EP0876465B1 - Agent detergent pour lave-vaisselle - Google Patents

Agent detergent pour lave-vaisselle Download PDF

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Publication number
EP0876465B1
EP0876465B1 EP96934751A EP96934751A EP0876465B1 EP 0876465 B1 EP0876465 B1 EP 0876465B1 EP 96934751 A EP96934751 A EP 96934751A EP 96934751 A EP96934751 A EP 96934751A EP 0876465 B1 EP0876465 B1 EP 0876465B1
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EP
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Prior art keywords
weight
detergent
water
inorganic
soluble
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Expired - Lifetime
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EP96934751A
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German (de)
English (en)
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EP0876465A1 (fr
Inventor
Rainer Sorg
Willi Buchmeier
Peter Jeschke
Jürgen Härer
Christian Nitsch
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0073—Anticorrosion compositions

Definitions

  • the invention is in the field of machine dishwashing detergents and relates to the use of a combination of active ingredients to prevent the Tarnishing of silver or silver-plated wash ware.
  • active oxygen compounds such as Sodium perborate or sodium percarbonate were used, which to remove bleachable stains, such as Tea stains / tea deposits, coffee residues, vegetable dyes, lipstick residues and the like serve.
  • W094 / 26859 which goes back to the applicant, proposes to prevent silver corrosion, inorganic redox-active substances, in particular salts or complex compounds, certain metals among those Manganese is preferred to add.
  • Draw the funds so produced are characterized by their excellent effect and have proven themselves in practice. Under unfavorable conditions, however, certain color decorations, like them be used on drinking glasses, or plastic objects that are often washed, changed color or deposited become. At least in the case of using manganese sulfate such deposits are colored brown and are therefore consumed by the consumer not accepted.
  • corrosion is in its broadest use in chemistry To interpret meaning, in particular "corrosion” is meant for everyone visually barely noticeable change in a metal surface, here silver stand, be it for example a selective discoloration, be it z. B. a large start-up. Corrosion refers in the sense of this application only on the corrosion of metals, not on the corrosion of surfaces, which are made from molten silicates. Such areas are generally not attacked by lower alkaline agents.
  • Inorganic redox-active substances are such inorganic substances that of an easily occurring reversible oxidation and / or reduction are accessible.
  • the oxides, hydroxides or halides fall ammonium salts or alkali or alkaline earth metals under this definition.
  • the salts or complex compounds of certain are particularly suitable Metals.
  • the use of metal salts and / or metal complexes is preferred selected from the group of transition elements of the periodic table, especially manganese, titanium, zirconium, hafnium, vanadium, Cobalt and cerium salts and / or complexes to prevent silver corrosion, the metals in one of the oxidation states II, III, IV, V or VI are present.
  • the metal salts or metal complexes used are said to be at least partially be soluble in water.
  • the counterions suitable for salt formation include all usual one, two or three times negatively charged inorganic Anions, e.g. B. oxide, sulfate, nitrate, fluoride, but also organic anions such as B. stearate.
  • metal complexes are compounds which consist of a Central atom and one or more ligands exist.
  • the central atom is one of the above Metals in one of the above Oxidation levels.
  • the ligands are neutral molecules or anions that are monodentate or multidentate; the The term "ligand" in the sense of the invention is e.g. in "Römpp Chemie Lexikon, Georg Thieme Verlag Stuttgart / New York, 9th edition, 1990, page 2507 "closer explained.
  • the charge of the central atom is complemented in a metal complex and the charge of the ligand (s) is not on zero, so, ever depending on whether there is a cationic or an anionic excess charge, either one or more of the above Anions or one or more Cations, e.g. B. sodium, potassium, ammonium ions for charge balance.
  • Suitable complexing agents are e.g. Citrate, acetylacetonate or 1-hydroxyethane-1,1-diphosphonate.
  • 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], salts of acids of vanadium, based on V 2 O 5 , V 2 O 4 , VO 2 (here: called vanadates), TiOSO 4 , CoSO 4 , Co (NO 3 ) 2 , Ce (NO 3 ) 3 and their mixtures. MnSO 4 is particularly preferred.
  • metal salts or metal complexes are generally commercially available substances which can be used for the purpose of the silver corrosion protection according to the invention without prior cleaning.
  • the mixture of pentavalent and tetravalent vanadium (V 2 O 5 , VO 2 , V 2 O 4 ) known from SO 3 production (contact process) is suitable, as is that by diluting a Ti (SO 4 ) 2 - Solution resulting titanyl sulfate, TiOSO 4 .
  • the inorganic redox-active substances are preferably coated, i.e. completely with one waterproof, but easily soluble at cleaning temperatures coated to prevent their premature decomposition or oxidation during storage to prevent.
  • Preferred coating materials according to known Processes, such as Sandwik melt coating processes from the food industry, are applied, paraffins, micro waxes, waxes are 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 melted State applied to the material to be coated, e.g.
  • the melting point must be selected that the coating material during the subsequent use of the Silver corrosion protection agent easily dissolves in the dishwasher or melts quickly.
  • the melting point should therefore be suitable for most applications ideally in the range between 45 ° C and 65 ° C and preferably in Range 50 ° C to 60 ° C.
  • Inorganic, water-soluble, ionic fluorine compounds from the class of the salts or complex salts which release fluoride ions under the conditions of automatic dishwashing can be used as fluorine compounds.
  • Salts of hydrofluoric acid or hexafluorosilicic acid or mono-, di- or pentafluorophosphoric acid are particularly suitable.
  • fluorides of the alkali salts such as sodium or potassium, ammonium fluoride, magnesium fluoride and complex fluorides such as magnesium hexafluorosilicate, sodium hexafluorosilicate, potassium hexafluorosilicate, sodium hexafluorosilicate, ammonium hexafluorosilicate.
  • Fluorophosphates of alkali metals or ammonium are also suitable.
  • Preferred among these compounds are the hexafluorosilicate, in particular sodium or magnesium hexafluorosilicate. It is also possible to use aluminum hexafluoride or tin tetrafluoride. However, these substances are not preferred.
  • the fluorine compounds mentioned are used in amounts of 0.1 to 6% by weight, preferably 0.1 to 5 and in particular 0.2 to 2.5% by weight, based on the mixture as a whole.
  • inorganic redox-active compounds described above are particularly suitable However, substances to prevent silver corrosion when in lower alkaline Cleaners for machine cleaning of dishes included are. This is all the more surprising than these silver corrosion inhibitors in effect not by the presence of usually in low alkaline cleaners contain oxygen-based bleaches be affected.
  • Another subject of the invention are therefore low-alkaline agents for machine cleaning of dishes, the 1% by weight solutions of which have a pH of 8 to 11.5, preferably 9 to 10.5, containing 15 to 60% by weight, preferably 30 to 50% by weight of a water-soluble builder component, 5 to 25% by weight, preferably 10 to 15% by weight of an oxygen-based bleach, 1 to 10% by weight, preferably 2 to 6% by weight of an organic , O- or N- (C 1 -C 12 ) -acyl group-containing bleach activator, 0.1 to 5% by weight, preferably 0.5 to 2.5% by weight of an enzyme, in each case based on the total agent, and Silver corrosion protection agent, an inorganic redox-active substance being contained as the silver corrosion protection agent.
  • Metal salts and / or metal complexes selected from the group consisting of manganese, titanium, zirconium, hafnium, vanadium, cobalt, cerium salts and / or complexes are particularly suitable, the metals being in one of the oxidation states II, III , IV, V or VI are present.
  • the inorganic redox-active substances are preferred, in particular Metal salts and / or metal complexes in the agents according to the invention in a total amount of 0.05 to 6% by weight, preferably 0.2 to 2.5% by weight, based on the total mean.
  • Organic, O- or N- (C 1 -C 12 -) acyl group-containing bleach activators are substances in which at least one C 1 -C 12 acyl group, preferably the acetyl group, is attached to a 0 or an N atom contained in the substance is bound, and the perhydrolysis thereof provides C 1 -C 12 -alkanic acids, preferably peracetic acid.
  • polymeric alkali metal phosphates which may be in the form of their alkaline neutral or acidic sodium or potassium salts.
  • examples include: tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium and potassium salts.
  • the amounts of phosphate are in the range of up to about 30% by weight, based on the total agent; however, the agents according to the invention are preferably free of such phosphates.
  • water-soluble builder components are e.g. B. organic polymers of native or synthetic origin, especially polycarboxylates, which act in particular in hard water systems as a co-builder.
  • polyacrylic acids and copolymers of maleic anhydride and acrylic acid and the sodium salts of these polymer acids are suitable.
  • Commercial products include Sokalan (R) CP 5 and PA 30 from BASF, Alcosperse (R) 175 or 177 from Alco, LMW (R) 45 N and SP02 N from Norsohaas.
  • the native polymers include, for example, oxidized starch (e.g. German patent application P 42 28 786.3) and polyamino acids such as polyglutamic acid or polyaspartic acid and NTA and their derivatives.
  • hydroxycarboxylic acids such as B. mono-, dihydroxysuccinic acid, ⁇ -hydroxypropionic acid and gluconic acid.
  • Preferred builder components are the salts of Citric acid, especially sodium citrate.
  • sodium citrate come anhydrous Trisodium citrate or preferably trisodium citrate dihydrate in Consideration. Trisodium citrate dihydrate can be fine or coarse crystalline Powder can be used.
  • citric acid available.
  • oxygen-based bleaches Sodium perborate mono- and tetrahydrate or sodium percarbonate are primarily considered as oxygen-based bleaches.
  • the oxygen-based bleach is therefore preferably a percarbonate salt, especially sodium percarbonate. Since active oxygen only develops its full effect on its own at elevated temperatures, so-called bleach activators are used to activate it in the dishwasher.
  • Organic bleach activators containing 0- or N- (C 1 -C 12 ) acyl groups such as PAG (pentaacetyl glucose), DADHT (1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine) are used as bleach activators ) and ISA (isatoic anhydride), but preferably N, N, N ', N'-tetraacetylethylene diamine (TAED).
  • PAG penentaacetyl glucose
  • DADHT 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine
  • ISA isatoic anhydride
  • TAED tetraacetylethylene diamine
  • bleach stabilizers such as, for example, phosphonates, borates or metaborates and metasilicates and magnesium salts such as magnesium sulfate may also be useful.
  • the dishwashing detergents according to the invention contain enzymes such as proteases, amylases, lipases and cellulases, for example proteases such as BLAP (R) 140 from Henkel; Optimase (R) -M-440, Optimase (R) -M-330, Opticlean (R) -M-375, Opticlean (R) -M-250 from Solvay Enzymes; Maxacal (R) CX 450,000, Maxapem (R) from Gist Brocades; Savinase (R) 4.0 T, 6.0 T, 8.0 T from Novo; Esperase (R) T from Ibis and amylases such as Termamyl (R) 60 T, 90 T from Novo; Amylase-LT (R) from Solvay Enzymes or Maxamyl (R) P 5000, CXT 5000 or CXT 2900 from Gist Brocades; Lipases
  • the agents according to the invention additionally contain the alkali carriers contained in conventional low-alkaline machine dishwashing detergents, such as, for. B. alkali silicates, alkali carbonates and / or alkali hydrogen carbonates.
  • Alkali silicates can be used in amounts of up to 30% by weight. %, based on the total, may be included.
  • the use of the highly alkaline metasilicates as alkali carriers is preferably avoided.
  • the alkali carrier system preferably used in the agents according to the invention is a mixture of essentially carbonate and hydrogen carbonate, preferably sodium carbonate and hydrogen carbonate, in an amount of up to 60% by weight, preferably 10 to 40% by weight, based on the total agent , is included.
  • the ratio of carbonate and bicarbonate used varies; Usually, however, an excess of sodium hydrogen carbonate is used, so that the weight ratio between hydrogen carbonate and carbonate is generally 1: 1 to 15: 1.
  • surfactants in particular low-foaming nonionic surfactants, can also be added to the agents according to the invention, which serve to better detach fatty food residues, as wetting agents, as granulating aids or as dispersing aids for better, homogeneous distribution of the aforementioned silver corrosion inhibitors in the washing liquor and on the silver surfaces.
  • Their amount is then up to 5% by weight, preferably up to 2% by weight.
  • Extremely low-foam connections are usually used. These preferably include C 12 -C 18 alkyl polyethylene glycol polypropylene glycol ethers, each containing up to 8 moles of ethylene oxide and propylene oxide units in the molecule.
  • low-foam nonionic surfactants such as.
  • B. C 12 -C 18 alkyl polyethylene glycol polybutylene glycol ether, each with up to 8 moles of ethylene oxide and butylene oxide units in the molecule, end-capped alkyl polyalkylene glycol mixed ethers and the foaming but ecologically attractive C 8 -C 14 alkyl polyglucosides with a degree of polymerization of about 1 - 4 ( e.g. APG (R) 225 and APG (R) 600 from Henkel) and / or C 12 -C 14 alkyl polyethylene glycols with 3 - 8 ethylene oxide units in the molecule.
  • APG (R) 225 and APG (R) 600 from Henkel e.g. APG (R) 225 and APG (R) 600 from Henkel
  • Bleached quality should be used, otherwise brown granules will result.
  • the cleaning agents foam too much during use, them up to 6% by weight, preferably about 0.5 to 4% by weight of one foam-suppressing compound, preferably from the group of silicone oils, Mixtures of silicone oil and hydrophobicized silica, paraffin oil / Guerbet alcohols, Paraffins, hydrophobized silica, the bisstearic acid amides and other other well known commercially available defoamers be added.
  • Other optional additives are e.g. B. Perfume oils.
  • the dishwashing detergents according to the invention are preferably in powder form, granular or tablet-like preparations that are in themselves customary, for example by mixing, granulating, roller compacting and / or can be produced by spray drying.
  • the procedure is preferably such that all constituents are mixed with one another in a mixer and the mixture by means of conventional tablet presses, for example eccentric presses or rotary presses, with compression pressures in the range from 200 ⁇ 10 5 Pa to 1 500 ⁇ 10 5 Pa pressed.
  • conventional tablet presses for example eccentric presses or rotary presses
  • compression pressures in the range from 200 ⁇ 10 5 Pa to 1 500 ⁇ 10 5 Pa pressed.
  • a tablet produced in this way preferably has a weight of 15 g to 40 g, in particular 20 g to 30 g, with a diameter of 35 mm to 40 mm.
  • machine dishwashing detergents in the form of non-dusting, storage-stable free-flowing powders and / or granules with high Bulk densities in the range from 750 to 1000 g / l are characterized by that in a first stage of the process with the builder components at least a proportion of liquid mixture components while increasing the Bulk density of this premix is mixed and subsequently - if desired after intermediate drying - the other components of the dishwasher detergent, including the inorganic redox-active substances combined with the premix obtained in this way.
  • the intermediate drying must be carried out so that the Disintegration of sodium bicarbonate to sodium carbonate as low as possible (or at least as constant as possible).
  • An additional through drying The resulting sodium carbonate portion should namely in the formulation of Granulate recipe are taken into account.
  • Low drying temperatures not only counteract sodium bicarbonate decay, but also also increase the solubility of the granulated detergent in the Application. It is therefore advantageous when drying a supply air temperature that on the one hand as low as possible to avoid bicarbonate decay should be and which, on the other hand, must be as high as necessary to produce a product with good storage properties. Drying is preferred an inlet air temperature of approx. 80 ° C.
  • the builder is usually mixed with at least a mixing process another component of the dishwashing detergent with the liquid components acted upon.
  • a preliminary stage can be considered, in which the builder component in admixture with perborate with the liquid non-ionic surfactants and / or the solution of the fragrances and is intimately mixed.
  • the remaining components added and worked through the entire mixture in the mixing device and homogenized.
  • the use of additional amounts of liquid, in particular the use of additional water is here in the Usually not required.
  • the resulting mixture of substances then lies as free-flowing, dust-free powder of the desired high bulk density about in the range of 750 to 1000 g / l.
  • the pre-granules are then mixed with the missing components of the dishwashing detergent, including inorganic redox-active substances, to the finished product mixed.
  • the mixing time is all shown here Cases both in the preliminary stage of the compacting mixture under influence of liquid components as in the final mix below with the other components in the range of a few minutes, for example in the range from 1 to 5 minutes.
  • it can be used in the manufacture of fine Granules may be useful by powdering the surface of the formed Granules a further stabilization and leveling adjust. Small amounts of water glass powder are particularly suitable for this or powdered alkali carbonate.
  • the funds to be used can be found both in household dishwashers as used in commercial dishwashers.
  • the addition takes place by hand or using suitable dosing devices.
  • the application concentrations in the cleaning liquor are preferably about 2 to 8 g / l 3 to 6 g / l.
  • the washing program of a household dishwasher is generally through some intermediate rinse cycles following the cleaning cycle with clear Water and a rinse aid supplemented with a common rinse aid and ended. After drying, you not only get a completely clean one and in terms of hygiene, perfect dishes, but in front especially bright silver cutlery.
  • a low-alkaline cleaner for household dishwashers was produced, whose 1% by weight solution in distilled water has a pH of 9.5. They were used for this 56.0% by weight Trisodium citrate dihydrate 36.1% by weight Sodium bicarbonate 6.1% by weight Sodium carbonate, anhydrous 1.8% by weight Mixture of nonionic surfactants from C 8 to C 10 alkyl oligoglucoside and C 12 to C 14 fatty alcohol 2EO ethoxylate in a ratio of 1: 1.
  • the base product obtained in this way was disassembled into a dishwashing detergent as follows: 81% by weight Basic product 12% by weight Sodium percarbonate 4% by weight Bleach activator TAED 2% by weight Manganese sulfate monohydrate coated with paraffin (1.5% by weight of manganese salt, based on the recipe) rest Enzymes, especially protease and amylase.
  • the product thus obtained was at a dosage of 30 g per Washing program, washing attempts in a Bosch SMS 7082 machine 65 ° C (universal program).
  • the machine was filled with water from fed about 16 ° dH.
  • Decorative glasses were used as wash ware, which contain high-bleach melting colors on the one hand or with lead-free colors based on bismuth were printed on the other side. The print showed red, blue, yellow, green and white swatches.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
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  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Claims (13)

  1. Utilisation d'une combinaison d'une combinaison de :
    composés métalliques à action Redox inorganique soluble dans l'eau et
    composés de fluor inorganiques et solubles dans l'eau, dans des agents pour lavage de vaisselle à la machine afin d'inhiber la corrosion de l'argent et la décoloration des décors.
  2. Mode de réalisation selon l'invention,
    caractérisé en ce que
    les sels métalliques et/ou les complexes métalliques sont choisis dans le groupe constitué par MnSO4, le citrate de Mn(II), le stéarate de Mn(II), l'acétylacétonate de Mn(II), le [1-hydroxyéthan-1,1-diphosphonate] de Mn(II).
  3. Mode de réalisation selon les revendications 1 et 2,
    caractérisé en ce qu'
    on utilise comme composés de fluor ionique, soluble dans l'eau, inorganique, des sels ou des sels complexes qui dans les conditions du lavage de la vaisselle à la machine libèrent des ions fluor, en particulier des sels de métaux alcalins ou d'ammonium de l'acide fluorhydrique, de l'acide hexafluorosilicique, de l'acide mono-, di- ou pentafluorophosphorique.
  4. Mode de réalisation selon les revendications 1 à 3,
    caractérisé en ce qu'
    on utilise les composés ioniques solubles dans l'eau inorganiques à des quantités de 0,1 à 6 % en poids.
  5. Mode de réalisation selon les revendications 1 à 4,
    caractérisé en ce qu'
    on utilise comme composés métalliques à action Redox inorganiques solubles dans l'eau le sulfate de manganèse.
  6. Agents faiblement alcalins pour le lavage à la machine de la vaisselle, dont la solution à 1 % en poids présente un pH de 8 à 11,5, de préférence de 9 à 10,5, contenant de 15 à 60 %, de préférence de 30 à 50 % en poids, d'un composant adjuvant soluble dans l'eau, de 5 à 25 % en poids, de préférence de 10 à 15 % en poids, d'un agent de blanchiment à base d'oxygène, de 1 à 10 % en poids, de préférence de 2 à 6 % en poids, d'un activateur d'agent de blanchiment organique contenant des groupes O- ou N-acyle en C1 à C12, de 0,1 à 5 % en poids, de préférence de 0,5 à 2,5 % en poids d'une enzyme, toujours par rapport à l'ensemble de l'agent, et des agents de protection contre la corrosion de l'argent,
    caractérisé en ce qu'
    on utilise comme agents de protection contre la corrosion de l'argent un composé métallique à action Redox soluble dans l'eau inorganique, et pour inhiber la décoloration des décors, un composé de fluor ionique soluble dans l'eau et inorganique.
  7. Agent selon la revendication 6,
    caractérisé en ce que
    le sel métallique est MnSO4.
  8. Agent selon les revendications 6 à 7,
    caractérisé en ce qu'
    on utilise comme composés de fluor les sels de l'acide fluorhydrique, de l'acide hexafluorosilicique ou des acides fluorophosphoriques avec les métaux alcalins, l'ammonium ou le magnésium.
  9. Agent selon les revendications 6 à 8,
    caractérisé en ce que
    les substances à action Redox inorganiques sont contenues en une quantité de 0,05 à 6 % en poids, de préférence de 0,2 à 2,5 % en poids, par rapport à l'ensemble des agents, et
    les composés de fluor ioniques, solubles dans l'eau, inorganiques, sont utilisés à des quantités de 0,1 à 5 % en poids, de préférence à des quantités de 0,2 à 2,5 % en poids.
  10. Agent selon les revendications 6 à 9,
    caractérisé en ce que
    le composant adjuvant soluble dans l'eau est un sel d'acide citrique, de préférence le citrate trisodique et/ou son dihydrate.
  11. Agent selon les revendications 6 à 10,
    caractérisé en ce que
    l'agent de blanchiment à base d'oxygène est un sel percarbonate, de préférence le percarbonate de sodium.
  12. Agent selon les revendications 6 à 11,
    caractérisé en ce que
    l'activateur de blanchiment organique contenant des groupes O- ou N-acyle en C1 à C12 est la N,N,N',N'-tétraacétyléthylène diamine (TAED).
  13. Agent selon les revendications 6 à 12,
    caractérisé en ce qu'
    on utilise comme enzyme en particulier des amylases, des protéases et/ou des lipases.
EP96934751A 1995-10-27 1996-10-18 Agent detergent pour lave-vaisselle Expired - Lifetime EP0876465B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19540087A DE19540087A1 (de) 1995-10-27 1995-10-27 Geschirrspülmittel
DE19540087 1995-10-27
PCT/EP1996/004542 WO1997016520A1 (fr) 1995-10-27 1996-10-18 Agent detergent pour lave-vaisselle

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EP0876465A1 EP0876465A1 (fr) 1998-11-11
EP0876465B1 true EP0876465B1 (fr) 2000-04-12

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EP (1) EP0876465B1 (fr)
DE (2) DE19540087A1 (fr)
ES (1) ES2146417T3 (fr)
WO (1) WO1997016520A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7243664B2 (en) 2005-03-04 2007-07-17 The Procter & Gamble Company Automatic dishwashing composition with corrosion inhibitors

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10114980A1 (de) * 2001-03-27 2002-10-17 Henkel Kgaa Haftvermittler für Lacke und Klebstoffe auf Metallen
US9144538B2 (en) 2013-02-08 2015-09-29 The Procter & Gamble Company Cosmetic compositions containing substituted azole and methods for alleviating the signs of photoaged skin
US9138393B2 (en) 2013-02-08 2015-09-22 The Procter & Gamble Company Cosmetic compositions containing substituted azole and methods for improving the appearance of aging skin

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3714451A1 (de) * 1987-04-30 1988-11-10 Hoechst Ag Mittel zur verhinderung von korrosion an keramischen oberflaechen
WO1994019445A1 (fr) * 1993-02-22 1994-09-01 Unilever N.V. Composition de lavage pour lave-vaisselle
PL177936B1 (pl) * 1993-05-08 2000-01-31 Henkel Kgaa Niskoalkaliczny środek do maszynowego zmywania naczyń
DE4344215A1 (de) * 1993-12-23 1995-06-29 Cognis Bio Umwelt Silberkorrosionsschutzmittelhaltige Enzymzubereitung

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7243664B2 (en) 2005-03-04 2007-07-17 The Procter & Gamble Company Automatic dishwashing composition with corrosion inhibitors

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ES2146417T3 (es) 2000-08-01
WO1997016520A1 (fr) 1997-05-09
EP0876465A1 (fr) 1998-11-11
DE59604975D1 (de) 2000-05-18
DE19540087A1 (de) 1997-04-30

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