EP0697036B1 - Silberkorrosionsschutzmittel ii - Google Patents

Silberkorrosionsschutzmittel 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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European Patent Office
Prior art keywords
weight
detergent
silver
primary
group
Prior art date
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EP94917579A
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German (de)
English (en)
French (fr)
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EP0697036A1 (de
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/de
Application granted granted Critical
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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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Anti-Oxidant Or Stabilizer Compositions (AREA)
EP94917579A 1993-05-08 1994-05-02 Silberkorrosionsschutzmittel ii Expired - Lifetime EP0697036B1 (de)

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
DE4338724 1993-11-12
DE19934338724 DE4338724A1 (de) 1993-11-12 1993-11-12 Silberkorrosionsschutzmittel II
PCT/EP1994/001387 WO1994026860A1 (de) 1993-05-08 1994-05-02 Silberkorrosionsschutzmittel ii

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025174581A1 (en) * 2024-02-15 2025-08-21 Rohm And Haas Company Automatic dishwashing composition with gallic acid (salt)
WO2025178722A1 (en) * 2024-02-20 2025-08-28 Rohm And Haas Company Automatic dishwashing composition with 1,2,4-trihydroxybenzene (salt)

Families Citing this family (182)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5468410A (en) * 1993-10-14 1995-11-21 Angevaare; Petrus A. Purine class compounds in detergent compositions
US5480576A (en) * 1993-10-14 1996-01-02 Lever Brothers Company, Division Of Conopco, Inc. 1,3-N azole containing detergent compositions
DE4344215A1 (de) * 1993-12-23 1995-06-29 Cognis Bio Umwelt Silberkorrosionsschutzmittelhaltige Enzymzubereitung
DE19501645A1 (de) * 1995-01-20 1996-07-25 Henkel Kgaa Silberkorrosionsschutzmittel
DE19518695A1 (de) * 1995-05-22 1996-11-28 Henkel Kgaa Redoxaktive Substanzen enthaltende saure Granulate
DE19518693A1 (de) * 1995-05-22 1996-11-28 Henkel Kgaa Maschinelle Geschirrspülmittel mit Silberkorrosionsschutzmittel
US6194368B1 (en) 1995-07-13 2001-02-27 Joh A. Benckiser, Gmbh Dishwasher product in tablet form
DE19631787C2 (de) * 1996-08-07 2000-06-29 Henkel Kgaa Benzotriazolhaltige, granulare Komponente für den Einsatz in Maschinengeschirrspülmitteln (MGSM) und Verfahren zu dessen Herstellung
DE19817964A1 (de) * 1998-04-22 1999-10-28 Henkel Kgaa Umhüllte Reinigungsmittelkomponente
DE19946844A1 (de) * 1999-09-30 2001-04-05 Henkel Kgaa Maschinelles Silberreinigungsmittel
CA2564250A1 (en) 2004-04-28 2005-11-10 The Procter & Gamble Company Laundry detergent compositions comprising substituted 3-pyridinols
DE102004039921A1 (de) * 2004-08-18 2006-03-02 Henkel Kgaa Klarspülhaltige Wasch- und Reinigungsmittel mit schwefelhaltigen Aminosäuren
GB0522658D0 (en) 2005-11-07 2005-12-14 Reckitt Benckiser Nv Composition
GB0611206D0 (en) 2006-06-07 2006-07-19 Reckitt Benckiser Nv Detergent composition
GB0615487D0 (en) 2006-08-04 2006-09-13 Reckitt Benckiser Nv Detergent composition
GB0700929D0 (en) 2007-01-18 2007-02-28 Reckitt Benckiser Nv Dosage element and a method of manufacturing a dosage element
DE102007041215B3 (de) * 2007-08-31 2009-04-30 Clariant International Limited Verwendung von Zusammensetzungen als Korrosionsinhibitoren enthaltend nichtionische Tenside und die Zusammensetzungen
DE102007041204B3 (de) * 2007-08-31 2009-04-30 Clariant International Limited Verwendung von Zusammensetzung als Korrosionsinhibitoren enthaltend anionische Tenside und die Zusammensetzungen
GB0718944D0 (en) 2007-09-28 2007-11-07 Reckitt Benckiser Nv Detergent composition
US20090209447A1 (en) 2008-02-15 2009-08-20 Michelle Meek Cleaning compositions
EP2100948A1 (en) 2008-03-14 2009-09-16 The Procter and Gamble Company Automatic dishwashing detergent composition
EP2100947A1 (en) 2008-03-14 2009-09-16 The Procter and Gamble Company Automatic dishwashing detergent composition
EP2166092A1 (en) 2008-09-18 2010-03-24 The Procter and Gamble Company Detergent composition
GB0818804D0 (en) 2008-10-14 2008-11-19 Reckitt Benckiser Nv Compositions
WO2010056671A1 (en) 2008-11-11 2010-05-20 Danisco Us Inc. Compositions and methods comprising a subtilisin variant
MX2011004801A (es) 2008-11-11 2011-06-16 Danisco Inc Composiciones y metodos que comprenden una variante de subtilisina.
RU2560978C2 (ru) 2008-11-11 2015-08-20 ДАНИСКО ЮЭс ИНК. Протеазы, содержащие одну или несколько комбинируемых мутаций
US20100192985A1 (en) 2008-11-11 2010-08-05 Wolfgang Aehle Compositions and methods comprising serine protease variants
EP2216393B1 (en) 2009-02-09 2024-04-24 The Procter & Gamble Company Detergent composition
GB0906281D0 (en) 2009-04-09 2009-05-20 Reckitt Benckiser Nv Detergent compositions
GB0911428D0 (en) 2009-07-02 2009-08-12 Reckitt Benckiser Nv Composition
GB0915572D0 (en) 2009-09-07 2009-10-07 Reckitt Benckiser Nv Detergent composition
JP5561987B2 (ja) * 2009-09-30 2014-07-30 小林製薬株式会社 義歯洗浄剤
GB0917740D0 (en) 2009-10-09 2009-11-25 Reckitt Benckiser Nv Detergent composition
AR079338A1 (es) 2009-12-09 2012-01-18 Danisco Us Inc Variantes de proteasa de bacillus y acidos nucleicos que codifican dichas variantes
ES2423580T5 (es) 2009-12-10 2021-06-17 Procter & Gamble Método y uso de una composición para lavado de vajillas
PL2333042T3 (pl) 2009-12-10 2015-12-31 Procter & Gamble Produkt do automatycznych zmywarek do mycia naczyń i jego wykorzystanie
EP2333041B1 (en) 2009-12-10 2013-05-15 The Procter & Gamble Company Method and use of a dishwasher composition
EP2333040B2 (en) 2009-12-10 2019-11-13 The Procter & Gamble Company Detergent composition
US20120258507A1 (en) 2009-12-21 2012-10-11 Danisco Us Inc. Detergent compositions containing thermobifida fusca lipase and methods of use thereof
BR112012017056A2 (pt) 2009-12-21 2016-11-22 Danisco Us Inc "composições detergentes contendo lipase de bacillus subtilis e métodos para uso das mesmas"
EP2516611A1 (en) 2009-12-21 2012-10-31 Danisco US Inc. Detergent compositions containing geobacillus stearothermophilus lipase and methods of use thereof
DE102010006099A1 (de) * 2010-01-28 2011-08-18 EXCOR Korrosionsforschung GmbH, 01067 Zusammensetzungen von Dampfphasen-Korrosionsinhibitoren, Verfahren zu deren Herstellung und deren Verwendung für den temporären Korrosionsschutz
PL2361964T3 (pl) 2010-02-25 2013-05-31 Procter & Gamble Kompozycja detergentu
GB201003892D0 (en) 2010-03-09 2010-04-21 Reckitt Benckiser Nv Detergent composition
JP5641759B2 (ja) * 2010-03-31 2014-12-17 小林製薬株式会社 義歯洗浄剤
PL2558573T3 (pl) 2010-04-15 2017-08-31 Danisco Us Inc. Kompozycje i sposoby obejmujące warianty proteazy
JP6448904B2 (ja) 2010-05-06 2019-01-09 ダニスコ・ユーエス・インク サブチリシン変異体を含む組成物及び方法
WO2011150157A2 (en) 2010-05-28 2011-12-01 Danisco Us Inc. Detergent compositions containing streptomyces griseus lipase and methods of use thereof
GB201014328D0 (en) 2010-08-27 2010-10-13 Reckitt Benckiser Nv Detergent composition comprising manganese-oxalate
GB201019623D0 (en) 2010-11-19 2010-12-29 Reckitt Benckiser Nv Coated bleach materials
GB201019628D0 (en) 2010-11-19 2010-12-29 Reckitt Benckiser Nv Dyed coated bleach materials
GB201021541D0 (en) 2010-12-21 2011-02-02 Reckitt Benckiser Nv Bleach catalyst particle
GB201104244D0 (en) 2011-03-14 2011-04-27 Reckitt Benckiser Nv Detergent composition with improved drying performance
GB201105397D0 (en) 2011-03-31 2011-05-11 Reckitt Benckiser Nv Detergent composition
AR086214A1 (es) 2011-04-29 2013-11-27 Danisco Us Inc Composiciones detergentes que contienen mananasa de bacillus agaradhaerens y sus metodos de uso
EP2712363A1 (en) 2011-04-29 2014-04-02 Danisco US Inc. Detergent compositions containing geobacillus tepidamans mannanase and methods of use thereof
WO2012149333A1 (en) 2011-04-29 2012-11-01 Danisco Us Inc. Detergent compositions containing bacillus sp. mannanase and methods of use thereof
JP6105560B2 (ja) 2011-05-05 2017-03-29 ダニスコ・ユーエス・インク セリンプロテアーゼ変異体を含む組成物及び方法
US9434932B2 (en) 2011-06-30 2016-09-06 Novozymes A/S Alpha-amylase variants
EP2751263A1 (en) 2011-08-31 2014-07-09 Danisco US Inc. Compositions and methods comprising a lipolytic enzyme variant
GB2496132A (en) 2011-10-31 2013-05-08 Reckitt Benckiser Nv Pthalimidopercaproic acid sugar suspension
PL2794836T3 (pl) 2011-12-22 2016-12-30 Detergentowa kompozycja zawierająca glutamino- n,n-dioctan, wodę oraz środek bielący
BR112014014410A2 (pt) 2011-12-22 2019-09-24 Danisco Us Inc composições e métodos que compreendem uma variante de enzima lipolítica
US20140018278A1 (en) 2012-07-11 2014-01-16 Xinbei Song Dishwashing composition with improved protection against aluminum corrosion
EP3842531A1 (en) 2012-10-12 2021-06-30 Danisco US Inc. Compositions and method comprising a lipolytic enzyme variant
CN104781400A (zh) 2012-11-05 2015-07-15 丹尼斯科美国公司 包含嗜热菌蛋白酶变体的组合物和方法
WO2014100018A1 (en) 2012-12-19 2014-06-26 Danisco Us Inc. Novel mannanase, compositions and methods of use thereof
JP2016506442A (ja) 2012-12-20 2016-03-03 ザ プロクター アンド ギャンブルカンパニー ケイ酸塩でコーティングされた漂白剤を含む洗剤組成物
WO2014194034A2 (en) 2013-05-29 2014-12-04 Danisco Us Inc. Novel metalloproteases
EP3004342B1 (en) 2013-05-29 2023-01-11 Danisco US Inc. Novel metalloproteases
WO2014194032A1 (en) 2013-05-29 2014-12-04 Danisco Us Inc. Novel metalloproteases
US20160108388A1 (en) 2013-05-29 2016-04-21 Danisco Us Inc. Novel metalloproteases
EP3008159B1 (en) 2013-06-12 2016-11-16 Unilever N.V. Pourable detergent composition comprising suspended particles
EP3696264B1 (en) 2013-07-19 2023-06-28 Danisco US Inc. Compositions and methods comprising a lipolytic enzyme variant
EP3044313B1 (en) 2013-09-12 2019-11-06 Danisco US Inc. Compositions and methods comprising lg12-clade protease variants
EP3910057A1 (en) 2013-12-13 2021-11-17 Danisco US Inc. Serine proteases of the bacillus gibsonii-clade
DK3080262T3 (da) 2013-12-13 2019-05-06 Danisco Us Inc Serinproteaser af bacillus-arter
US20170096653A1 (en) 2014-03-21 2017-04-06 Danisco Us Inc. Serine proteases of bacillus species
GB201413859D0 (en) 2014-08-05 2014-09-17 Reckitt Benckiser Brands Ltd New automatic washing machine and method
DK3207129T3 (da) 2014-10-17 2020-02-24 Danisco Us Inc Serinproteaser af bacillus-arten
CN107148472A (zh) 2014-10-27 2017-09-08 丹尼斯科美国公司 芽孢杆菌属物种的丝氨酸蛋白酶
DK3212662T3 (da) 2014-10-27 2020-07-20 Danisco Us Inc Serinproteaser
EP3212783B1 (en) 2014-10-27 2024-06-26 Danisco US Inc. Serine proteases
DK3212781T3 (da) 2014-10-27 2019-12-16 Danisco Us Inc Serinproteaser
EP3957729A1 (en) 2014-10-27 2022-02-23 Danisco US Inc. Serine proteases
CN107454914B (zh) 2015-03-12 2021-09-21 丹尼斯科美国公司 包含lg12进化枝蛋白酶变体的组合物和方法
CN107835855B (zh) 2015-05-13 2022-05-13 丹尼斯科美国公司 AprL-进化枝蛋白酶变体及其用途
US11499146B2 (en) 2015-06-17 2022-11-15 Danisco Us Inc. Bacillus gibsonii-clade serine proteases
EP4141113A1 (en) 2015-11-05 2023-03-01 Danisco US Inc Paenibacillus sp. mannanases
JP7364330B2 (ja) 2015-11-05 2023-10-18 ダニスコ・ユーエス・インク パエニバチルス（Ｐａｅｎｉｂａｃｉｌｌｕｓ）属種及びバチルス（Ｂａｃｉｌｌｕｓ）属種のマンナナーゼ
AR107753A1 (es) 2016-03-02 2018-05-30 Unilever Nv Suspensión de detergente que se puede verter que comprende una fase fluida coloreada y partículas suspendidas
JP2019508539A (ja) 2016-03-02 2019-03-28 ユニリーバー・ナームローゼ・ベンノートシヤープ 懸濁液の形態の洗剤組成物
AR107756A1 (es) 2016-03-02 2018-05-30 Unilever Nv Composición detergente fluida y procedimiento para prepararla
JP2019507808A (ja) 2016-03-11 2019-03-22 ユニリーバー・ナームローゼ・ベンノートシヤープ 漂白触媒顆粒を含む流動性洗剤懸濁液
JP2019518440A (ja) 2016-05-03 2019-07-04 ダニスコ・ユーエス・インク プロテアーゼ変異体およびその使用
CN109072213A (zh) 2016-05-05 2018-12-21 丹尼斯科美国公司 蛋白酶变体及其用途
WO2017210295A1 (en) 2016-05-31 2017-12-07 Danisco Us Inc. Protease variants and uses thereof
EP3472313B1 (en) 2016-06-17 2022-08-31 Danisco US Inc. Protease variants and uses thereof
ES2842600T3 (es) 2016-12-01 2021-07-14 Clariant Int Ltd Uso de una composición que contiene al menos un compuesto de azúcar-amida biodegradable en combinación con al menos un agente sinérgico basado en azufre para inhibir la corrosión de un equipo metálico en aplicaciones de campos de petróleo
EP3559226B1 (en) 2016-12-21 2023-01-04 Danisco US Inc. Bacillus gibsonii-clade serine proteases
CN110312795B (zh) 2016-12-21 2024-07-23 丹尼斯科美国公司 蛋白酶变体及其用途
US11453871B2 (en) 2017-03-15 2022-09-27 Danisco Us Inc. Trypsin-like serine proteases and uses thereof
US11208639B2 (en) 2017-03-31 2021-12-28 Novozymes A/S Polypeptides having DNase activity
WO2018177936A1 (en) 2017-03-31 2018-10-04 Novozymes A/S Polypeptides having dnase activity
US11149233B2 (en) 2017-03-31 2021-10-19 Novozymes A/S Polypeptides having RNase activity
CN110651040A (zh) 2017-03-31 2020-01-03 诺维信公司 具有dna酶活性的多肽
CN114480034A (zh) 2017-04-04 2022-05-13 诺维信公司 糖基水解酶
EP3607039A1 (en) 2017-04-04 2020-02-12 Novozymes A/S Polypeptides
WO2018185269A1 (en) 2017-04-06 2018-10-11 Novozymes A/S Cleaning compositions and uses thereof
EP3967756B1 (en) 2017-04-06 2025-03-05 Novozymes A/S Detergent compositions and uses thereof
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US20200190438A1 (en) 2017-04-06 2020-06-18 Novozymes A/S Cleaning compositions and uses thereof
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MX2019011764A (es) 2017-04-06 2019-11-28 Novozymes As Composiciones limpiadoras y usos de las mismas.
EP3478811B1 (en) 2017-04-06 2019-10-16 Novozymes A/S Cleaning compositions and uses thereof
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ES2954295T3 (es) 2017-05-12 2023-11-21 Unilever Ip Holdings B V Composición detergente libre de fosfatos para lavavajillas automático
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WO2019076800A1 (en) 2017-10-16 2019-04-25 Novozymes A/S CLEANING COMPOSITIONS AND USES THEREOF
DE102017125560A1 (de) 2017-11-01 2019-05-02 Henkel Ag & Co. Kgaa Reinigungszusammensetzungen, die dispersine iii enthalten
EP3704240A1 (en) 2017-11-01 2020-09-09 Novozymes A/S Polypeptides and compositions comprising such polypeptides
WO2019086530A1 (en) 2017-11-01 2019-05-09 Novozymes A/S Polypeptides and compositions comprising such polypeptides
EP3704220B1 (en) 2017-11-01 2026-04-15 Novozymes A/S Methods for cleaning medical devices
US20200354708A1 (en) 2017-11-29 2020-11-12 Danisco Us Inc. Subtilisin variants having improved stability
GB201809123D0 (en) 2018-06-04 2018-07-18 Reckitt Benckiser Finish Bv Composition
EP3799601A1 (en) 2018-06-19 2021-04-07 Danisco US Inc. Subtilisin variants
WO2019245704A1 (en) 2018-06-19 2019-12-26 Danisco Us Inc Subtilisin variants
EP3814472A1 (en) 2018-06-28 2021-05-05 Novozymes A/S Detergent compositions and uses thereof
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US12012573B2 (en) 2018-07-02 2024-06-18 Novozymes A/S Cleaning compositions and uses thereof
EP3818138B1 (en) 2018-07-03 2025-05-14 Henkel AG & Co. KGaA Cleaning compositions and uses thereof
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0346112A2 (en) * 1988-06-09 1989-12-13 The Procter & Gamble Company Liquid automatic dishwashing compositions providing silver protection
WO1994007981A1 (de) * 1992-09-25 1994-04-14 Henkel Kommanditgesellschaft Auf Aktien Schwachalkalische geschirreinigungsmittel
WO1994016045A1 (en) * 1993-01-18 1994-07-21 Unilever N.V. Machine dishwashing composition containing a corrosion inhibitor

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2788329A (en) * 1953-12-02 1957-04-09 American Cyanamid Co Surface active composition containing a corrosion inhibitor
NL6704601A (da) * 1966-04-06 1967-10-09
US3549539A (en) * 1967-10-23 1970-12-22 Lever Brothers Ltd Dishwashing powders
GB8321924D0 (en) * 1983-08-15 1983-09-14 Unilever Plc Enzymatic machine-dishwashing compositions
DK166548B1 (da) * 1991-03-15 1993-06-07 Cleantabs As Phosphatfrit maskinopvaskemiddel

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0346112A2 (en) * 1988-06-09 1989-12-13 The Procter & Gamble Company Liquid automatic dishwashing compositions providing silver protection
WO1994007981A1 (de) * 1992-09-25 1994-04-14 Henkel Kommanditgesellschaft Auf Aktien Schwachalkalische geschirreinigungsmittel
WO1994016045A1 (en) * 1993-01-18 1994-07-21 Unilever N.V. Machine dishwashing composition containing a corrosion inhibitor

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025174581A1 (en) * 2024-02-15 2025-08-21 Rohm And Haas Company Automatic dishwashing composition with gallic acid (salt)
WO2025178722A1 (en) * 2024-02-20 2025-08-28 Rohm And Haas Company Automatic dishwashing composition with 1,2,4-trihydroxybenzene (salt)

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

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