EP1794269B1 - Constituants de produits nettoyants - Google Patents

Constituants de produits nettoyants Download PDF

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Publication number
EP1794269B1
EP1794269B1 EP05783106A EP05783106A EP1794269B1 EP 1794269 B1 EP1794269 B1 EP 1794269B1 EP 05783106 A EP05783106 A EP 05783106A EP 05783106 A EP05783106 A EP 05783106A EP 1794269 B1 EP1794269 B1 EP 1794269B1
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Prior art keywords
weight
zinc
liquid
cleaning agent
group
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EP05783106A
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German (de)
English (en)
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EP1794269A1 (fr
Inventor
Peter Schmiedel
Ulrich Pegelow
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to PL05783106T priority Critical patent/PL1794269T3/pl
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    • 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
    • C11D3/2093—Esters; Carbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C11D1/721—End blocked ethers

Definitions

  • the present invention relates to liquid detergent compositions which comprise at least one compound from the group of hydroxy mixed ethers, one or more esters of glycerol with monocarboxylic acids and optionally further detergent ingredients and the use of these liquid detergent compositions for improving the rinse-off result of automatic dishwashing processes.
  • non-aqueous i. essentially anhydrous detergent.
  • non-aqueous mostly solvent-based and aqueous dishwashing detergents for washing dishes in a domestic dishwasher.
  • liquid detergent compositions containing 14 to 35 wt .-% sodium tripolyphosphate, 0.1 to 50 wt .-% of a potassium and / or ammonium salt of an inorganic or organic acid, water and optionally surfactants, solubilizers, sequestering agents, persalts and other ingredients.
  • Linear viscoelastic automatic dishwashing detergent compositions are also described in the European patent application EP 446,761 (Colgate ).
  • the compositions disclosed herein contain up to 2% by weight of a long chain fatty acid or salt thereof, 0.1 to 5% by weight of surfactant, 5 to 40% by weight of water soluble builder, and up to 20% by weight of chlorine bleach and a polycarboxylate thickener wherein the ratio of potassium to sodium ions in the compositions is 1: 1 to 45: 1.
  • compositions disclosed herein contain a polyacrylate thickener which forms a gel matrix with water, surfactant, bleach, builder and water.
  • Gelled automatic dishwashing detergents are also disclosed in the European patent application EP 611 206 (Colgate ). These compositions contain 1 to 12% by weight of a liquid nonionic surfactant, 2 to 70% by weight of builder, as well as enzymes and a stabilizing system composed of swelling substances and hydroxypropylcellulose.
  • Viscose elastic, thixotropic Geschirquessmittel with 0.001 to 5 wt .-% surfactant and enzymes and an enzyme stabilization system of boric acid and polyhydroxy compounds are described in the international patent application WO93 / 21299 (Procter & Gamble ).
  • the agents disclosed herein also contain from 0.1% to 10% by weight of one or more thickeners.
  • the composition should provide an improved rinse-off result of machine dishwashing as compared to prior art agents.
  • the agent should be assembled in an attractive product design.
  • Detergent compositions according to the invention which contain from 35 to 95% by weight of nonionic surfactant from the group of the hydroxy mixed ethers of the abovementioned formula (a) and from 5 to 65% by weight of glycerol triacetate have a melting point which is well below room temperature and are therefore at room temperature which varies according to country, season and consumer habits, in a liquid consistency.
  • the melting point or the melting range of the composition is preferably below 20 ° C., preferably below 17.5 ° C., more preferably below 15 ° C., very preferably below 12.5 ° C. and in particular below 10 ° C.
  • liquid also includes those states of the compositions which are commonly referred to as viscous or gel-like.
  • nonionic surfactants from the group of hydroxy mixed ethers are contained in the detergent compositions according to the invention.
  • the washing or cleaning agent according to the invention preferably comprises hydroxy mixed ethers in a proportion of 35 to 80% by weight, particularly preferably 40 to 70% by weight and in particular 50 to 70% by weight, based on the total agent.
  • Hydroxymix ethers 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 denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1.5 and y is a value of at least 15, are particularly preferred.
  • R 1 and R 2 are as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18.
  • Particular preference is given to hydroxy mixed ethers in which the radicals R 1 and R 2 are 9 have up to 14 C atoms, R 3 is H and x assumes values of 6 to 15.
  • end-capped hydroxy mixed ethers of the formula R 1 O [CH 2 CH (R 3 ) O] x CH 2 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 is values between 1 and 30, j is values between 1 and 12, preferably between 1 and 5, preference being given to hydroxymix ethers 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.
  • hydroxy mixed ethers of the general formula R 1 O [CH 2 CH 2 O] x CH 2 CH (OH) R 2 , which in addition to a radical R 1 , which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, further a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R 2 having 1 to 30 carbon atoms, preferably 2 to 22 carbon atoms, which is adjacent to a monohydroxylated intermediate group -CH 2 CH (OH) - and in which x is between 40 and 80, preferably between 40 and 60.
  • R 1 which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, preferably 2 to 22 carbon atoms, which is adjacent to a monohydroxylated intermediate group -CH 2 CH (OH) - and in which x is between 40 and 80, preferably
  • R 1 O [CH 2 CH 2 O] x [CH 2 CH (CH 3 ) O] y CH 2 CH (OH) R 2 in which R 1 and R 2 independently of one another are a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R 3 is independently selected from -CH 3 -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , CH (CH 3 ) 2 , but preferably -CH 3 , and x and y independently of one another represent values between 1 and 32, wherein hydroxy mixed ethers having values of x of 15 to 32 and y of 0, 5 and 1.5 are very particularly preferred.
  • Hydroxymix ethers of the general formula R 1 O [CH 2 CH 2 O] x [CH 2 CH (R 3 ) O] y CH 2 CH (OH) R 2 in which R 1 and R 2 independently of one another are a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R 3 is independently selected from -CH 3 -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , CH (CH 3 ) 2 , but preferably represents -CH 3 , and x and y independently of one another are values between 1 and 32 are preferred according to the invention, wherein hydroxy mixed ethers with values of x from 15 to 32 and y of 0.5 and 1.5 are very particularly preferred.
  • the stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the abovementioned hydroxy mixed ethers represent statistical average values which, for a specific product, may be an integer or a fractional number. Due to the manufacturing process, commercial products of the formulas mentioned are usually not made of an individual representative, but of mixtures, which may result in mean values for the C chain lengths as well as for the degrees of ethoxylation or degrees of alkoxylation and subsequently broken numbers.
  • hydroxy mixed ethers can be used not only as individual substances but also as mixtures of two, three, four or more hydroxy mixed ethers.
  • Mixtures are not mixtures of hydroxy mixed ethers which fall in their entirety under one of the abovementioned general forms, but rather those mixtures which contain two, three, four or more hydroxy mixed ethers which can be described by different of the abovementioned general formulas.
  • hydroxy mixed ethers which have a melting point below 60.degree.
  • Hydroxy mixed ethers having a melting point below 50 ° C, preferably below 45 ° C and especially between 26.6 and 43.3 ° C are particularly preferred.
  • the quantitative ratio of the hydroxy mixed ethers contained in the agent is preferably within narrow limits. If a mixture of two hydroxy mixed ethers is used, the weight ratio of the hydroxy mixed ethers used is preferably between 10: 1 and 1:10, preferably between 8: 1 and 1: 8, more preferably between 6: 1 and 1: 6 and in particular between 4 : 1 and 1: 4.
  • the machine dishwashing detergent according to the invention contains a mixture of two, three, four or more hydroxy mixed ethers, it is preferred if at least one of the hydroxy mixed ethers has a weight fraction above 1.0% by weight, preferably above 2% by weight and in particular above 5% by weight. , based on the total mean.
  • the second essential constituent of the detergent compositions according to the invention is the glycerol triacetate.
  • the content of this ester based on the composition is preferably 10 to 60 wt .-%, preferably 20 to 50 wt .-% and in particular 30 to 45 wt .-%.
  • compositions according to the invention solidify at temperatures well below room temperature.
  • the resulting compositions have increased rinse performance in automatic dishwashing processes compared to the prior art agents.
  • the weight ratio of hydroxy mixed ethers to the glycerol triacetate employed is between 20: 1 and 1: 2, preferably between 15: 1 and 1: 1.75, more preferably between 10: 1 and 1: 1.5, all particularly preferably between 5: 1 and 1: 1.25 and in particular between 2.5: 1 and 1: 1.
  • the present invention relates to liquid non-aqueous automatic dishwashing detergent compositions.
  • non-aqueous is to be understood as meaning a state in which the content of free water in the agents is significantly below 10% by weight, based on the agent. It is preferred that the detergent compositions according to the invention contain less than 7.5% by weight of free water, preferably less than 5% by weight and in particular less than 2.5% by weight of free water.
  • compositions according to the invention have a total water content of not more than 15% by weight, preferably not more than 10% by weight and in particular not more than 5% by weight.
  • Non-aqueous, especially organic solvents may be contained in the compositions according to the invention as further constituents.
  • solvents include, but are not limited to, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycols and polypropylene glycols, ethanol, n- or i-propanol, butanols, glycol, propane or butane diol, glycerol, glycerin carbonate, diglycol, propyl or butyl diglycol, hexylene glycol , Ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, di-ethylene glycol ethyl ether, propylene glycol methyl, -ethyl or -propyl ether, dipropylene glycol methyl or e
  • said organic solvents in amounts less than 15 wt .-%, preferably less than 10 wt .-%, more preferably less than 5 wt .-%, most preferably less than 2 wt .-% and in particular less than 1 wt .-% based used on the entire agent.
  • Particularly preferred agents according to the invention are free from nonaqueous organic solvents.
  • compositions of the invention it may be desirable to provide silver protection and / or protection from glass corrosion during the automatic dishwashing process.
  • the agent according to the invention optionally corrosion inhibitors from the group of silver corrosion inhibitors and / or glass corrosion inhibitors are added.
  • the content of the corrosion inhibitors in the compositions according to the invention is preferably from 0.01 to 15% by weight, preferably from 0.1 to 10% by weight, preferably from 0.2 to 5% by weight, particularly preferably from 0.25 to 2.5 Wt .-% and in particular 0.25 to 2 wt .-%, based on the total agent.
  • composition of the invention is used, inter alia, as a special agent in the field of corrosion protection.
  • content of the abovementioned corrosion inhibitors is between 1 and 25% by weight, preferably between 1.5 and 20% by weight, more preferably between 2 and 15% by weight and in particular between 2 and 10% by weight.
  • the weight ratio between hydroxy mixed ethers and corrosive agents in agents according to the invention is preferably between 9000: 1 and 2: 1, more preferably between 1000: 1 and 10: 1 and in particular between 280: 1 and 25: 1.
  • esters of glycerol with C 1-10 monocarboxylic acids to the corrosive agents have a weight ratio between 6000: 1 and 1: 5, preferably between 1000: 1 and 3: 1 and in particular between 180: 1 and 15: 1.
  • silver protectants selected from the group of triazoles, the Benzotriazole, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes are used. Particularly preferred to use are benzotriazole and / or alkylaminotriazole.
  • Examples of the 3-amino-5-alkyl-1,2,4-triazoles preferably used according to the invention can be: propyl, butyl, pentyl, heptyl, octyl, nonyl, decyl -, undecyl, - dodecyl, -sononyl, -Versatic-10-alkyl, -phenyl, -p-tolyl, - (4-tert-butylphenyl) -, - (4-methoxyphenyl) -, - (2-, 3-, 4-pyridyl) -, - (2-thienyl) -, - (5-methyl-2-furyl) -, - (5-oxo-2-pyrrolidinyl) -, -3 amino-1,2,4-triazole.
  • Preferred acids for salt formation are hydrochloric acid, sulfuric acid, phosphoric acid, carbonic acid, sulphurous acid, organic carboxylic acids such as acetic, glycolic, citric, succinic acid.
  • cleaner formulations often contain active chlorine-containing agents which can markedly reduce the corrosion of the silver surface.
  • active chlorine-containing agents which can markedly reduce the corrosion of the silver surface.
  • oxygen- and nitrogen-containing organic redox-active compounds such as di- and trihydric phenols, e.g. Hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, pyrogallol or derivatives of these classes of compounds used.
  • salt and complex inorganic compounds such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used.
  • transition metal salts which are selected from the group of the manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) - Complexes, the chlorides of cobalt or manganese and manganese sulfate. Also, zinc compounds can be used to prevent corrosion on the items to be washed.
  • redox-active substances can be used. These substances are preferably inorganic redox-active substances from the group of manganese, titanium, zirconium, hafnium, vanadium, cobalt and cerium salts and / or complexes, wherein the metals preferably in one of the oxidation states II, III, IV, V or VI are present.
  • the metal salts or metal complexes used should be at least partially soluble in water.
  • the counterions suitable for salt formation comprise all customary mono-, di- or tri-positively negatively charged inorganic anions, for example oxide, sulfate, nitrate, fluoride, but also organic anions such as stearate.
  • Metal complexes in the context of the invention are compounds which consist of a central atom and one or more ligands and optionally additionally one or more of the abovementioned anions.
  • the central atom is one of the above-mentioned metals in one of the abovementioned oxidation states.
  • the ligands are neutral molecules or anions that are mono- or polydentate;
  • the term "ligands" within the meaning of the invention is, for example, in " Römpp Chemie Lexikon, Georg Thieme Verlag Stuttgart / New York, 9th edition, 1990, page 2507 If, in a metal complex, the charge of the central atom and the charge of the ligand (s) are not zero, either one or more of the abovementioned anions or one or more, depending on whether there is a cationic or an anionic charge surplus Cations, for example sodium, potassium and ammonium ions, for charge balance Suitable complexing agents are, for example, citrate, acetylacetonate or 1-hydroxyethane-1,1-diphosphonate.
  • the well-known in chemistry definition for "oxidation state” is eg in " Römpp Chemie Lexikon, Georg Thieme Verlag Stuttgart / New York, 9th edition, 1991, page 3168 "reproduced.
  • metal salts and / or metal complexes are selected from the group MnSO 4 , Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [1-hydroxyethane-1,1- diphosphonate], V 2 O 5 , V 2 O 4 , VO 2 , TiOSO 4 , K 2 TiF 6 , K 2 ZrF 6 , CoSO 4 , CO (NO 3 ) 2 , Ce (NO 3 ) 3 , and mixtures thereof, such that the metal salts and / or metal complexes are selected from the group MnSO 4 , Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [1-hydroxyethane-1,1- diphosphonate], V 2 O 5 , V 2 O 4 , VO 2 , TiOSO 4 ,
  • metal salts or metal complexes are generally commercially available substances which can be used for the purpose of silver corrosion protection without prior purification in detergents or cleaners.
  • the mixture of pentavalent and tetravalent vanadium (V 2 O 5 , VO 2 , V 2 O 4 ) known from the SO 3 preparation (contact method) is suitable, as is the case by diluting a Ti (SO 4 ) 2 - Solution resulting titanyl sulfate, TiOSO 4 .
  • the inorganic redox-active substances are preferably coated, ie completely coated with a waterproof material which is readily soluble in the cleaning temperatures, in order to prevent their premature decomposition or oxidation during storage.
  • Preferred coating materials which are applied by known methods, such as Sandwik from the food industry, are paraffins, microwaxes, waxes of natural origin such as carnauba wax, candellila wax, beeswax, higher melting alcohols such as hexadecanol, soaps or fatty acids.
  • the coating material which is solid at room temperature is applied in the molten state to the material to be coated, for example by adding finely divided material coating material is spun in continuous stream through a likewise continuously generated spray zone of the molten coating material.
  • the melting point must be selected so that the coating material dissolves easily during the silver treatment or melts quickly.
  • the melting point should ideally be in the range between 45 ° C and 65 ° C and preferably in the range 50 ° C to 60 ° C.
  • 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 / or zinc salts and / or magnesium and / or zinc complexes.
  • a preferred class of compounds that can be used to prevent glass corrosion are insoluble zinc salts.
  • Insoluble zinc salts in the context of this preferred embodiment are zinc salts which have a solubility of a maximum of 10 grams of zinc salt per liter of water at 20 ° C.
  • Examples of particularly preferred insoluble zinc salts according to the invention are zinc silicate, zinc carbonate, zinc oxide, basic zinc carbonate (Zn 2 (OH) 2 CO 3 ), zinc hydroxide, zinc oxalate, zinc monophosphate (Zn 3 (PO 4 ) 2 ) and zinc pyrophosphate (Zn 2 (P 2 O 7 )).
  • zinc silicate zinc carbonate
  • zinc oxide zinc oxide
  • basic zinc carbonate Zn 2 (OH) 2 CO 3 )
  • zinc hydroxide zinc oxalate
  • zinc monophosphate Zn 3 (PO 4 ) 2
  • zinc pyrophosphate Zn 2 (P 2 O 7 )
  • zinc nitrate hexahydrate is also preferred.
  • the zinc compounds mentioned are preferably used in amounts which have a content of the zinc ions of between 0.02 and 10% by weight, preferably between 0.1 and 5.0% by weight and in particular between 0.2 and 1.0% by weight .-%, each based on the total glass corrosion inhibitor-containing agent effect.
  • the exact content of the agent on the zinc salt or zinc salts is naturally dependent on the type of zinc salts - the less soluble the zinc salt used, the higher its concentration should be in the funds.
  • the particle size of the salts is a criterion to be observed, so that the salts do not adhere to glassware or machine parts.
  • the insoluble zinc salts have a particle size below 1.7 millimeters.
  • the insoluble zinc salt has an average particle size which is significantly below this value in order to further minimize the risk of insoluble residues, for example an average particle size of less than 250 ⁇ m. Again, this is even more true the less the zinc salt is soluble. In addition, rising the glass corrosion inhibiting effectiveness with decreasing particle size.
  • the average particle size is preferably below 100 microns. For still less soluble salts, it may be even lower; For example, average particle sizes below 60 ⁇ m are preferred for the very poorly soluble zinc oxide.
  • Another preferred class of compounds are magnesium and / or zinc salt (s) of at least one monomeric and / or polymeric organic acid. These have the effect that, even with repeated use, the surfaces of glassware do not undergo corrosive changes, in particular no clouding, streaks or scratches, but also no iridescence of the glass surfaces.
  • magnesium and / or zinc salt (s) of monomeric and / or polymeric organic acids can be used, yet the magnesium and / or zinc salts of monomeric and / or polymeric organic acids from the groups of unbranched saturated or unsaturated monocarboxylic acids, the branched saturated or unsaturated monocarboxylic acids, the saturated and unsaturated dicarboxylic acids, the aromatic mono-, di- and tricarboxylic acids, the sugar acids, the hydroxy acids, the oxo acids, the amino acids and / or the polymeric carboxylic acids are preferred.
  • the spectrum of the inventively preferred zinc salts of organic acids, preferably organic carboxylic acids, ranges 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 mg / l have, 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 water temperature).
  • the first group of zinc salts includes, for example, zinc citrate, zinc oleate and zinc stearate
  • the group of soluble zinc salts includes, for example, zinc formate, zinc acetate, zinc lactate and zinc gluconate.
  • the glass corrosion inhibitor used is at least one zinc salt of an organic carboxylic acid, more preferably a zinc salt from the group zinc stearate, zinc oleate, zinc gluconate, zinc acetate, zinc lactate and / or zinc citrate.
  • Zinc ricinoleate, zinc abietate and zinc oxalate are also preferred.
  • the content of cleaning agents to zinc salt is preferably between 0.1 to 5 wt .-%, preferably between 0.2 to 4 wt .-% and in particular between 0.4 to 3 wt.%, Or Content of zinc in oxidized form (calculated as Zn 2+ ) between 0.01 to 1% by weight, preferably between 0.02 to 0.5% by weight and in particular between 0.04 to 0.2 wt .-%, each based on the total weight of the glass corrosion inhibitor-containing agent.
  • the washing or cleaning agent according to the invention preferably contains polymers having a cationic functional group which belong to the group of cationic polymers. Preference is given to polymers having a cationic monomer unit in the detergent composition according to the invention in an amount of from 0.01 to 7.5% by weight, preferably from 0.02 to 5% by weight, particularly preferably from 0.03 to 2.5% by weight, most preferably 0.04 to 1 wt .-% and in particular 0.05 to 1 wt.%, Based on the total agent used.
  • “Cationic polymers” or for the purposes 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.
  • particularly preferred cationic polymers contain as monomer unit a compound of the general formula in which R 1 and R 4 are each independently H or a linear or branched hydrocarbon radical having 1 to 6 carbon atoms; R 2 and R 3 are independently an alkyl, hydroxyalkyl, or aminoalkyl group in which the alkyl group is linear or branched and has from 1 to 6 carbon atoms, preferably a methyl group; x and y independently represent integers between 1 and 3.
  • X - represents a counterion, preferably a counterion from the group chloride, bromide, iodide, sulfate, hydrogen sulfate, methosulfate, lauryl sulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate), cumene sulfonate, xylenesulfonate, phosphate, citrate, formate, acetate or mixtures thereof.
  • Preferred radicals R 1 and R 4 in the above formula are selected from -CH 3, -CH 2 -CH 3, - CH 2 -CH 2 -CH 3, -CH (CH 3) -CH 3, -CH 2 -OH , -CH 2 -CH 2 -OH, -CH (OH) -CH 3 , -CH 2 -CH 2 -OH, -CH 2 -CH (OH) -CH 3 , -CH (OH) -CH 2 -CH 3 , and - (CH 2 CH 2 -O) n H.
  • cationic polymers comprise a monomer unit of the general formula in which R 1 , R 2 , R 3 , R 4 and R 5 independently of one another are a linear or branched, saturated or unsaturated alkyl or hydroxyalkyl radical having 1 to 6 carbon atoms, preferably a linear or branched alkyl radical selected from -CH 3 , -CH 2 -CH 3 , -CH 2 -CH 2 -CH 3 , -CH (CH 3 ) -CH 3 , -CH 2 -OH, -CH 2 -CH 2 -OH, -CH (OH) -CH 3 , -CH 2 -CH 2 -CH 2 -OH, -CH 2 -CH (OH) -CH 3 , -CH (OH) -CH 3 , and - (CH 2 CH 2 -O) n H and x is an integer between 1 and 6.
  • amphoteric polymers have not only cationic groups but also anionic groups or monomer units.
  • 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 nonionogenic mono
  • the agents according to the invention optionally contain from 0.001 to 3% by weight, preferably from 0.05 to 2.5% by weight and in particular from 0.1 to 2% by weight, of water-binding agents from the group of urea, sorbitol, trimethylamine, oxalic acid, boric acid, Borax, dimethylolurea, glyoxal, diepoxides, divinylsulfones and / or the water-soluble formaldehyde derivatives.
  • water-binding agents from the group of urea, sorbitol, trimethylamine, oxalic acid, boric acid, Borax, dimethylolurea, glyoxal, diepoxides, divinylsulfones and / or the water-soluble formaldehyde derivatives.
  • Liquid agents of the invention may further contain water-soluble builders.
  • Water-soluble builders are used in the compositions of the invention especially for binding calcium and magnesium.
  • the builders are in the context of the invention preferably in amounts below 15 wt .-%, preferably below 12 wt .-%, more preferably below 9 wt .-% and in particular from 0.01 to 6 wt .-%, each based on the Detergent composition added.
  • Particularly preferred liquid agents according to the invention are free of builders. Examples of suitable builders are the low molecular weight polycarboxylic acids and their salts, the homopolymeric and copolymeric polycarboxylic acids and their salts, the carbonates, phosphates and sodium and potassium silicates.
  • Low molecular weight polycarboxylic acids in the context of the present invention are substances which carry two or more carboxyl functions and have molar masses below 2000.
  • the group includes the acids mentioned below and their salts: tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and in particular citric acid.
  • Commercially available and is also preferred in the context of the present invention is Sokalan ® DCS (trademark of BASF), a mixture of succinic acid (max. 31 wt .-%), glutaric acid (max. 50 wt .-%) and adipic acid (max. 33% by weight).
  • Trisodium citrate and / or pentasodium tripolyphosphate and silicatic builders from the class of alkali disilicates are preferably used for the cleaning agents according to the invention.
  • the potassium salts are preferable to the sodium salts because they often have a higher water solubility.
  • Preferred water-soluble builders are, for example, tripotassium citrate, potassium carbonate and the potassium water glasses.
  • Particularly preferred detergent compositions contain as water-soluble builders phosphates, preferably alkali metal phosphates with particular preference of pentasodium or Pentakaliumtriphosphat (sodium or potassium tripolyphosphate).
  • phosphates preferably alkali metal phosphates with particular preference of pentasodium or Pentakaliumtriphosphat (sodium or potassium tripolyphosphate).
  • cleaning compositions according to the invention which contain as water-soluble builders citrates and / or phosphates, preferably alkali metal phosphates with particular preference of pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate). It may be preferred to use citrates in mixtures with phosphates or to dispense entirely with the addition of citrates.
  • citrates and / or phosphates preferably alkali metal phosphates with particular preference of pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate).
  • compositions of the invention are preferably in a clear, transparent form.
  • transparency is to be understood as meaning that the permeability within the visible spectrum of the light (410 to 800 nm) is greater than 20%, preferably greater than 30%, very preferably greater than 40% and in particular greater than 50%.
  • a wavelength of the visible spectrum of the light has a transmittance greater than 20%, it is to be regarded as transparent within the meaning of the invention.
  • Staining of the detergent composition also increases the attractiveness of the final product. For example, it is preferred to color the composition with blue, red, yellow, green, violet, orange or even turquoise dyes and / or dye mixtures. It is conceivable that the entire agent is dyed in one color. The division of the agent into different receiving chambers of the receptacle explained below and different staining of the chamber contents, that is, the individual central portions, but is also possible.
  • the detergent compositions according to the invention are preferably coated with a water-soluble or water-dispersible material, that is filled in a water-soluble or water-dispersible container.
  • the packaging material is preferably transparent and can be colored if necessary.
  • an air bubble is contained in the packaged liquid composition. This increases the attractiveness of the product and allows the consumer to directly recognize that the agent according to the invention is a liquid. With the liquid consistency of the agent, the consumer combines a rapid release of the active ingredients.
  • the air bubble preferably occupies less than 20% by volume, preferably less than 15% by volume, more preferably between 1 and 10% by volume and especially between 2 and 8% by volume of the packaged liquid agent.
  • the water-soluble or water-dispersible containers are in principle accessible by any means known in the art. However, particularly preferred are containers made by the deep drawing method, the injection molding method or the melt casting method were. These containers preferably have more than one receiving chamber, more preferably more than two and in particular more than three receiving chambers.
  • deep-drawing or “deep-drawing process” refers to processes for processing packaging materials in which these are prepared by optional pretreatment by heat and / or solvent and / or conditioning by means of relative atmospheric humidities and / or temperatures modified by ambient conditions molded mold can be shaped.
  • the packaging material for example, as a plate or foil between the two parts of the tool, the positive and the negative, introduced and deformed by compression of these parts, but the deformation can also without the use of a negative tool by the action of a vacuum and / or Compressed air and / or the weight of the trapped detergents or cleaners done.
  • the deep-drawing process can be between methods in which the shell material is guided horizontally in a forming station and from there in a horizontal manner for filling and / or sealing and / or separating and methods in which the shell material via a continuously rotating Matrizenformwalze (optionally with optional a counter-guided Patrizenformwalze, which lead the forming upper punch to the cavities of the Matrizenformwalze) is different.
  • the first-mentioned process variant of the flat bed process is to operate both continuously and discontinuously, the process variant using a molding roll is usually continuous. All of the mentioned deep drawing methods are suitable for the production of the inventively preferred means.
  • the receiving troughs located in the matrices can be arranged "in series" or staggered.
  • the water-soluble or water-dispersible containers can also be produced by injection molding.
  • Injection molding refers to the forming of a molding material such that the mass contained in a mass cylinder for more than one injection molding plastically softens under heat and flows under pressure through a nozzle into the cavity of a previously closed tool.
  • the method is mainly applied to non-hardenable molding compounds which solidify in the tool by cooling.
  • Injection molding is a very economical modern process for producing non-cutting shaped articles and is particularly suitable for automated mass production.
  • thermoplastic molding compounds are heated to liquefaction (up to 180 ° C) and injected under high pressure (up to 140 MPa) in closed, two-piece, that is from Gesenk (earlier Die) and core (formerly male) existing, preferably water-cooled molds, where they cool and solidify.
  • Suitable molding compositions are water-soluble polymers, for example the abovementioned cellulose ethers, pectins, polyethylene glycols, polyvinyl alcohols, polyvinylpyrrolidones, alginates, gelatin or starch.
  • melt-casting is used to produce the water-soluble or water-dispersible container.
  • Melt-casting is the shaping of a molding compound in such a way that the mass contained in a mass cylinder, preferably for more than one melt-casting process, softens plastically under the effect of heat and flows into the cavity of a previously closed tool.
  • melt casting is also preferred for non-hardenable molding compounds which solidify in the mold by cooling (thermoplastics). But it is also the processing of thermosets and elastomers possible; Here, however, an electric heater of the tool for curing or vulcanization of the injected material is used.
  • the molding compositions are potted in the preferred method and solidify subsequently to a dimensionally stable casting.
  • “Solidify” hereby denotes any curing mechanism that provides a deformable, preferably flowable mixture or such a substance or such a mass solid at room temperature body without pressing or Kompaktier modifier are necessary.
  • “Solidification” in the context of the present invention is therefore, for example, the curing of melts of solid substances at room temperature by cooling.
  • “Solidification processes” in the context of the present application are also the curing of formable materials by time-delayed water binding, by evaporation of solvents, by chemical reaction, crystallization, etc. and the reactive curing of flowable powder mixtures to form stable hollow bodies.
  • the production of preferred casting is carried out by casting a molding compound into a mold and subsequent demolding of the solidified cast body to form a (trough) shaped body.
  • a "mold” are preferably tools that have cavities that can be filled with pourable substances. Such tools may be formed, for example, in the form of individual cavities but also in the form of plates having a plurality of cavities.
  • the individual cavities or cavity plates are preferably mounted in industrial processes on horizontally circulating conveyor belts, which allow a continuous or discontinuous transport of the cavities, for example along a number of different workstations (eg: casting, cooling, filling, sealing, demolding, etc.).
  • the shaping of the above-mentioned depressions preferably succeeds by subsequent impressions of a correspondingly shaped tool into the already flowing molding compound. It is particularly preferred that at the time of pressing the tool, the viscosity of the molding composition already by 1-50%, preferably 1 - 35%, in particular 1 - 20% compared to the viscosity, which had the molding material when flowing into the mold, has increased.
  • shell materials which can be processed by deep-drawing methods, injection molding methods or melt-casting methods can be used, although the use of water-soluble or water-dispersible packaging materials is preferred.
  • Water-soluble polymers in the context of the invention are those polymers which are soluble in water at room temperature in excess of 2.5% by weight.
  • the container comprises one or more water-soluble polymer (s), preferably a material from the group (optionally acetalized) polyvinyl alcohol (PVAL), polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose, and derivatives thereof and mixtures thereof.
  • PVAL polyvinyl alcohol
  • PVP polyvinylpyrrolidone
  • the coating material used in the process according to the invention at least partially comprises a polyvinyl alcohol whose degree of hydrolysis 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.
  • the first shell material used in the method according to the invention comprises at least 20% by weight, particularly preferably at least 40% by weight, very particularly preferably at least 60% by weight and in particular at least 80% by weight. of a polyvinyl alcohol whose degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol%, and especially 82 to 88 mol%.
  • Polyvinyl alcohols of a certain molecular weight range are preferably used as materials for the containers, it being preferred according to the invention that the coating material comprises a polyvinyl alcohol whose molecular weight is in the range from 10,000 to 100,000 gmol -1 , preferably from 11,000 to 90,000 gmol -1 , particularly preferably 12,000 to 80,000 gmol -1 and in particular from 13,000 to 70,000 gmol -1 .
  • the degree of polymerization of such preferred polyvinyl alcohols is between about 200 to about 2100, preferably between about 220 to about 1890, more preferably
  • polyvinyl alcohols described above are widely available commercially, for example under the trade name Mowiol ® (Clariant).
  • Mowiol ® Commercially, for example under the trade name Mowiol ® (Clariant).
  • particularly suitable polyvinyl alcohols are, for example, Mowiol ® 3-83, Mowiol ® 4-88, Mowiol ® 5-88 and Mowiol ® 8-88.
  • polyvinyl alcohols are as shell material ® ELVANOL 51-05, 52-22, 50-42, 85-82, 75-15, T-25, T-66, 90-50 (trademark of Du Pont), ALCOTEX 72.5 ®, 78, B72, F80 / 40, F88 / 4, F88 / 26, F88 / 40, F88 / 47 (trademark of Harlow Chemical Co.), Gohsenol ® NK-05, A-300, AH-22, C-500, GH-20, GL-03, GM-14L, KA-20, KA-500, KH-20, KP-06, N-300, NH-26, NM11Q, KZ-06 (Trademark of Nippon Gohsei KK).
  • the water solubility of PVAL can be altered by post-treatment with aldehydes (acetalization) or ketones (ketalization).
  • Polyvinyl alcohols which are acetalated or ketalized with the aldehyde or keto groups of saccharides or polysaccharides or mixtures thereof have proven to be particularly advantageous and particularly advantageous on account of their pronounced cold water solubility.
  • To use extremely advantageous are the reaction products of PVAL and starch.
  • PVAL films under the name "SOLUBLON® ®” from Syntana bottlesgesellschaft E. Harke GmbH & Co. available PVAL films. Their solubility in water can be adjusted to the exact degree, and they are foils of this product series available, which are soluble in aqueous phase in all relevant for the application temperature ranges.
  • Shell materials which comprise a polymer from the group of starch and starch derivatives, cellulose and cellulose derivatives, in particular methyl cellulose, and mixtures thereof are preferred within the scope of the process according to the invention.
  • starch-derivatives which are obtainable from starch by polymer-analogous reactions are also suitable for the preparation of water-soluble coatings of the detergent, detergent and cleaner portions in the context of the present invention.
  • Such chemically modified starches include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. But even starches in which the hydroxy groups have been replaced by functional groups that are not bound by an oxygen atom, can be used as starch derivatives.
  • the group of starch derivatives includes, for example, alkali starches, carboxymethyl starch (CMS), starch esters and ethers, and amino starches.
  • cellulosic derivatives obtainable by polymer-analogous reactions of cellulose can also be used as the cellulose-based shell material.
  • Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted.
  • Celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives.
  • the group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses.
  • Suitable matrix materials for casting bodies which are produced by melt solidification are, in particular, fusible substances from the group of fats and / or triglycerides and / or fatty acids and / or fatty alcohols and / or waxes and / or paraffins.
  • the casting bodies used as packaging additionally contain wash-active substances which are included in the above-mentioned matrix.
  • the filled hollow body is subsequently closed with a water-soluble or water-dispersible film. If the liquid composition according to the invention has a sufficiently high viscosity, the sealing by means of a film can be dispensed with.
  • the hollow body optionally other agents such as tablets or in water-soluble or water-dispersible Foil-packed liquids / gels / powder before or after filling with the liquid composition are introduced.
  • the washing-active substances in the casting body are preferably in the form of a dispersion.
  • Suitable dispersants are preferably the water-soluble or water-dispersible polymers, in particular the water-soluble or water-dispersible nonionic polymers.
  • the dispersant may be both a single polymer and mixtures of various water-soluble or water-dispersible polymers.
  • the dispersant or at least 50% by weight of the polymer mixture consists of water-soluble or water-dispersible nonionic polymers from the group of polyvinylpyrrolidones, vinylpyrrolidone-vinyl ester copolymers, cellulose ethers, polyvinyl alcohols, polyalkylene glycols, in particular polyethylene glycol and / or polypropylene glycol.
  • all substances which are solid or washing or are active at room temperature are suitable as dispersed substances, but especially washing or cleaning substances from the group of builders (builders and cobuilders), detergents or cleaners, bleaching agents, bleach activators , the glass corrosion inhibitor, the silver protectant and / or the enzymes.
  • the automatic cleaning of dishes in household dishwashers usually includes a pre-wash, a main wash, and a rinse cycle interrupted by intermediate rinses.
  • the pre-rinse for heavily soiled dishes is switchable, but is selected only in exceptional cases by the consumer, so that in most machines a main rinse, an intermediate rinse with pure water and a rinse cycle are performed.
  • the temperature of the main wash cycle varies between 40 and 65 ° C, depending on the machine type and program level selection.
  • rinse aids are added from a dosing tank in the machine, which usually contain nonionic surfactants as the main constituent. Your task is primarily to prevent limescale and deposits on the cleaned dishes.
  • the present invention is a liquid composition which is used as a special agent in addition to dishwashing detergent and thus makes the filling of rinse aid in the dosing tank superfluous.
  • the liquid composition according to the invention is preferably used in a dosage unit of 5 to 30 g, more preferably 10 to 25 g and especially 15 to 25 g or 5 to 40 ml, preferably 8 to 30 ml and preferably 14 to 30 ml.
  • Dosage units of 15 are also preferred to 75 ml, preferably from 20 to 70 ml and in particular from 30 to 60 ml. These are used especially in the case of less concentrated, that is to say with a lower concentration of nonionic surfactant in the liquid composition.
  • a further subject of the present invention is a combination product in which, in addition to the liquid composition, further cleaning-active agents, e.g. in the form of tablets and / or solid or liquid Pouches are included.
  • the means are preferably filled in containers with a plurality of receiving chambers.
  • the liquid compositions according to the invention preferably take up 10 to 90%, preferably 20 to 80%, particularly preferably 30 to 70% and in particular 40 to 60% of the volume of the combination product.
  • the proportion by weight of the liquid composition in the combination product is preferably below 80%, preferably below 70%, particularly preferably below 60% and in particular between 20 and 50%.
  • the combination of the abovementioned ready-to-use forms of solid and liquid detergents with the liquid compositions according to the invention now offers a number of possibilities.
  • the following tables describe some preferred embodiments.
  • the filled with liquid, powder or granules receiving chambers preferably have a seal. In the case of compartments filled with compacts, extrudates, castings or rigid gels, the seal is optional, but is preferred.
  • the liquid detergent compositions according to the invention are referred to below as liquid according to the invention. If several liquids are filled in a receiving chamber, they are preferably immiscible. When combining two liquids according to the invention, these preferably have different properties, such as color, turbidity, viscosity or the presence of suspended constituents in the liquid.
  • Receiving chamber 1 Liquid and liquid according to the invention Inventive liquid and powder Inventive liquid and granules Inventive liquid and Kompaktat Liquid and extrudate according to the invention Inventive liquid and casting Inventive liquid and dimensionally stable gel
  • Receiving chamber 1 Receiving chamber 2 Liquid according to the invention liquid Liquid according to the invention powder Liquid according to the invention granules Liquid according to the invention compacted Liquid according to the invention extrudate Liquid according to the invention casting body Liquid according to the invention Dimensionally stable gel Liquid according to the invention Liquid according to the invention 2 Inventive liquid and powder liquid Inventive liquid and powder powder Inventive liquid and powder granules Inventive liquid and powder compacted Inventive liquid and powder extrudate Inventive liquid and powder casting body Inventive liquid and powder Dimensionally stable gel Inventive liquid and powder Liquid according to the invention 2 Inventive liquid and granules liquid Inventive liquid and granules powder Inventive liquid and granules granules Inventive liquid and granules compacted Inventive liquid and granules extrudate Inventive liquid and granules
  • Another object of the present application is the use of an agent according to the invention as a cleaning agent in a dishwasher.
  • liquid detergent compositions of the present invention may be formulated alone or in combination with other liquid or solid detergents (e.g., powders, extrudates, compacts).
  • Both the liquid detergent compositions according to the invention and the further liquid or solid detergents optionally combined with these compositions to form a combination product may contain, in addition to the active substances described above, further active substances from the group of builders, surfactants, polymers, bleaches, bleach activators, enzymes, glass corrosion inhibitors, corrosion inhibitors, Disintegration aids, fragrances and perfume carriers included.

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Claims (14)

  1. Compositions liquides d'agents de nettoyage, contenant :
    a) à concurrence de 35 à 95 % en poids, un agent tensioactif non ionique du groupe des hydroxyéthers mixtes répondant à la formule

            R1-O-[CH2CH(R3)O]x-[CH2CH(OH)]-R2

    dans laquelle R1 et R2 peuvent être identiques ou différents, R1 représente un radical d'hydrocarbure aliphatique ou aromatique, saturé ou insaturé, linéaire ou ramifié, contenant de 1 à 30 atomes de carbone, ou leurs mélanges, R2 représente un radical d'hydrocarbure aliphatique ou aromatique, saturé ou insaturé, linéaire ou ramifié, contenant de 1 à 30 atomes de carbone, qui contient de manière facultative jusqu'à 5 fonctions hydroxyle et/ou jusqu'à 3 fonctions éther, R3 représente un atome d'hydrogène, un radical méthyle, un radical éthyle, un radical n-propyle, un radical isopropyle, un radical n-butyle, un radical 2-butyle ou un radical 2-méthylbutyle, chaque radical R3 dans lequel x ≥ 2 pouvant être différent et x représentant des valeurs supérieures à 1, et
    b) à concurrence de 5 à 65 % en poids, du triacétate de glycérol.
  2. Compositions d'agents de nettoyage selon la revendication 1, caractérisées en ce qu'elles contiennent, à concurrence de 35 à 80 % en poids, de manière particulièrement préférée à concurrence de 40 à 70 % en poids et en particulier à concurrence de 50 à 70 % en poids, un ou plusieurs hydroxyéthers mixtes.
  3. Compositions d'agents de nettoyage selon l'une quelconque des revendications 1 ou 2, caractérisées en ce qu'elles contiennent, à concurrence de 10 à 60 % en poids, de préférence à concurrence de 20 à 50 % en poids et en particulier à concurrence de 30 à 45 % en poids, du triacétate de glycérol.
  4. Compositions d'agents de nettoyage selon l'une quelconque des revendications 1 à 3, caractérisées en ce qu'elles contiennent, à concurrence de moins de 10 % en poids, de l'eau libre, de préférence à concurrence de moins de 7,5 % en poids, de manière particulièrement préférée à concurrence de moins de 5 % en poids et en particulier à concurrence de moins de 2,5 % en poids, de l'eau libre.
  5. Compositions d'agents de nettoyage selon l'une quelconque des revendications 1 à 4, caractérisées en ce qu'elles contiennent des inhibiteurs de la corrosion du groupe des inhibiteurs de la corrosion de l'argent et/ou ou des inhibiteurs de la corrosion du verre.
  6. Compositions d'agents de nettoyage selon la revendication 5, caractérisées en ce qu'elles contiennent, à concurrence de 0,01 à 15 % en poids, de préférence à concurrence de 0,1 à 10 % en poids, à titre préférentiel à concurrence de 0,2 à 5 % en poids, de manière particulièrement préférée à concurrence de 0,25 à 2,5 % en poids et en particulier à concurrence de 0,25 à 2 % en poids, des inhibiteurs de la corrosion, rapportés à l'agent dans sa totalité.
  7. Compositions d'agents de nettoyage selon l'une quelconque des revendications 5 ou 6, caractérisées en ce qu'elles contiennent des inhibiteurs de la corrosion de l'argent choisis parmi le groupe des triazoles, des benzotriazoles, des bisbenzotriazoles, des aminotriazoles, des alkylaminotriazoles et des sels ou des complexes de métaux de transition, de préférence le benzotriazole et/ou des alkylaminotriazoles.
  8. Compositions d'agents de nettoyage selon l'une quelconque des revendications 5 ou 6, caractérisées en ce qu'elles contiennent des inhibiteurs de la corrosion du verre choisis parmi le groupe des sels de magnésium et/ou du zinc et/ou des complexes du magnésium et/ou du zinc, de préférence le silicate de zinc, le carbonate de zinc, l'oxyde de zinc, le carbonate de zinc basique (Zn2(OH)2CO3), l'hydroxyde de zinc, l'oxalate de zinc, le monophosphate de zinc (Zn3(PO4)2) et le pyrophosphate de zinc (Zn2(P2O7)), le stéarate de zinc, l'oléate de zinc, le gluconate de zinc, l'acétate de zinc, le lactate de zinc, le citrate de zinc, le ricinoléate de zinc, l'abiétate de zinc, le nitrate-hexahydrate de zinc et/ou l'oxalate de zinc.
  9. Compositions d'agents de nettoyage selon l'une quelconque des revendications 1 à 8, caractérisées en ce qu'elles contiennent en outre des substances de soutien, la fraction des substances de soutien, rapportée à la composition totale étant inférieure à 15 % en poids, de préférence inférieure à 12 % en poids, de préférence inférieure à 9 % en poids et en particulier s'élevant de 0,01 à 6 % en poids.
  10. Compositions d'agents de nettoyage selon l'une quelconque des revendications 1 à 9, caractérisées en ce qu'elles contiennent des substances de soutien soluble dans l'eau, de préférence celles du groupe des citrates et/ou des phosphates, de préférence des phosphates de métaux alcalins, avec une préférence particulière pour le triphosphate pentasodique, respectivement pentapotassique (le tripolyphosphate de sodium, respectivement de potassium).
  11. Compositions d'agents de nettoyage selon l'une quelconque des revendications 1 à 10, caractérisées en ce qu'elles sont enveloppées d'une feuille mince soluble dans l'eau/apte à être dispersée dans l'eau.
  12. Compositions d'agents de nettoyage selon l'une quelconque des revendications 1 à 11, caractérisées en ce qu'elles sont confectionnées de manière conjointe avec d'autres compositions solides et/ou liquides d'agents de nettoyage.
  13. Utilisation d'un agent de nettoyage selon l'une quelconque des revendications 1 à 12, pour améliorer le résultat de rinçage d'une opération de lavage mécanique de la vaisselle.
  14. Procédé de lavage mécanique de la vaisselle avec mise en oeuvre d'une composition liquide d'agents de nettoyage selon l'une quelconque des revendications 1 à 12.
EP05783106A 2004-09-17 2005-09-08 Constituants de produits nettoyants Not-in-force EP1794269B1 (fr)

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EP (1) EP1794269B1 (fr)
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DE10042514A1 (de) * 2000-08-30 2002-03-14 Clariant Gmbh Wässerige Flüssigkeiten enthaltend ein Tensid und ein Acetal
WO2002061025A1 (fr) * 2001-02-01 2002-08-08 Cognis Deutschland Gmbh & Co. Kg Hydroxy-ethers mixtes a haut degre d'ethoxylation utilises comme agents antimoussants
DE10162696A1 (de) * 2001-02-01 2002-09-19 Cognis Deutschland Gmbh Spül- und Reinigungsmittel
DE10153554A1 (de) * 2001-07-07 2003-05-15 Henkel Kgaa Wäßrige "3in1"-Geschirrspülmittel II
DE10243661A1 (de) * 2002-09-19 2004-04-01 Clariant Gmbh Flüssige Wasch-und Reinigungsmittel mit Konsistenz-gebenden Polymeren

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WO2006032371A1 (fr) 2006-03-30
ATE434030T1 (de) 2009-07-15
DE102004045685A1 (de) 2006-04-06
PL1794269T3 (pl) 2009-12-31
EP1794269A1 (fr) 2007-06-13
DE502005007527D1 (de) 2009-07-30
US20080045441A1 (en) 2008-02-21

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