-triazacyclononane (Me 3 -TACN) or 1,2 , 4,7-tetramethyl-1,4,7-triazacyclononane (Me 4 -TACN) are preferred according to the invention, since in particular the cleaning result can be significantly improved by the aforementioned bleach catalysts.
  • the aforementioned bleach-enhancing transition metal complexes are used in customary amounts, preferably in an amount of up to 5% by weight, in particular of 0.0025% by weight to 1% by weight and more preferably of 0 , 01 wt .-% to 0.30 wt .-%, each based on the total weight of the agents used. In special cases, however, more bleach catalyst can be used.
  • Preferred automatic dishwashing agents according to the invention additionally comprise a complexing agent, preferably a phosphonic acid or a phosphonate and / or an aminocarboxylic acid, among these preferably methylglycinediacetic acid (MGDA) and / or nitrilotriacetic acid (NTA), provided their use is not objectionable for ecological reasons.
  • a complexing agent preferably a phosphonic acid or a phosphonate and / or an aminocarboxylic acid, among these preferably methylglycinediacetic acid (MGDA) and / or nitrilotriacetic acid (NTA)
  • the complex-forming phosphonates comprise a number of different compounds such as, for example, diethylenetriaminepenta (methylenephosphonic acid) (DTPMP).
  • DTPMP diethylenetriaminepenta
  • hydroxyalkane or aminoalkanephosphonates are preferred.
  • 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9).
  • Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B. as the hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP used.
  • 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.
  • automatic dishwashing detergents which contain as phosphonates 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or diethylenetriaminepenta (methylenephosphonic acid) (DTPMP).
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • DTPMP diethylenetriaminepenta
  • automatic dishwashing agents according to the invention may also contain two or more different phosphonates and / or aminicarboxylic acids. Particular preference is given to those automatic dishwashing compositions which contain as phosphonates both 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and diethylenetriaminepenta (methylenephosphonic acid) (DTPMP), the weight ratio of HEDP to DTPMP being between 20: 1 and 1:20, preferably between 15: 1 and 1:15 and in particular between 10: 1 and 1:10.
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • DTPMP diethylenetriaminepenta
  • the proportion by weight of these complexing agents in particular the sum of the proportions by weight of 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and methylglycinediacetic acid (MGDA) is preferably 0.5 to 14% by weight, preferably 1 to 12% by weight and in particular 2 to 8 wt .-%.
  • an agent according to the invention contains up to 5% by weight, in particular from 0.5% by weight to 2% by weight, of phosphonate.
  • preferred automatic dishwasher detergents contain further ingredients, preferably active ingredients from the group of polymers, enzymes, corrosion inhibitors and fragrances and / or dyes.
  • the group of washing- or cleaning-active polymers includes, for example, the polymers and rinse-aid polymers which act as softeners and, if desired, can be used in addition to the active ingredient used according to the invention.
  • cationic, anionic and amphoteric polymers can be used in detergents or cleaners in addition to nonionic polymers.
  • the carboxylic acid and / or sulfonic acid groups may be wholly or partially in neutralized form, i.
  • the acidic acid hydrogen atom may be exchanged in some or all of the acid groups for metal ions, preferably alkali metal ions and especially sodium ions.
  • metal ions preferably alkali metal ions and especially sodium ions.
  • partially or fully neutralized sulfonic acid-containing copolymers is preferred according to the invention.
  • “Cationic polymers” in the context of the present invention are polymers which carry a positive charge in the polymer molecule. This can be realized, for example, by (alkyl) ammonium groups or other positively charged groups present in the polymer chain.
  • Particularly preferred cationic polymers come from the groups of quaternized cellulose derivatives, the polysiloxanes with quaternary groups, the cationic guar derivatives, the polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, the copolymers of vinylpyrrolidone with quaternized derivatives of dialkylamino and methacrylates, the vinylpyrrolidone-methoimidazolinium chloride copolymers, the quaternized polyvinyl alcohols or the polymers specified under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.
  • Amphoteric polymers in the sense of the present invention have not only cationic groups but also anionic groups or monomer units. Such anionic monomer units are derived, for example, from the group of linear or branched, saturated or unsaturated carboxylates, linear or branched, saturated or unsaturated phosphonates, linear or branched, saturated or unsaturated sulfates or linear or branched, saturated or unsaturated sulfonates.
  • Preferred monomer units are acrylic acid, (meth) acrylic acid, (dimethyl) acrylic acid, (ethyl) acrylic acid, cyanoacrylic acid, vinylessingic acid, allylacetic acid, crotonic acid, maleic acid, fumaric acid, cinnamic acid and its derivatives, allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid or the allylphosphonic acids.
  • Preferred employable amphoteric polymers are from the group of the alkylacrylamide / acrylic acid copolymers, the alkylacrylamide / methacrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid copolymers, the alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth ) -acrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / alkymethacrylate / alkylaminoethylmethacrylate / alkylmethacrylate copolymers and the copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally further ionic or non
  • Preferred zwitterionic polymers are from the group of acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali metal and ammonium salts, the acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali metal and ammonium salts and the methacroylethylbetaine / methacrylate copolymers.
  • G - represents a counterion, preferably a counterion from the group chloride, bromide, iodide, sulfate, hydrogen sulfate, methosulfate, lauryl sulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate), cumenesulfonate, xylenesulfonate, phosphate, citrate, formate, acetate or mixtures thereof.
  • R 19 and R 22 in the above formula are selected from -CH 3 , -CH 2 -CH 3 , -CH 2 -CH 2 -CH 3 , -CH (CH 3 ) -CH 3 , -CH 2 -OH , -CH 2 -CH 2 -OH, -CH (OH) -CH 3 , -CH 2 -CH 2 -CH 2 -OH, -CH 2 -CH (OH) -CH 3 , -CH (OH) -CH 2 -CH 3 , and - (CH 2 CH 2 -O) n H.
  • Detergents contain the abovementioned cationic and / or amphoteric polymers, preferably in amounts of up to 10% by weight, in particular between 0.01 and 10% by weight, in each case based on the total weight of the composition.
  • enzymes can be used. These include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents or cleaning agents, which are preferably used accordingly.
  • Detergents or cleaning agents contain enzymes preferably in total amounts of 1 ⁇ 10 -6 to 5 wt .-% based on active protein. The protein concentration can be determined by known methods, for example the BCA method or the biuret method.
  • subtilisin type those of the subtilisin type are preferable.
  • these are the subtilisins BPN 'and Carlsberg and their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase which can no longer be assigned to the subtilisins in the narrower sense, Proteinase K and the proteases TW3 and TW7.
  • amylases which can be used according to the invention are the ⁇ -amylases from Bacillus licheniformis, B. amyloliquefaciens, B. stearothermophilus, Aspergillus niger and A. oryzae, as well as the further developments of the aforementioned amylases which are improved for use in detergents and cleaners. Furthermore, for this purpose, the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).
  • DSM 12368 Bacillus sp. A 7-7
  • CTTase cyclodextrin glucanotransferase
  • lipases or cutinases are also usable according to the invention.
  • these include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L.
  • the cutinases can be used, which have been originally isolated from Fusarium solani pisi and Humicola insolens. It is also possible to use lipases, or cutinases, whose initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii.
  • Oxidoreductases for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention to increase the bleaching effect.
  • the enzymes can be used in any form known in the art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or stabilizers.
  • the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer.
  • further active ingredients for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied.
  • Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes.
  • such granules for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.
  • a protein and / or enzyme may be particularly protected during storage against damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage.
  • damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage.
  • inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases.
  • Detergents may contain stabilizers for this purpose; the provision of such means constitutes a preferred embodiment of the present invention.
  • Glass corrosion inhibitors prevent the occurrence of haze, streaks and scratches, but also iridescence of the glass surface of machine-cleaned glasses.
  • Preferred glass corrosion inhibitors come from the group of magnesium and zinc salts and magnesium and zinc complexes.
  • the spectrum of the invention preferred zinc salts preferably organic acids, particularly preferably organic carboxylic 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 below 0.01 have mg / l, to those 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.
  • the first group of zinc salts includes, for example, zinc citrate, zinc oleate and zinc stearate, and the group of soluble zinc salts includes, for example, zinc formate, zinc acetate, zinc lactate and zinc gluconate.
  • the glass corrosion inhibitor at least one zinc salt of an organic carboxylic acid, particularly preferably a zinc salt from the group zinc stearate, zinc oleate, zinc gluconate, zinc acetate, zinc lactate and zinc citrate.
  • Zinc ricinoleate, zinc abietate and zinc oxalate are also preferred.
  • the content of zinc salt in detergents or cleaners is preferably between 0.1 and 5% by weight, preferably between 0.2 and 4% by weight and in particular between 0.4 and 3% by weight.
  • the content of zinc in oxidized form (calculated as Zn 2+ ) between 0.01 to 1 wt .-%, preferably between 0.02 to 0.5 wt .-% and in particular between 0.04 to 0, 5 wt .-%, each based on the total weight of the glass corrosion inhibitor-containing agent.
  • Corrosion inhibitors serve to protect the items to be washed or the machine, with particular silver protectants being of particular importance in the field of automatic dishwashing. It is possible to use the known substances of the prior art. In general, silver protectants selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes can be used in particular. Particularly preferred to use are benzotriazole and / or alkylaminotriazole.
  • 3-amino-5-alkyl-1,2,4-triazoles or their physiologically tolerated salts preference is given to using 3-amino-5-alkyl-1,2,4-triazoles or their physiologically tolerated salts, these substances being particularly preferably used in a concentration of 0.001 to 10% by weight, preferably 0.0025 to 2 Wt .-%, particularly preferably 0.01 to 0.04 wt .-% are used.
  • disintegration aids so-called tablet disintegrants
  • disintegration aids in amounts of from 0.5 to 10% by weight, preferably from 1 to 7% by weight and in particular from 1 to 5% by weight, based in each case on the total weight of the disintegration assistant-containing agent.
  • Disintegrating agents based on cellulose are used as preferred disintegrating agents, so that preferred washing or cleaning agents comprise such cellulose-based disintegrating agents in amounts of from 0.5 to 10% by weight, preferably from 1 to 7% by weight and in particular from 1 to 5% by weight. % contain.
  • the cellulose used as a disintegration aid is preferably not used in finely divided form, but converted into a coarser form, for example granulated or compacted, before it is added to the premixes to be tabletted.
  • the particle sizes of such disintegrating agents are usually above 200 .mu.m, preferably at least 90 wt .-% between 300 .mu.m and 1600 .mu.m and in particular at least 90 wt .-% between 400 .mu.m and 1200 .mu.m.
  • Preferred disintegration aids preferably a disintegration aid based on cellulose, preferably in granular, cogranulated or compacted form, are present in the disintegrating agent-containing agents in amounts of from 0.5 to 10% by weight, preferably from 1 to 7% by weight and in particular from 1 to 5 wt .-%, each based on the total weight of the disintegrating agent-containing agent.
  • gas-evolving effervescent systems can furthermore be used as tablet disintegration auxiliaries.
  • the gas-evolving effervescent system may consist of a single substance that releases a gas upon contact with water.
  • these compounds mention should be made in particular of magnesium peroxide, which liberates oxygen on contact with water.
  • preferred effervescent systems consist of at least two components which react with one another to form gas, for example of alkali metal carbonate and / or bicarbonate and an acidifying agent which is suitable for liberating carbon dioxide from the alkali metal salts in aqueous solution.
  • Acidificationsmittel which release carbon dioxide from the alkali metal salts in aqueous solution, for example, boric acid and alkali metal hydrogen sulfates, alkali metal dihydrogen phosphates and other inorganic salts can be used.
  • organic acidifying agents preference is given to using organic acidifying agents, the citric acid being a particularly preferred acidifying agent. Acidifying agents in the effervescent system from the group of organic di-, tri- and oligocarboxylic acids or mixtures are preferred.
  • fragrance compounds e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used.
  • mixtures of different fragrances are used, which together produce an attractive fragrance.
  • perfume oils may also contain natural fragrance mixtures such as are available from vegetable sources, e.g. Pine, Citrus, Jasmine, Patchouly, Rose or Ylang-Ylang oil.
  • the fragrances can be processed directly, but it can also be advantageous to apply the fragrances on carriers that provide a slower fragrance release for long-lasting fragrance.
  • carrier materials for example, cyclodextrins have been proven, the cyclodextrin-perfume complexes can be additionally coated with other excipients.
  • Preferred dyes the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the agents and to light and no pronounced substantivity to the substrates to be treated with the dye-containing agents such as textiles, glass, ceramics or plastic dishes do not stain them.
  • the automatic dishwashing compositions according to the invention can be formulated in solid or liquid form but can also be present, for example, as a combination of solid and liquid forms.
  • Powder, granules, extrudates or compactates, in particular tablets, are particularly suitable as firm supply forms.
  • the liquid supply forms based on water and / or organic solvents may be thickened, in the form of gels.
  • Inventive agents can be formulated as single-phase or multi-phase products.
  • automatic dishwashing detergents with one, two, three or four phases are preferred.
  • Machine dishwashing detergents characterized in that they are in the form of a prefabricated dosing unit with two or more phases, are particularly preferred.
  • the individual phases of multiphase agents may have the same or different states of matter.
  • Machine dishwashing detergents which have at least two different solid phases and / or at least two liquid phases and / or at least one solid and at least one liquid phase are preferred.
  • Automatic dishwasher detergents according to the invention are preferably prefabricated to form metering units. These metering units preferably comprise the necessary for a cleaning cycle amount of washing or cleaning-active substances. Preferred metering units have a weight between 6 g and 30 g, preferably between 14 g and 26 g and in particular between 15 g and 22 g.
  • the volume of the aforementioned metering units and their spatial form are selected with particular preference so that a metering of the prefabricated units is ensured via the metering chamber of a dishwasher.
  • the volume of the dosing unit is therefore preferably between 10 ml and 35 ml, preferably between 12 ml and 30 ml and in particular between 15 and 25 ml.
  • the automatic dishwasher detergents according to the invention in particular the prefabricated metering units, have a water-soluble coating, with particular preference.
  • the present application further relates to a method for cleaning dishes in a dishwasher using automatic dishwashing agents according to the invention, wherein the automatic dishwashing agents are preferably metered into the interior of a dishwasher during the passage of a dishwashing program, before the main wash cycle or during the main wash cycle.
  • the dosing or the entry of the agent according to the invention in the interior of the dishwasher can be done manually, but preferably the agent is metered by means of the dosing of the dishwasher in the interior of the dishwasher.
  • no additional rinse aid and no additional water softening is metered into the interior of the dishwasher.
  • compositions according to the invention are distinguished from conventional automatic dishwasher detergents by an improved rinsing action and an improved drying action.
  • a dishwasher detergent according to the invention as a rinse aid in automatic dishwashing and the use of a dishwasher detergent according to the invention as a drying accelerator in automatic dishwashing are therefore further objects of the present application.

Claims (13)

  1. Agent pour le lavage mécanique de la vaisselle, caractérisé en ce qu'il contient un composé polycarbonate-, polyuréthane- et/ou polyurée-polyorganosiloxane, contenant au moins un élément structural de la Formule (I) :

            -Y-A-(C=O)-A-     (I),

    dans laquelle chaque A est indépendamment choisi parmi S, O et NR1,
    Y est choisi parmi des radicaux hydrocarbure bivalents à polyvalents, en particulier tétravalents, à chaîne droite, cycliques ou ramifiés, saturés, insaturés ou aromatiques, substitués ou non substitués comprenant jusqu'à 1 000 atomes de carbone (les atomes de carbone d'un motif polyorganosiloxane éventuellement contenu n'étant pas comptés), qui peuvent contenir un ou plusieurs groupes choisis parmi -O-, -(CO)-, -NH-, - NR2-, -(N+R2R3)- et un motif polyorganosiloxane comprenant de 2 à 1 000 atomes de silicium,
    R1 est l'hydrogène ou un radical hydrocarbure à chaîne droite, cyclique ou ramifié, saturé, insaturé ou aromatique comprenant jusqu'à 40 atomes de carbone, qui peut contenir un ou plusieurs groupes choisis parmi -O-, -(CO)-, -NH- et -NR2-,
    R2 est un radical hydrocarbure à chaîne droite, cyclique ou ramifié, saturé, insaturé ou aromatique comprenant jusqu'à 40 atomes de carbone, qui peut contenir un ou plusieurs groupes choisis parmi -O-, -(CO)- et -NH-,
    R3 est un radical hydrocarbure à chaîne droite, cyclique ou ramifié, saturé, insaturé ou aromatique comprenant jusqu'à 100 atomes de carbone, qui peut contenir un ou plusieurs groupes choisis parmi -O-, -(CO)- et -NH-, ou est un radical bivalent qui constitue des structures cycliques à l'intérieur du radical Y,
    ou bien l'un des radicaux A voisins de Y, ou les deux, peuvent former un radical hétérocyclique contenant de l'azote avec le radical Y qui se trouve entre eux,
    et, dans le composé total, les radicaux A, respectivement Y, respectivement R1, respectivement R2, respectivement R3 figurant dans la Formule (I) ne doivent pas être tous identiques, à la condition que, dans le composé total,
    au moins l'un des radicaux Y comprenne un motif polyorganosiloxane comprenant de 2 à 1 000 atomes de silicium, et au moins l'un des motifs Y selon l'élément structural de la Formule (I) comprenne un groupement - (N+R2R3)-, ou son composé d'addition acide et/ou sel.
  2. Agent selon la revendication 1, caractérisé en ce que l'élément structural polyorganosiloxane présent dans les composés polycarbonate-, polyuréthane- et/ou polyurée-polyorganosiloxane possède la structure -(SiR4 2O)p-(SiR4 2)-, dans laquelle R4 est un radical hydrocarbure à chaîne droite, cyclique ou ramifié, saturé, insaturé ou aromatique comprenant jusqu'à 20 atomes de carbone, et p = de 1 à 999.
  3. Agent selon la revendication 2, caractérisé en ce que les composés polycarbonate-, polyuréthane- et/ou polyurée-polyorganosiloxane dans le produit contiennent au moins deux, en particulier au moins trois, desdits éléments structuraux polyorganosiloxane.
  4. Agent selon l'une des revendications 1 à 3, caractérisé en ce que, dans au moins l'un des motifs Y, R1, R2 et/ou R3 selon l'élément structural de la Formule (I), sont présents des groupes oligoéthoxy et/ou oligopropoxy dont les degrés d'oligomérisation se situent en particulier dans la gamme allant de 2 à 60.
  5. Agent selon l'une quelconque des revendications 1 à 4, caractérisé en ce que, dans au moins l'un des motifs Y, R1, R2 et/ou R3 selon l'élément structural de la Formule (I), sont présents des groupes oligoéthylène imine dont les degrés d'oligomérisation se situent en particulier dans la gamme allant de 10 à 15 0000.
  6. Agent selon l'une des revendications 1 à 5, caractérisé en ce que le composé de la Formule (I) est un composé polycarbonate- et/ou polyuréthane-polyorganosiloxane qui contient au moins un élément structural de la Formule (II) ou de la Formule (III) :

            -A-Y-A-(CO)-O-Z-(CHOH)-Z-O-(CO)-     (II),

            -A-Y-A-(CO)-O-(CHCH2OH)-Z-O-(CO)-     (III),

    dans lesquelles A et Y ont les significations énoncées pour la Formule (I) et Z est choisi parmi les radicaux hydrocarbure bivalents, à chaîne droite, cycliques ou ramifiés, saturés ou insaturés, éventuellement substitués comprenant de 1 à 12 atomes de carbone.
  7. Agent selon l'une des revendications 1 à 6, caractérisé en ce qu'il contient de 0,01 % en poids à 5 % en poids, en particulier de 0,5 % en poids à 3 % en poids de la substance active.
  8. Agent selon l'une des revendications 1 à 7, caractérisé en ce qu'il contient un agent tensioactif non ionique de la formule générale

            R6-CH(OH)CH2O-(AO)w-(A'O)x-(A"O)y-(A"'O)z-R7,

    dans laquelle
    R6 représente un radical alkyle ou alcényle en C6 à C24 à chaîne droite ou ramifié, saturé ou mono- ou polyinsaturé ;
    R7 représente un radical hydrocarbure linéaire ou ramifié comprenant de 2 à 26 atomes de carbone ;
    A, A', A" et A'" représentent indépendamment les uns des autres un radical issu du groupe -CH2CH2, -CH2CH2-CH2, -CH2-CH(CH3), -CH2-CH2-CH2-CH2, -CH2-CH(CH3)-CH2-, -CH2-CH(CH2-CH3),
    w, x, y et z représentent indépendamment les uns des autres des valeurs comprises entre 0,5 et 120, x, y et/ou z pouvant également être 0.
  9. Agent selon l'une des revendications 1 à 8, caractérisé en ce qu'il contient de 1 % en poids à 10 % en poids, de préférence de 2 % en poids à 8 % en poids et en particulier de 2 % en poids à 6 % en poids d'un agent tensioactif non ionique et/ou jusqu'à 60 % en poids, en particulier de 35 % en poids à 50 % en poids de phosphate.
  10. Agent selon l'une des revendications 1 à 9, caractérisé en ce qu'il contient de 5 % en poids à 60 % en poids, de préférence de 10 % en poids à 50 % en poids et en particulier de 15 % en poids à 45 % en poids de citrate et est exempt de phosphate ou contient de 15 % en poids à 25 % en poids de phosphate.
  11. Agent selon l'une des revendications 1 à 10, caractérisé en ce qu'il contient un polymère de rinçage supplémentaire choisi parmi les copolymères comprenant des monomères issus d'au moins deux des groupes suivants
    i) des monomères issus du groupe des acides carboxyliques mono- ou polyinsaturés de la formule générale

            R8(R9)C=C(R10)COOH,

    dans laquelle R8 à R10 représentent indépendamment les uns des autres -H, -CH3, un radical alkyle à chaîne droite ou ramifié saturé comprenant de 2 à 12 atomes de carbone, un radical alcényle à chaîne droite ou ramifié, mono- ou polyinsaturé comprenant de 2 à 12 atomes de carbone, des radicaux alkyle ou alcényle substitués par -NH2, -OH ou -COOH tels que précédemment définis, ou bien -COOH ou -COOR4, R4 étant un radical hydrocarbure saturé ou insaturé, à chaîne droite ou ramifié comprenant de 1 à 12 atomes de carbone,
    ii) des monomères de la formule générale

            R11(R12)C=C(R13)-X-R14,

    dans laquelle R11 à R13 représentent indépendamment les uns des autres -H, -CH3 ou -C2H5, X représente un groupe espaceur facultativement présent qui est choisi parmi -CH2-, -C(O)O- et -C(O)-NH-, et R14 représente un radical alkyle à chaîne droite ou ramifié saturé comprenant de 2 à 22 atomes de carbone ou un radical insaturé, de préférence aromatique, comprenant de 6 à 22 atomes de carbone,
    iii) des monomères contenant des groupes acide sulfonique de la formule générale

            R15(R16)C=C(R17)-X'-SO3H,

    dans laquelle R15 à R17 représentent indépendamment les uns des autres -H, -CH3, un radical alkyle à chaîne droite ou ramifié saturé comprenant de 2 à 12 atomes de carbone, un radical alcényle à chaîne droite ou ramifié, mono- ou polyinsaturé comprenant de 2 à 12 atomes de carbone, des radicaux alkyle ou alcényle substitués par -NH2, -OH ou -COOH, ou bien -COOH ou -COOR18, R18 étant un radical hydrocarbure saturé ou insaturé, à chaîne droite ou ramifié comprenant de 1 à 12 atomes de carbone, et X' représente un groupe espaceur facultativement présent qui est choisi parmi -(CH2)n- avec n = de 0 à 4, -COO-(CH2)k- avec k = de 1 à 6, -C(O)-NH-C(CH3)2- et -C(O)-NH-CH(CH2CH3)-,
    iv) d'autres monomères ioniques et/ou non ionogènes.
  12. Procédé pour le nettoyage de vaisselle dans une machine à laver la vaisselle utilisant l'agent pour le lavage mécanique de la vaisselle selon l'une des revendications 1 à 11.
  13. Utilisation d'un agent pour le lavage mécanique de la vaisselle selon l'une des revendications 1 à 11 en tant que produit de rinçage et/ou en tant qu'accélérateur de séchage lors du lavage mécanique de la vaisselle.
EP08735746.3A 2007-04-03 2008-04-03 Détergents Not-in-force EP2129761B1 (fr)

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DE102007016389A DE102007016389A1 (de) 2007-04-03 2007-04-03 Mittel zur Behandlung harter Oberflächen
DE102007023875A DE102007023875A1 (de) 2007-05-21 2007-05-21 Reinigungsmittel
DE200710038482 DE102007038482A1 (de) 2007-08-14 2007-08-14 Reinigungsmittel
PCT/EP2008/053997 WO2008119834A1 (fr) 2007-04-03 2008-04-03 Détergents

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US20100016203A1 (en) 2010-01-21
KR20090128445A (ko) 2009-12-15
US20120006358A1 (en) 2012-01-12
WO2008119834A1 (fr) 2008-10-09
EP2487232A1 (fr) 2012-08-15
EP2129761A1 (fr) 2009-12-09
EP2487232B1 (fr) 2014-12-03
US8318649B2 (en) 2012-11-27
US8044011B2 (en) 2011-10-25

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