EP0697036B1 - Produits de protection de l'argent contre la corrosion ii - Google Patents

Produits de protection de l'argent contre la corrosion ii Download PDF

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Publication number
EP0697036B1
EP0697036B1 EP94917579A EP94917579A EP0697036B1 EP 0697036 B1 EP0697036 B1 EP 0697036B1 EP 94917579 A EP94917579 A EP 94917579A EP 94917579 A EP94917579 A EP 94917579A EP 0697036 B1 EP0697036 B1 EP 0697036B1
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EP
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Prior art keywords
weight
detergent
silver
primary
group
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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EP94917579A
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German (de)
English (en)
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EP0697036A1 (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 DE19934338724 external-priority patent/DE4338724A1/de
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0697036A1 publication Critical patent/EP0697036A1/fr
Application granted granted Critical
Publication of EP0697036B1 publication Critical patent/EP0697036B1/fr
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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
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38609—Protease or amylase in solid compositions only
    • 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
    • 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
    • C11D3/02—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
    • 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
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2065—Polyhydric alcohols
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2096—Heterocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/28—Heterocyclic compounds containing nitrogen in the ring
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/30—Amines; Substituted amines ; Quaternized amines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/34—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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—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.
  • organic redox-active substances especially those commonly used in oxidation dyes not previously described as a silver corrosion inhibitor Coupler and / or developer compounds the corrosion of silver in mechanical Prevent dishwashers effectively.
  • the invention relates to the use of organic redox-active substances in dishwashing preparations as silver corrosion inhibitors, the organic redox-active substance being a coupler and / or developer compound, selected from the group of the diaminopyridines, aminohydroxypyridines, dihydroxypyridines, heterocyclic hydrazones, aminohydroxypyrimidines, dihydroxypyrimidines, tetraaminopyrimidines, tetraaminopyrimidines, tetraaminopyrimidines, and tetraaminopyrimidines , Diaminodihydroxypyrimidines, dihydroxynaphtalines, naphthols, hydroxyquinolines, aminoquinolines, the primary aromatic amines, the ortho, meta or para position a further free or substituted by C 1 -C 4 alkyl or C 2 -C 4 hydroxyalkyl groups hydroxy or have amino group, and the di- or trihydroxybenzenes.
  • 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.
  • Organic redox-active substances are those organic substances accessible to easily reversible oxidation and / or reduction are.
  • Typical complexing agents such as e.g. B. EDTA or hydroxyethane diphosphonic acid and related compounds not under this definition.
  • the developer used according to the invention to prevent silver corrosion and coupler compounds are common in oxidation colorants substances used from the above groups. Examples for such developer and coupler connections there are e.g. in "Venkataraman, The Chemistry of synthetic dyes, Vol. V, Academic Press New York / London, 1971, pages 478-495 ", as well as in the literature cited there.
  • the developers are particularly suitable for preventing silver corrosion.
  • coupler compounds selected from the group p-hydroxyphenylglycine, 2,4-diaminophenol, 5-chloro-2,3-pyridinediol, 1- (p-aminophenyl) morpholine, Hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, Phloroglucin, pyrogallol.
  • the organic redox-active substances are preferably coated, i.e. completely with a waterproof, but at the cleaning temperatures easily soluble material coated for their premature decomposition or To prevent oxidation during storage.
  • Preferred coating materials those according to known processes, such as the melt coating process according to Sandwik from the food industry, are paraffins, micro waxes, Waxes of natural origin such as carnauba wax, candella wax, Beeswax, higher melting alcohols such as hexadecanol, Soaps or fatty acids.
  • the coating material is solid at room temperature applied to the material to be coated in the molten state, e.g.
  • the melting point must be like this be chosen so that the coating material during subsequent use the silver corrosion inhibitor in the dishwasher easily dissolves or melts quickly.
  • the melting point should therefore be for most applications ideally in the range between 45 ° C and 65 ° C and are preferably in the range from 50 ° C. to 60 ° C.
  • organic 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 Bleach activator, 0.1 to 5 wt .-%, preferably 0.5 to 2.5 wt .-% of an enzyme, in each case based on the total agent, and silver corrosion protection agent, wherein as a silver corrosion protection agent a coupler and / or developer compounds selected from the group of Diaminopyridines, aminohydroxypyridines, dihydroxypyridines, heterocyclic hydrazones, aminohydroxypyrimidines, dihydroxypyrimidines, tetraaminopyrimidines, triaminohydroxypyrimidines, diaminodihydroxypyrimidines,
  • Preferred dish detergents contain coupler and / or developer compounds selected from the group p-hydroxyphenylglycine, 2,4-diaminophenol, 5-chloro-2,3-pyridine, 1- (p-aminophenyl) morpholine, hydroquinone, Catechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol as well as their mixtures.
  • the organic redox-active substances are preferably in the inventive Average in a total amount of 0.05 to 6 wt .-%, preferably 0.2 to 2.5 wt .-%, based on the total agent.
  • polymeric alkali 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.
  • the oxygen-based bleach is therefore preferably a percarbonate salt, in particular Sodium percarbonate. Since active oxygen only at elevated temperatures of only its full effect unfolds to be activated in the Dishwasher so-called bleach activators used. As organic bleach activators serve e.g.
  • PAG penentaacetyl glucose
  • DADHT 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine
  • ISA isatoic anhydride
  • bleach stabilizers such as phosphonates, borates or Metaborates and metasilicates as well as magnesium salts such as magnesium sulfate 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 Lipo
  • 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 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
  • 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 organic 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 organic 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 about 2 to 8 g / l, preferably 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 silver spoons were consistently rated 0 to 1, i.e. "no to very weak Tarnish ", rated. Identical compositions, however each without silver corrosion inhibitor A - D caused on silver spoons Yellow to violet colors (rating: 2 to 4).
  • 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).

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Claims (13)

  1. Utilisation de substances organiques à activité redox dans des préparations de nettoyants pour la vaisselle comme agents de protection contre la corrosion de l'argent, caractérisée en ce que la substance organique à activité redox est un composé copulateur et/ou développateur, sélectionné parmi le groupe des diaminopyridines, aminohydroxypyridines, dihydroxypyridines, hydrazones hétérocycliques, aminohydroxypyrimidines, dihydroxypyrimidines, tétraaminopyrimidines, triaminohydroxypyrimidines, diaminodihydroxypyrimidines, dihydroxynaphtalénes, naphtols, hydroxyquinoléines et aminoquinoléines, des amines aromatiques primaires. qui possèdent en position ortho, méta ou para un autre groupe hydroxy ou amino libre ou substitué par des groupes alkyle en C1-C4 ou hydroxyalkyle en C2-C4, et des di- ou des trihydroxybenzènes.
  2. Utilisation selon la revendication 1, caractérisée en ce que le composant copulateur et/ou développateur est sélectionné parmi le groupe de substances suivant: p-hydroxyphénylglycine. 2,4-diaminophénol, 5-chloro-2,3-pyridinediol, 1-(p-aminophényl)-morpholine, hydroquinone, pyrocatéchine, hydroxyhydroquinone, acide gallique, phloroglucine et pyrogallol.
  3. Produit faiblement alcalin pour le lavage de la vaisselle en machine, dont les solutions à 1 % en poids présentent un pH de 8 à 11,5, de préférence de 9 à 10,5, renfermant 15 à 60 % en poids, de préférence 30 à 50 % en poids d'un composant adjuvant soluble dans l'eau, 5 à 25 % en poids, de préférence 10 à 15 % en poids d'un agent de blanchiment à base d'oxygène, 1 à 10 % en poids, de préférence 2 à 6 % en poids, d'un activateur de blanchiment organique, 0,1 à 5 % en poids, de préférence 0,5 à 2,5 % en poids d'une enzyme, dans chaque cas par rapport à la totalité du produit, ainsi que des agents de protection contre la corrosion de l'argent, caractérisé en ce qu'est contenu comme agent de protection contre la corrosion de l'argent, un composé copulateur et/ou développateur sélectionné parmi le groupe des diaminopyridines, aminohydroxypyridines, dihydroxypyridines, hydrazones hétérocycliques, aminohydroxypyrimidines, dihydroxypyrimidines, tétraaminopyrimidines, triaminohydroxypyrimidines, diaminodihydroxypyrimidines, dihydroxynaphtalènes, naphtols. hydroxyquinoléines et aminoquinoléines, des amines aromatiques primaires. qui possèdent en position ortho, méta ou para un autre groupe hydroxy ou amino libre ou substitué par des groupes alkyle en C1-C4 ou hydroxyalkyle en C2-C4, et des di- ou des trihydroxybenzènes.
  4. Produit selon la revendication 3, caractérisé en ce que le composé copulateur ou développateur est sélectionné parmi le groupe de substances suivant: p-hydroxyphénylglycine, 2,4-diaminophénol, 5-chloro-2,3-pyridinediol, 1-(p-aminophényl)-morpholine, hydroquinone, pyrocatéchine, hydroxyhydroquinone, acide gallique, phloroglucine et pyrogallol.
  5. Produit selon les revendications 3 à 4, caractérisé en ce que les substances organiques à activité redox sont contenues dans une proportion de 0,05 à 6 % en poids, de préférence de 0.2 à 2.5 % en poids par rapport à la totalité du produit.
  6. Produit selon les revendications 3 à 5, caractérisé en ce que le composant adjuvant soluble dans l'eau est un sel de l'acide citrique, de préférence le citrate de sodium.
  7. Produit selon les revendications 3 à 6, caractérisé en ce que l'agent de blanchiment à base d'oxygène est un sel percarbonate. de préférence le percarbonate de sodium.
  8. Produit selon les revendications 3 à 7, caractérisé en ce que l'activateur de blanchiment est la N,N,N',N'-tétraacétyléthylènediamine (TAED).
  9. Produit selon les revendications 3 à 8, caractérisé en ce que l'enzyme est une amylase etlou une protéase.
  10. Produit selon les revendications 3 à 9, caractérisé en ce qu'il renferme en plus jusqu'à 60 % en poids, de préférence 10 à 40 % en poids par rapport à la totalité du produit d'un système de matières porteuses de métaux alcalins, constitué essentiellement de carbonate et d'hydrogénocarbonate, de préférence de carbonate et d'hydrogénocarbonate de sodium.
  11. Produit selon les revendications 3 à 10, caractérisé en ce qu'il renferme en plus jusqu'à 5 % en poids, de préférence jusqu'à 2 % en poids par rapport à la totalité du produit de tensioactifs, de préférence de surfactifs non ioniques faiblement moussants.
  12. Produit selon les revendications 3 à 11, caractérisé en ce qu'il est présent sous forme de comprimés et obtenable par mélange de tous ses ingrédients dans un mélangeur et pressage du mélange à l'aide d'une machine à fabriquer les comprimés ou pastilleuse à des pressions de compression atteignant 200 . 105 à 1 500 . 105 Pa.
  13. Produit selon les revendications 3 à 12, caractérisé en ce qu'il est présent sous forme de poudre ou de granulé et possède une densité en vrac de 750 à 1000 g/l.
EP94917579A 1993-05-08 1994-05-02 Produits de protection de l'argent contre la corrosion ii Expired - Lifetime EP0697036B1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE19934315397 DE4315397A1 (de) 1993-05-08 1993-05-08 Reinigungsmittel mit Verhinderung des Anlaufens von Tafelsilber in Geschirrspülmaschinen
DE4315397 1993-05-08
DE19934338724 DE4338724A1 (de) 1993-11-12 1993-11-12 Silberkorrosionsschutzmittel II
DE4338724 1993-11-12
PCT/EP1994/001387 WO1994026860A1 (fr) 1993-05-08 1994-05-02 Produits de protection de l'argent contre la corrosion ii

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EP0697036A1 EP0697036A1 (fr) 1996-02-21
EP0697036B1 true EP0697036B1 (fr) 1999-07-28

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JP (1) JPH08509778A (fr)
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CA (1) CA2162459A1 (fr)
CZ (1) CZ287850B6 (fr)
DE (1) DE59408548D1 (fr)
DK (1) DK0697036T3 (fr)
ES (1) ES2134944T3 (fr)
HU (2) HU218008B (fr)
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PL177935B1 (pl) 2000-01-31
HU218021B (hu) 2000-05-28
DK0697036T3 (da) 2000-01-31
ATE182615T1 (de) 1999-08-15
HU9503200D0 (en) 1996-01-29
HU9503201D0 (en) 1995-12-28
HU218008B (hu) 2000-05-28
JPH08509778A (ja) 1996-10-15
PL311624A1 (en) 1996-03-04
WO1994026860A1 (fr) 1994-11-24
CZ262595A3 (en) 1996-02-14
CZ287850B6 (en) 2001-02-14
HUT73025A (en) 1996-06-28
HUT73028A (en) 1996-06-28
DE59408548D1 (de) 1999-09-02
CA2162459A1 (fr) 1994-11-24
EP0697036A1 (fr) 1996-02-21
ES2134944T3 (es) 1999-10-16

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