EP0697035B1 - Produit i de protection de l'argent contre la corrosion - Google Patents

Produit i de protection de l'argent contre la corrosion Download PDF

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Publication number
EP0697035B1
EP0697035B1 EP94916181A EP94916181A EP0697035B1 EP 0697035 B1 EP0697035 B1 EP 0697035B1 EP 94916181 A EP94916181 A EP 94916181A EP 94916181 A EP94916181 A EP 94916181A EP 0697035 B1 EP0697035 B1 EP 0697035B1
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EP
European Patent Office
Prior art keywords
weight
detergent
silver
salts
metal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP94916181A
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German (de)
English (en)
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EP0697035A1 (fr
Inventor
Jürgen Härer
Helmut Blum
Birgit Burg
Thomas Holderbaum
Willi Buchmeier
Peter Jeschke
Horst-Dieter Speckmann
Frank Wiechmann
Christian Nitsch
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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 DE19934315397 external-priority patent/DE4315397A1/de
Priority claimed from DE19934325922 external-priority patent/DE4325922A1/de
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0697035A1 publication Critical patent/EP0697035A1/fr
Application granted granted Critical
Publication of EP0697035B1 publication Critical patent/EP0697035B1/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
    • C11D3/02—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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0091—Dishwashing tablets
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0042—Reducing agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0073—Anticorrosion compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • C11D3/048—Nitrates or nitrites
    • 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
    • C11D3/12—Water-insoluble 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/1213—Oxides or hydroxides, e.g. Al2O3, TiO2, CaO or Ca(OH)2
    • 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
    • C11D3/12—Water-insoluble compounds
    • C11D3/122—Sulfur-containing, e.g. sulfates, sulfites or gypsum
    • 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
    • C11D3/2072—Aldehydes-ketones
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2079—Monocarboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/34—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
    • C11D3/361—Phosphonates, phosphinates or phosphonites
    • 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
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2041—Dihydric alcohols
    • C11D3/2058—Dihydric alcohols aromatic
    • 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
    • C11D3/3472—Organic compounds containing sulfur additionally containing -COOH groups or derivatives thereof

Definitions

  • 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.
  • inorganic redox-active substances in particular the salts or complex compounds of certain, so far metals not yet described as silver anticorrosion agents which Effectively prevent corrosion of silver in automatic dishwashers.
  • the invention relates to Use of inorganic redox-active substances in dishwashing preparations as a silver corrosion inhibitor, characterized in that the inorganic redox-active substances are at least partially soluble in water Metal salts and / or metal complexes selected from the group of manganese, Titanium, zirconium, hafnium, vanadium, cobalt and cerium salts and / or complexes and the metals in one of the oxidation states II, III, IV, V or VI are present.
  • 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 z. B. a selective discoloration, be it z. B. a large area Start up.
  • 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 suitable Metals, i.e. the use of metal salts and / or metal complexes selected from the group of manganese, titanium, zirconium, hafnium, Vanadium, cobalt and cerium salts and / or complexes for prevention the silver corrosion, the metals in one of the oxidation stages 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; of 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], 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.
  • 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 for most Applications ideally in the range between 45 ° C and 65 ° C and preferred are in the range of 50 ° C to 60 ° C.
  • 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 , 0- 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 anticorrosive, wherein as silver anticorrosive 0.05 to 6 wt .-% at least partially water-soluble metal salts and / or metal complexes selected from the group of manganese, titanium, zirconium, hafnium, vanadium, cobalt, cerium salts and / or complexes, the metals being in one of the
  • Preferred dish detergents contain metal salts or metal complexes 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.
  • MnSO 4 is particularly preferred.
  • 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 0.2 to 2.5% by weight, based on the total mean.
  • Organic, 0 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 N atom contained in the substance is bound, and the perhydrolysis thereof provides C 1 -C 12 alkanoic 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, e.g. B. from the companies Cygnus and SRCHEM.
  • 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.
  • Trisodium citrate dihydrate can be fine or coarse crystalline Powder can be used.
  • Depending on the ultimately in the pH set according to the invention can also be adjusted to citrate corresponding acids are present.
  • Sodium perborate mono- and tetrahydrate or sodium percarbonate are primarily considered as oxygen-based bleaches.
  • the use of sodium percarbonate has advantages because it has a particularly favorable effect on the corrosion behavior on glasses.
  • 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 Ibis; 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 Ibis; Lipases such as Lipolase (L) (R) P 5000, CXT 5000 or C
  • the agents according to the invention preferably additionally contain the alkali carriers contained in customary low-alkaline machine dishwashing agents, 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.
  • 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 2 to 5 g / l.
  • the rinse program is generally followed by some on the cleaning cycle following intermediate rinse cycles with clear water and a rinse cycle with supplemented with a common rinse aid and finished. After drying you don't just get a completely clean and hygienic one flawless crockery, but above all bright silver silver cutlery.
  • Silver spoons (type WMF, hotel cutlery, form Berlin) were cleaned with a silver cleaner, degreased with petrol and dried. Three spoons each were then placed in the cutlery basket of a Bosch S 712 household dishwasher (HGSM). The cleaning program (65 ° C, 16 ° dH) has now been started and 50 g of soiling (1) and 30 g of the detergent have been dosed directly into the machine. After the rinsing and drying process had ended, the HGSM were opened for 10 minutes, the machine was closed again and rinsed again in the same way. After the 10th rinse, the spoons were removed and evaluated.
  • HGSM Bosch S 712 household dishwasher
  • 16 l of cold city water (16 ° d) are briefly heated to boiling in a water treatment boiler.
  • 96 g of black tea are drawn in the nylon net with the lid closed for 5 minutes and the tea is transferred to a diving apparatus with heating and agitator.
  • 60 teacups are dipped into the prepared tea brew 25 times at one-minute intervals at 70 ° C. The cups are then removed and placed on a tray with the opening facing down to dry.
  • the following low-alkaline base product was first prepared, whose 1% by weight solution in distilled water gave a pH of 9.5: 56.0% Trisodium citrate dihydrate 36.1% Sodium bicarbonate 6.1% Sodium carbonate, anhydrous 1.8% Mixture of nonionic surfactants from APG 225 (C 8 -C 10 alkyl oligoglucoside) and dehydol (R) LS2 (C 12 -C 14 fatty alcohol 2EO ethoxylate) (1: 1)
  • the silver spoons were consistently rated 0 to 1, i.e. "no to very weak Tarnishing ", evaluated.
  • the compositions 1 up to 20 against bleachable stains such as B. Excellent tea Cleaning services.
  • Electrolytes and electrodes are Electrolytes and electrodes:
  • the experiments were carried out in a Duran glass cell.
  • the counter electrode consisted of a gold plate (99.99%) with an area of 1 cm 2 .
  • a Hg / Hg0 / 0.1 m NaOH electrode was chosen as the reference electrode due to the alkaline electrolyte solutions, which was connected to the electrolytes via a Haber-Luggin capillary.
  • the measurements were carried out with 5 g / l cleaner in tap water of 16 ° d and a salt load of approx. 600 mg (dry residue).
  • the lower alkaline solution was used first Base product (see above) dissolved and the solution heated to 65 ° C. Directly Before the measurement, the bleach and the bleach activator and / or the silver anticorrosive agent is added. Then the electrochemical measurement. During the electrochemical experiments the electrolyte solutions are heated to 65 ° C and flushed with air.
  • the electrode potential was used to record the current-voltage curves from - 0.62, V based on the standard hydrogen electrode (SHE), increased at a constant speed. After a total increase The potential then became 1.1 V at the same speed degraded.
  • SHE standard hydrogen electrode
  • a standard potentiostat consisting of positive feedback amplifier was used for this, Differential amplifier, adder and impedance converter, as well a function generator (Prodis 16 from Intelligent Controls CLZ GmbH).
  • the corrosion behavior was characterized using current voltage curves.
  • Essential information comes from the zero crossing of the current-voltage curve (rest potential, which arises automatically even without external influence on the potential) and the slope of the curve at the zero crossing (reciprocal polarization resistance)
  • the addition of the silver corrosion inhibitor shifts the potential for zero crossing to lower values and the slope decreases. Silver corrosion is also significantly reduced by the addition of silver corrosion protection agents, which can be measured electrochemically.
  • Composition cleaner Position zero crossing E (mV) (SHE) Slope at zero crossing di / dE (mA / V) Basic product (87%) 435 25th + 12% percarbonate + 1% TAED Basic product (87%) 360 0.3 + 12% percarbonate + 1% silver corrosion inhibitor Basic product (86.5%) 405 7 + 12% percarbonate + 1% TAED + 0.5% anticorrosive silver Basic product (86%) 375 0.6 + 12% percarbonate + 1% TAED + 1% silver corrosion inhibitor

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  • Inorganic Chemistry (AREA)
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  • Detergent Compositions (AREA)
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Claims (15)

  1. Utilisation de substances minérales actives dans les systèmes redox, dans des préparations de nettoyage de la vaisselle, en tant qu'agent de protection de l'argent contre la corrosion,
    caractérisée en ce que
    les substances minérales actives dans les systèmes redox sont des sels métalliques et/ou des complexes de métaux au moins partiellement solubles dans l'eau, choisis dans le groupe des sels et/ou des complexes du manganèse, du titane, du zirconium, du hafnium, du vanadium, du cobalt, et du cérium et en ce que les métaux se présentent dans un des degrés d'oxydation II, III, IV, ou VI.
  2. Utilisation selon la revendication 1,
    caractérisée en ce que
    les sels métalliques et/ou les complexes de métaux sont choisis dans le groupe formé de SO4Mn, le citrate de Mn (II), du stéarate de Mn (II), de l'acétylacéconate de Mn (II), du [1-hydroxyéthane 1,1-diphosphonate] de Mn (II), de V2O5, de V2O4, de VO2, de TiOSO4, de K2TiF6, de K2ZrF6, de CoSO4, de (NO3)2Co et de (NO)3)3Ce.
  3. Utilisation selon la revendication 2,
    caractérisée en ce que
    le sel métallique est SO4Mn.
  4. Agent faiblement alcalin pour le lavage à la machine de la vaisselle dont la solution à 1 % en poids possède une valeur de pH de 8 à 11,5, de préférence de 9 à 10,5, contenant de 15 à 60 % en poids, de préférence de 30 à 50 % en poids d'un composant de structuration 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 contenant des groupes O- ou N-acyl en C1 à C12, de 0,1 à 5 % en poids, de préférence de 0,5 à 2,5 % en poids d'un enzyme, à chaque fois rapporté au produit total et un produit de protection de l'argent contre le corrosion,
    caractérisé en ce que
    comme produit de protection de l'argent contre la corrosion sont contenus 0,05 à 6 % en poids de sels métalliques et/ou de complexes de métaux au moins partiellement solubles dans l'eau choisis dans le groupe des sels et/ou des complexes du manganèse, du titane, du zirconium, du Hafnium, du vanadium, du cobalt et du cérium et en ce que les métaux se présentent dans l'un des degrés d'oxydation II, III, IV, V ou VI.
  5. Produit selon la revendication 4,
    caractérisé en ce que
    les sels métalliques et/ou les complexes de métaux sont choisis dans le groupe formé de SO4Mn, du citrate de Mn (Il), du stéarate de Mn (II), de l'acétylacetonate de Mn (II), du (1-hydroxyéthane-1,1-diphosphonate) de Mn (II), de V2O5, de V2O4, de VO2, de TiOSO4, de K2TiF6, de K2ZrF6, de CoSO4, de (NO3)2Co et de (NO)3)3Ce.
  6. Produit selon la revendication 5,
    caractérisé en ce que
    le sel métallique est SO4Mn.
  7. Produit selon les revendications 4 à 6,
    caractérisé en ce que
    les produits de protection de l'argent contre la corrosion sont ccntenus en une quantité allant de 0,2 à 2,5 % en poids rapporté au produit total.
  8. Produit selon les revendications 4 à 7,
    caractérisé en ce que
    le composant d'agent de structuration soluble dans l'eau est un sel d'acide citrique, de préférence le citrate de sodium.
  9. Produit selon les revendications 4 à 8,
    caractérisé en ce que
    l'agent de blanchiment à base d'oxygène est un sel de percarbonate, de préférence le percarbonate de sodium.
  10. Produit selon les revendications 4 à 9,
    caractérisé en ce que
    l'activateur d'agent de blanchiment organique contenant des groupes O- ou N-acyle en C1 à C12 est la N,N,N',N'-tétraacétyléthylènediamine.
  11. Produit selon les revendications 4 à 10,
    caractérisé en ce que
    l'enzyme est une amylase et/ou une protéase.
  12. Produit selon les revendications 4 à 11,
    caractérisé en ce qu'
    il renferme en supplément jusqu'à 60 % en poids, de préférence de 10 à 40 % en poids rapporté au produit total, d'un système vecteur d'alcali qui consiste essentiellement en du carbonate et de l'hydrogénocarbonate, de préférence en du carbonate de sodium et de l'hydrogénocarbonate de sodium.
  13. Produit selon les revendications 4 à 12,
    caractérisé en ce qu'
    il renferme en supplément jusqu'à 5 % en poids, de préférence jusqu'à 2 % en poids, rapporté au produit total, d'agents tensioactifs, de préférence des agents tensioactifs non ioniques faiblement moussants.
  14. Produit selon les revendications 4 à 13,
    caractérisé en ce qu'
    il se présente sous forme de comprimés et en ce qu'il est accessible par mélange de tous ses constituants dans en mélangeur et compression du mélange à l'aide d'une presse à comprimés à des pressions de compression allant de 2 x 107 Pa à 1,5 x 108 Pa.
  15. Produit selon les revendications 4 à 14,
    caractérisé en ce qu'
    il se présente sous forme de poudre ou de granulé et qu'il possède une densité apparente allant de 750 g/l à 1000 g/l.
EP94916181A 1993-05-08 1994-05-02 Produit i de protection de l'argent contre la corrosion Expired - Lifetime EP0697035B1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE4315397 1993-05-08
DE19934315397 DE4315397A1 (de) 1993-05-08 1993-05-08 Reinigungsmittel mit Verhinderung des Anlaufens von Tafelsilber in Geschirrspülmaschinen
DE4325922 1993-08-02
DE19934325922 DE4325922A1 (de) 1993-08-02 1993-08-02 Silberkorrosionsschutzmittel I
PCT/EP1994/001386 WO1994026859A1 (fr) 1993-05-08 1994-05-02 Produit i de protection de l'argent contre la corrosion

Publications (2)

Publication Number Publication Date
EP0697035A1 EP0697035A1 (fr) 1996-02-21
EP0697035B1 true EP0697035B1 (fr) 1998-02-11

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EP94916181A Expired - Lifetime EP0697035B1 (fr) 1993-05-08 1994-05-02 Produit i de protection de l'argent contre la corrosion

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EP (1) EP0697035B1 (fr)
JP (1) JPH08509777A (fr)
AT (1) ATE163191T1 (fr)
CA (1) CA2162460A1 (fr)
CZ (1) CZ286401B6 (fr)
DE (1) DE59405259D1 (fr)
DK (1) DK0697035T3 (fr)
ES (1) ES2112542T3 (fr)
PL (1) PL177936B1 (fr)
WO (1) WO1994026859A1 (fr)

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PL311594A1 (en) 1996-02-19
WO1994026859A1 (fr) 1994-11-24
CZ286401B6 (en) 2000-04-12
DK0697035T3 (da) 1998-09-28
CA2162460A1 (fr) 1994-11-24
ATE163191T1 (de) 1998-02-15
ES2112542T3 (es) 1998-04-01
EP0697035A1 (fr) 1996-02-21
CZ234895A3 (en) 1996-01-17
JPH08509777A (ja) 1996-10-15
DE59405259D1 (de) 1998-03-19

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