EP0697035B1 - Silver-corrosion protection agent (i) - Google Patents
Silver-corrosion protection agent (i) Download PDFInfo
- 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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- European Patent Office
- Prior art keywords
- weight
- detergent
- silver
- salts
- metal
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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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/046—Salts
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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
- 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
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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
- 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
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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
- 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
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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
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0042—Reducing agents
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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
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0073—Anticorrosion compositions
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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
- C11D3/02—Inorganic compounds ; Elemental compounds
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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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/046—Salts
- C11D3/048—Nitrates or nitrites
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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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
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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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/1213—Oxides or hydroxides, e.g. Al2O3, TiO2, CaO or Ca(OH)2
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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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/122—Sulfur-containing, e.g. sulfates, sulfites or gypsum
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2072—Aldehydes-ketones
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2079—Monocarboxylic acids-salts thereof
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2086—Hydroxy carboxylic acids-salts thereof
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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
- C11D3/34—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
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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
- C11D3/36—Organic compounds containing phosphorus
- C11D3/361—Phosphonates, phosphinates or phosphonites
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2003—Alcohols; Phenols
- C11D3/2041—Dihydric alcohols
- C11D3/2058—Dihydric alcohols aromatic
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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
- C11D3/34—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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Abstract
Description
Es ist eine allgemein bekannte Tatsache, daß Silber, auch dann, wenn es nicht in Gebrauch ist, "anläuft". Es ist nur eine Frage der Zeit, bis es dunkle, bräunliche, bläuliche bis blauschwarze Flecken bekommt oder sich insgesamt verfärbt und damit im üblichen Sprachgebrauch "angelaufen" ist.It is a well known fact that silver, even if it is is not in use, "tarnishes". It's only a matter of time before it gets dark, brownish, bluish to bluish-black spots overall discolored and thus "tarnished" in common usage.
Auch bei der maschinellen Reinigung von Tafelsilber treten in der Praxis immer wieder Probleme in Form von Anlaufen und Verfärben der Silberoberflächen auf. Silber kann hier auf schwefelhaltige Substanzen, die im Spülwasser gelöst bzw. dispergiert sind, reagieren, denn bei der Reinigung von Geschirr in Haushaltsgeschirrspülmaschinen (HGSM) werden ja Speisereste und damit u. a. auch Senf, Erbsen, Ei und sonstige schwefelhaltige Verbindungen wie Mercaptoaminosäure in die Spülflotte eingebracht. Auch die während des maschinellen Spülens viel höheren Temperaturen und die längeren Kontaktzeiten mit den schwefelhaltigen Speiseresten begünstigen im Vergleich zum manuellen Spülen das Anlaufen von Silber. Durch den intensiven Reinigungsprozeß in der Spülmaschine wird die Silberoberfläche außerdem vollständig entfettet und dadurch empfindlicher gegenüber chemischen Einflüssen.Even in the mechanical cleaning of silverware occur in practice problems in the form of tarnishing and discoloration of the silver surfaces on. Silver can be found here on sulfur-containing substances in the rinse water are dissolved or dispersed, because when cleaning Dishes in household dishwashers (HGSM) are leftovers and thus u. a. also mustard, peas, egg and other sulfur-containing compounds like mercaptoamino acid introduced into the washing liquor. Even during machine washing much higher temperatures and the longer ones Contact times with the sulfur-containing food residues favor in comparison tarnishing silver for manual rinsing. Because of the intense Cleaning process in the dishwasher will also silver surface completely degreased and therefore more sensitive to chemical influences.
Bei der Anwendung aktivchlorhaltiger Reiniger kann das Anlaufen durch schwefelhaltige Verbindungen weitgehend verhindert werden, da diese Verbindungen durch Oxidation der sulfidischen Funktionen in Sekundärreaktion zu Sulfonen oder Sulfaten umgesetzt werden.When using active chlorine-containing cleaners, tarnishing can occur Sulfur-containing compounds are largely prevented because of these compounds by oxidation of the sulfidic functions in a secondary reaction to be converted into sulfones or sulfates.
Das Problem des Silberanlaufens wurde jedoch wieder aktuell, als alternativ zu den Aktivchlorverbindungen Aktivsauerstoffverbindungen, wie beispielsweise Natriumperborat oder Natriumpercarbonat eingesetzt wurden, welche zur Beseitigung bleichbarer Anschmutzungen, wie beispielsweise Teeflecken/Teebeläge, Kaffeerückstände, Farbstoffe aus Gemüse, Lippenstiftreste und dergleichen dienen.However, the problem of tarnishing silver has become topical again, as an alternative to the active chlorine compounds 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.
Diese Aktivsauerstoffverbindungen werden vor allem in modernen niederalkalischen maschinellen Spülmitteln der neuen Reinigergeneration zusammen mit Bleichaktivatoren eingesetzt. Diese modernen Mittel bestehen im allgemeinen aus den folgenden Funktionsbausteinen: Builderkomponente (Komplexbildner/Dispergiermittel), Alkaliträger, Bleichsystem (Bleichmittel + Bleichaktivator), Enzyme und Netzmittel (Tenside).These active oxygen compounds are mainly used in modern lower alkaline machine dishwashing detergents of the new generation of cleaners used with bleach activators. These modern means generally exist from the following function blocks: builder component (complexing agent / dispersant), Alkali carrier, bleaching system (bleach + Bleach activator), enzymes and wetting agents (surfactants).
Auf die veränderten Rezepturparameter der neuen aktivchlorfreien Reinigergeneration mit abgesenkten pH-Werten und aktivierter Sauerstoffbleiche reagieren die Silberoberflächen grundsätzlich empfindlicher. Während des maschinellen Spülens setzen diese Mittel im Reinigungsgang das eigentlich bleichende Agens Wasserstoffperoxid bzw. Aktivsauerstoff frei. Die bleichende Wirkung der aktivsauerstoffhaltigen Reiniger wird durch Bleichaktivatoren verstärkt, so daß schon bei niedrigen Temperaturen eine gute Bleichwirkung erzielt wird. In Gegenwart dieser Bleichaktivatoren bildet sich als reaktive Zwischenverbindung Peressigsäure. Unter diesen veränderten Spülbedingungen bilden sich in Gegenwart von Silber nicht nur sulfidische, sondern durch den oxidierenden Angriff der intermediär gebildeten Peroxide bzw. des Aktivsauerstoffs bevorzugt oxidische Beläge auf den Silberoberflächen. Unter hoher Salzbelastung können zusätzlich chloridische Beläge entstehen. Verstärkt wird das Anlaufen des Silbers außerdem durch höhere Restwasserhärten während des Reinigungsganges.On the changed recipe parameters of the new generation of active chlorine-free cleaners with lowered pH values and activated oxygen bleaching the silver surfaces are generally more sensitive. During the machine dishwashing these agents actually do that in the cleaning cycle bleaching agent free hydrogen peroxide or active oxygen. The bleaching Effect of active oxygen-containing cleaners is through bleach activators reinforced so that a good one even at low temperatures Bleaching effect is achieved. Forms in the presence of these bleach activators peracetic acid as a reactive intermediate. Among these changed Flushing conditions not only form sulfidic in the presence of silver, but through the oxidizing attack of the intermediates Peroxides or the active oxygen preferably oxidic coatings on the Silver surfaces. Chloride can also be present under high salt loads There are deposits. The tarnishing of the silver is also increased due to higher residual water hardness during the cleaning cycle.
Die Vermeidung der Silberkorrosion, d.h. die Bildung sulfidischer, oxidischer oder chloridischer Beläge auf Silber ist das Thema zahlreicher Veröffentlichungen. Die Korrosion von Silber wird in diesen Beschreibungen vor allem durch sogenannte Silberschutzmittel verhindert.Avoiding silver corrosion, i.e. the formation of sulfidic, oxidic or chloride coatings on silver is the subject of numerous publications. The corrosion of silver is described in these descriptions especially prevented by so-called silver protection agents.
Aus der britischen Patentschrift GB 1 131 738 sind alkalische Geschirrspülmittel bekannt, die als Korrosionsinhibitor für Silber Benzotriazole enthalten. In der amerikanischen Patentschrift US 3 549 539 werden stark alkalische, maschinell anwendbare Geschirreinigungsmittel beschrieben, die als Oxidationsmittel u.a. Perborat mit einem organischen Bleichaktivator enthalten können. Als Anlaufverhinderungsmittel werden Zusätze u.a. ebenfalls von Benzotriazol, Zinn(II)chlorid und auch Eisen(III)chlorid empfohlen. Dabei werden pH-Werte von vorzugsweise 7 - 11,5 genannt. In den europäischen Patentschriften EP 135 226 und EP 135 227 werden schwach alkalische, maschinell anwendbare Geschirrspülmittel mit einem Gehalt an Peroxyverbindungen und Aktivatoren beschrieben, die als Silberschutzmittel u.a. Benzotriazole und Fettsäuren enthalten können. Schließlich ist aus der deutschen Offenlegungsschrift DE 41 28 672 bekannt, daß Peroxyverbindungen, die durch Zusatz bekannter organischer Bleichaktivatoren aktiviert werden, in stark alkalischen Reinigungsmitteln das Anlaufen von Silberteilen verhindern.From the British patent GB 1 131 738 are alkaline dishwashing detergents known as a corrosion inhibitor for silver benzotriazoles contain. In the American patent US 3 549 539 strong alkaline, machine-applicable dishwashing detergent described as an oxidizing agent Perborate with an organic bleach activator can contain. As a preventive agent, additives are used Likewise recommended by benzotriazole, tin (II) chloride and also iron (III) chloride. In doing so pH values of preferably 7-11.5. In the European patent specifications EP 135 226 and EP 135 227 become weakly alkaline, mechanically applicable dishwashing detergent containing peroxy compounds and Activators described as silver protection agents, among others. Benzotriazoles and May contain fatty acids. Finally, is from the German published application DE 41 28 672 discloses that peroxy compounds by addition known organic bleach activators are activated in strong alkaline cleaning agents prevent silver parts from tarnishing.
Überraschenderweise wurde nun gefunden, daß anorganische redoxaktive Substanzen, insbesondere die Salze bzw. Komplexverbindungen bestimmter, bisher noch nicht als Silberkorrosionsschutzmittel beschriebener Metalle, die Korrosion von Silber in maschinellen Geschirrspülmaschinen wirksam verhindern.Surprisingly, it has now been found that 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.
Gegenstand der Erfindung ist die Verwendung von anorganischen redoxaktiven Substanzen in Geschirreinigerzubereitungen als Silberkorrosionsschutzmittel, dadurch gekennzeichnet, daß die anorganischen redoxaktiven Substanzen zumindest teilweise in Wasser lösliche Metallsalze und/oder Metallkomplexe ausgewählt aus der Gruppe der Mangan-, Titan-, Zirkonium-, Hafnium-, Vanadium-, Cobalt- und Cer-Salze und/oder -Komplexe sind und die Metalle in einer der Oxidationsstufen II, III, IV, V oder VI vorliegen.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.
Das Wort "Korrosion" ist in seiner weitesten in der Chemie gebräuchlichen Bedeutung auszulegen, insbesondere soll hier "Korrosion" für jede visuell gerade noch erkennbare Veränderung einer Metalloberfläche, hier Silber, stehen, sei es z. B. eine punktuelle Verfärbung, sei es z. B. ein großflächiges Anlaufen.The word "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.
"Anorganische redoxaktive Substanzen" sind solche anorganischen Substanzen, die einer leicht ablaufenden reversiblen Oxidation und/oder Reduktion zugänglich sind. So fallen beispielsweise die Oxide, Hydroxide oder Halogenide von Ammoniumsalzen oder von Alkali- oder Erdalkalimetallen nicht unter diese Definition. "Inorganic redox-active substances" are such inorganic substances that of an easily occurring reversible oxidation and / or reduction are accessible. For example, the oxides, hydroxides or halides fall ammonium salts or alkali or alkaline earth metals under this definition.
Es eignen sich jedoch die Salze bzw. Komplexverbindungen bestimmter Metalle, d.h. die Verwendung von Metallsalzen und/oder Metallkomplexen ausgewählt aus der Gruppe der Mangan-, Titan-, Zirkonium-, Hafnium-, Vanadium-, Cobalt- und Cer-Salze und/oder -Komplexe zur Verhinderung der Silberkorrosion, wobei die Metalle in einer der Oxidationsstufen II, III, IV, V oder VI vorliegen.However, 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.
Die in der Chemie geläufige Definition für "Oxidationsstufe" ist z.B. in "Römpp Chemie Lexikon, Georg Thieme Verlag Stuttgart/New York, 9. Auflage, 1991, Seite 3168" wiedergegeben.The common definition in chemistry for "oxidation level" is e.g. in "Römpp Chemie Lexikon, Georg Thieme Verlag Stuttgart / New York, 9th edition, 1991, page 3168 "reproduced.
Die verwendeten Metallsalze bzw. Metallkomplexe sollen zumindest teilweise in Wasser löslich sein. Die zur Salzbildung geeigneten Gegenionen umfassen alle üblichen ein-, zwei-, oder dreifach negativ geladenen anorganischen Anionen, z. B. Oxid, Sulfat, Nitrat, Fluorid, aber auch organische Anionen wie z. B. Stearat.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.
Metallkomplexe im Sinne der Erfindung sind Verbindungen, die aus einem Zentralatom und einem oder mehreren Liganden bestehen. Das Zentralatom ist eines der o.g. Metalle in einer der o.g. Oxidationsstufen. Die Liganden sind neutrale Moleküle oder Anionen, die ein- oder mehrzähnig sind; der Begriff "Ligand" im Sinne der Erfindung ist z.B. in "Römpp Chemie Lexikon, Georg Thieme Verlag Stuttgart/New York, 9. Auflage, 1990, Seite 2507" näher erläutert. Ergänzen sich in einem Metallkomplex die Ladung des Zentralatoms und die Ladung des/der Liganden nicht auf Null, so sorgt, je nachdem, ob ein kationischer oder ein anionischer Ladungsüberschuß vorliegt, entweder eines oder mehrere der o.g. Anionen oder ein oder mehrere Kationen, z. B. Natrium-, Kalium-, Ammoniumionen, für den Ladungsausgleich. Geeignete Komplexbildner sind z.B. Citrat, Acetylacetonat oder 1-Hydroxyethan-1,1-diphosphonat.For the purposes of the invention, 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.
Besonders bevorzugte Metallsalze und/oder Metallkomplexe sind ausgewählt aus der Gruppe MnSO4, Mn(II)-citrat, Mn(II)-stearat, Mn(II)-acetylacetonat, Mn(II)-[1-Hydroxyethan-1,1-diphosphonat], V2O5, V2O4, VO2, TiOSO4, K2TiF6, K2ZrF6, CoSO4, Co(NO3)2, Ce(NO3)3 sowie deren Gemischen. Insbesondere bevorzugt ist MnSO4.Particularly preferred 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.
Bei diesen Metallsalzen bzw. Metallkomplexen handelt es sich im allgemeinen um handelsübliche Substanzen, die zum Zwecke des erfindungsgemäßen Silberkorrosions-Schutzes ohne vorherige Reinigung eingesetzt werden können. So ist z.B. das aus der SO3-Herstellung (Kontaktverfahren) bekannte Gemisch aus fünf- und vierwertigem Vanadium (V2O5, VO2, V2O4) geeignet, ebenso wie das durch Verdünnen einer Ti(SO4)2-Lösung entstehende Titanylsulfat, TiOSO4.These 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. For example, 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 .
Die anorganischen redoxaktiven Substanzen, insbesondere Metallsalze bzw. Metallkomplexe sind vorzugsweise gecoatet, d.h. vollständig mit einem wasserdichten, bei den Reinigungstemperaturen aber leichtlöslichen Material überzogen, um ihre vorzeitige Zersetzung oder Oxidation bei der Lagerung zu verhindern. Bevorzugte Coatingmaterialien, die nach bekannten Verfahren, etwa Schmelzcoatingverfahren nach Sandwik aus der Lebensmittelindustrie, aufgebracht werden, sind Paraffine, Mikrowachse, Wachse natürlichen Ursprungs wie Carnaubawachs, Candellilawachs, Bienenwachs, höherschmelzende Alkohole wie beispielsweise Hexadecanol, Seifen oder Fettsäuren. Dabei wird das bei Raumtemperatur feste Coatingmaterial in geschmolzenem Zustand auf das zu coatende Material aufgebracht, z.B. indem feinteiliges zu coatendes Material in kontinuierlichem Strom durch eine ebenfalls kontinuierlich erzeugte Sprühnebelzone des geschmolzenen Coatingmaterials geschleudert wird. Der Schmelzpunkt muß so gewählt sein, daß sich das Coatingmaterial während der anschließenden Verwendung der Silberkorrosionsschutzmittel in der Geschirrspülmaschine leicht löst bzw. schnell aufschmilzt. Der Schmelzpunkt sollte daher für die meisten Anwendungen idealerweise im Bereich zwischen 45°C und 65°C und bevorzugt im Bereich 50°C bis 60°C liegen.The inorganic redox-active substances, in particular metal salts or Metal complexes 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. by doing finely divided material to be coated in a continuous flow through a also continuously generated spray zone of the melted Coating material is thrown. 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.
Insbesondere eignen sich die oben beschriebenen anorganischen redoxaktiven Substanzen jedoch zur Verhinderung der Silberkorrosion, wenn sie in niederalkalischen Reinigern zum maschinellen Reinigen von Geschirr enthalten sind. Dies ist um so überraschender, als diese Silberkorrosionsschutzmittel in ihrer Wirkung nicht durch die Anwesenheit von üblicherweise in niederalkalischen Reinigern enthaltenen Bleichmitteln auf Sauerstoffbasis beeinträchtigt werden.The 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.
Ein weiterer Erfindungsgegenstand sind deshalb niederalkalische Mittel zum maschinellen Reinigen von Geschirr, deren 1 Gew.-%ige Lösungen einen pH-Wert von 8 bis 11,5, vorzugsweise 9 bis 10,5 aufweisen, enthaltend 15 bis 60 Gew.-%, vorzugsweise 30 bis 50 Gew.-% einer wasserlöslichen Builderkompcnente, 5 bis 25 Gew.-%, vorzugsweise 10 bis 15 Gew.-% eines Bleichmittels auf Sauerstoffbasis, 1 bis 10 Gew.-%, vorzugsweise 2 bis 6 Gew.-% eines organischen, 0- oder N-(C1-C12)-acylgruppenhaltigen Bleichmittelaktivators, 0,1 bis 5 Gew.-%, vorzugsweise 0,5 bis 2,5 Gew.-% eines Enzyms, jeweils bezogen auf das gesamte Mittel, und Silberkorrosionsschutzmittel, wobei als Silberkorrosionsschutzmittel 0,05 bis 6 Gew.-% zumindest teilweise in Wasser lösliche Metallsalze und/oder Metallkomplexe ausgewählt aus der Gruppe der Mangan-, Titan-, Zirkonium-, Hafnium-, Vanadium-, Cobalt-, Cer-Salze und/oder -Komplexe, wobei die Metalle in einer der Oxidationsstufen II, III, IV, V oder VI vorliegen, enthalten sind.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 oxidation states II, III, IV, V or VI, ent are holding.
Bevorzugte Geschirreinigungsmittel enthalten Metallsalze bzw. Metallkomplexe ausgewählt aus der Gruppe MnSO4, Mn(II)-citrat, Mn(II)-stearat, Mn(II)-acetylacetonat, Mn(II)-[1-Hydroxyethan-1,1-diphosphonat], V2O5, V2O4, VO2, TiOSO4, K2TiF6, K2ZrF6, CoSO4, Co(NO3)2, Ce(NO3)3, sowie deren Mischungen. Insbesondere ist MnSO4 bevorzugt. 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.
Vorzugsweise sind die anorganischen redoxaktiven Substanzen, insbesondere Metallsalze und/oder Metallkomplexe, in den erfindungsgemäßen Mitteln in einer Gesamtmenge von 0,2 bis 2,5 Gew.-%, bezogen auf das gesamte Mittel, enthalten.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.
Organische, 0- oder N- (C1-C12-)-acylgruppenhaltige Bleichmittelaktivatoren sind Substanzen, in denen mindestens eine C1-C12-Acylgruppe, vorzugsweise die Acetylgruppe, an ein in der Substanz enthaltenes 0- oder ein N-Atom gebunden ist, und deren Perhydrolyse C1-C12-Alkanpersäuren, vorzugsweise Peressigsäure, liefert.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.
Als wasserlösliche Builderkomponenten kommen prinzipiell alle in maschinellen Geschirreinigungsmitteln üblicherweise eingesetzten Builder in Frage, z. B. polymere Alkaliphosphate, die in Form ihrer alkalischen neutralen oder sauren Natrium- oder Kaliumsalze vorliegen können. Beispiele hierfür sind: Tetranatriumdiphosphat, Dinatriumdihydrogendiphosphat, Pentanatriumtriphosphat, sogenanntes Natriumhexametaphosphat sowie die entsprechenden Kaliumsalze bzw. Gemische aus Natriumhexametaphosphat sowie die entsprechenden Kaliumsalze bzw. Gemische aus Natrium- und Kaliumsalzen. Die Mengen an Phosphat liegen im Bereich von bis zu etwa 30 Gew.-%, bezogen auf das gesamte Mittel; vorzugsweise sind die erfindungsgemäßen Mittel jedoch frei von solchen Phosphaten. Weitere mögliche wasserlösliche Builderkomponenten sind z. B. organische Polymere nativen oder synthetischen Ursprungs, vor allem Polycarboxylate, die insbesondere in Hartwassersystemen als Co-Builder wirken. In Betracht kommen beispielsweise Polyacrylsäuren und Copolymere aus Maleinsäureanhydrid und Acrylsäure sowie die Natriumsalze dieser Polymersäuren. Handelsübliche Produkte sind z.B. Sokalan(R) CP 5 und PA 30 von BASF, Alcosperse(R) 175 oder 177 von Alco, LMW(R) 45 N und SP02 N von Norsohaas. Zu den nativen Polymeren gehören beispielsweise oxidierte Stärke (z. B. Deutsche Patentanmeldung P 42 28 786.3) und Polyaminosäuren wie Polyglutaminsäure oder Polyasparaginsäure, z. B. der Firmen Cygnus bzw. SRCHEM. In principle, all builders commonly used in machine dishwashing detergents are suitable as water-soluble builder components, eg. B. 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. Other possible 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. For example, 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.
Weitere mögliche Builderkomponenten sind natürlich vorkommende Hydroxycarbonsäuren wie z. B. Mono-, Dihydroxybernsteinsäure, α-Hydroxypropionsäure und Gluconsäure. Bevorzugte Builderkomponenten sind die Salze der Citronensäure, insbesondere Natriumcitrat. Als Natriumcitrat kommen wasserfreies Trinatriumcitrat bzw. vorzugsweise Trinatriumcitratdihydrat in Betracht. Trinatriumcitratdihydrat kann als fein- oder grobkristallines Pulver eingesetzt werden. In Abhängigkeit vom letztlich in den erfindungsgemäßen Mitteln eingestellten pH-Wert können auch die zu Citrat korrespondierenden Säuren vorliegen.Other possible builder components are naturally occurring hydroxycarboxylic acids such as B. mono-, dihydroxysuccinic acid, α-hydroxypropionic acid and gluconic acid. Preferred builder components are the salts of Citric acid, especially sodium citrate. As 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. Depending on the ultimately in the pH set according to the invention can also be adjusted to citrate corresponding acids are present.
Als Bleichmittel auf Sauerstoffbasis kommen in erster Linie Natriumperboratmono- und -tetrahydrat oder Natriumpercarbonat in Betracht. Der Einsatz von Natriumpercarbonat hat Vorteile, da sich dieses besonders günstig auf das Korrosionsverhalten an Gläsern auswirkt. Das Bleichmittel auf Sauerstoffbasis ist deshalb vorzugsweise ein Percarbonat-Salz, insbesondere Natriumpercarbonat. Da Aktivsauerstoff erst bei erhöhten Temperaturen von allein seine volle Wirkung entfaltet, werden zu seiner Aktivierung in der Geschirrspülmaschine sogenannte Bleichmittelaktivatoren eingesetzt. Als Bleichmittelaktivatoren dienen organische, 0- oder N-(C1-C12)-acylgruppenhaltige Bleichmittelaktivatoren, z.B. PAG (Pentaacetylglucose), DADHT (1,5-Diacetyl-2,4-dioxo-hexahydro-1,3,5-triazin) und ISA (Isatosäureanhydrid), vorzugsweise jedoch N,N,N',N'-Tetraacetylethylendiamin (TAED). Überdies kann auch der Zusatz geringer Mengen bekannter Bleichmittelstabilisatoren wie beispielsweise von Phosphonaten, Boraten bzw. Metaboraten und Metasilikaten sowie Magnesiumsalzen wie Magnesiumsulfat zweckdienlich sein.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). In addition, the addition of small amounts of known bleach stabilizers such as, for example, phosphonates, borates or metaborates and metasilicates and magnesium salts such as magnesium sulfate may also be useful.
Zur besseren Ablösung Eiweiß-, Fett- oder Stärke-haltiger Speisereste enthalten die erfindungsgemäßen Geschirreinigungsmittel Enzyme wie Proteasen, Amylasen, Lipasen und Cellulasen, beispielsweise Proteasen wie BLAP(R) 140 der Firma Henkel; Optimase(R) -M-440, Optimase(R) -M-330, Opticlean(R) -M-375, Opticlean(R) -M-250 der Firma Solvay Enzymes; Maxacal(R) CX 450.000, Maxapem(R) der Firma Ibis; Savinase(R) 4,0 T, 6,0 T, 8,0 T der Firma Novo; Esperase(R) T der Firma Ibis und Amylasen wie Termamyl(R) 60 T, 90 T der Firma Novo; Amylase-LT(R) der Firma Solvay Enzymes oder Maxamyl(R) P 5000, CXT 5000 oder CXT 2900 der Firma Ibis; Lipasen wie Lipolase(R) 30 T der Firm Novo; Cellulasen wie Celluzym(R) 0,7 T der Firma Novo Nordisk. Vorzugsweise enthalten die Geschirreinigungsmittel Proteasen und/oder Amylasen.To better detach protein, fat or starch-containing food residues, 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 (R) 30 T from Novo; Cellulases such as Celluzym (R) 0.7 T from Novo Nordisk. The dishwashing detergents preferably contain proteases and / or amylases.
Vorzugsweise enthalten die erfindungsgemäßen Mittel zusätzlich die in üblichen niederalkalischen maschinellen Geschirreinigungsmitteln enthaltenen Alkaliträger wie z. B. Alkalisilikate, Alkalicarbonate und/oder Alkalihydrogencarbonate. Zu den üblicherweise eingesetzten Alkaliträgern zählen Carbonate, Hydrogencarbonate und Alkalisilikate mit einem Molverhältnis SiO2 / M2O (M = Alkaliatom) von 1,5 : 1 bis 2,5 : 1. Alkalisilikate können dabei in Mengen von bis zu 30 Gew.-%, bezogen auf das gesamte Mittel, enthalten sein. Auf den Einsatz der hoch alkalischen Metasilikate als Alkaliträger wird vorzugsweise verzichtet. Das in den erfindungsgemäßen Mitteln bevorzugt eingesetzte Alkaliträgersystem ist ein Gemisch aus im wesentlichen Carbonat und Hydrogencarbonat, vorzugsweise Natriumcarbonat und Hydrogencarbonat, das in einer Menge von bis zu 60 Gew.-%, vorzugsweise 10 bis 40 Gew.-%, bezogen auf das gesamte Mittel, enthalten ist. Je nachdem, welcher pH-Wert letztendlich gewünscht bzw. eingestellt wird, variiert das Verhältnis von eingesetztem Carbonat und eingesetztem Hydrogencarbonat; üblicherweise wird jedoch ein Überschuß an Natriumhydrogencarbonat eingesetzt, so daß das Gewichtsverhältnis zwischen Hydrogencarbonat und Carbonat im allgemeinen 1 : 1 bis 15 : 1 beträgt.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. The alkali carriers usually used include carbonates, hydrogen carbonates and alkali silicates with a molar ratio SiO 2 / M 2 O (M = alkali atom) of 1.5: 1 to 2.5: 1. 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. Depending on which pH value is ultimately desired or set, 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.
Den erfindungsgemäßen Mitteln können gegebenenfalls auch noch Tenside, insbesondere schwach schäumende nichtionische Tenside zugesetzt werden, die der besseren Ablösung fetthaltiger Speisereste, als Netzmittel, als Granulierhilfsmittel oder als Dispergierhilfsmittel zur besseren, homogenen Verteilung der vorgenannten Silberkorrosionsschutzmittel in der Spülflotte und auf den Silberoberflächen dienen. Ihre Menge beträgt dann bis zu 5 Gew.-%, vorzugsweise bis zu 2 Gew.-%. Üblicherweise werden extrem schaumarme Verbindungen eingesetzt. Hierzu zählen vorzugsweise C12-C18-Alkylpolyethylenglykol-polypropylenglykolether mit jeweils bei zu 8 Mol Ethylenoxid- und Propylenoxideinheiten im Molekül. Man kann aber auch andere, als schaumarm bekannte nichtionische Tenside verwenden, wie z. B. C12-C18-Alkylpolyethylenglykol-polybutylenglykolether mit jeweils bis zu 8 Mol Ethylenoxid- und Butylenoxideinheiten im Molekül, endgruppenverschlossene Alkylpolyalkylenglykolmischether sowie die zwar schäumenden, aber ökologisch attraktiven C8-C14-Alkylpolyglucoside mit einem Polymerisierungsgrad von etwa 1 - 4 (z. B. APG(R) 225 und APG(R) 600 der Firma Henkel) und/oder C12-C14-Alkylpolyethylenglykole mit 3 - 8 Ethylenoxideinheiten im Molekül. Es sollte eine gebleichte Qualität verwendet werden, da sonst ein braunes Granulat entsteht. Ebenfalls geeignet sind Tenside aus der Familie der Glucamide wie zum Beispiel Alkyl-N-Methyl-Glucamide (Alkyl = Fettalkohol mit der C-Kettenlänge C6-C14). Es ist teilweise vorteilhaft, wenn die beschriebenen Tenside als Gemische eingesetzt werden, z. B. die Kombination Alkylpolyglykosid mit Fettalkoholethoxylaten oder Glucamide mit Alkylpolyglykosiden usw.If appropriate, 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. But you can also use other, known as 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. Bleached quality should be used, otherwise brown granules will result. Also suitable are surfactants from the family of glucamides, such as, for example, alkyl-N-methyl-glucamides (alkyl = fatty alcohol with the C chain length C 6 -C 14 ). It is partially advantageous if the surfactants described are used as mixtures, for. B. the combination of alkyl polyglycoside with fatty alcohol ethoxylates or glucamides with alkyl polyglycosides etc.
Sofern die Reinigungsmittel bei der Anwendung zu stark schäumen, können ihnen noch bis zu 6 Gew.-%, vorzugsweise etwa 0,5 bis 4 Gew.-% einer schaumdrückenden Verbindung, vorzugsweise aus der Gruppe der Silikonöle, Gemische aus Silikonöl und hydrophobierter Kieselsäure, Paraffinöl/Guerbetalkohole, Paraffine, hydrophobierter Kieselsäure, der Bisstearinsäureamide und sonstiger weiterer bekannter im Handel erhältliche Entschäumer zugesetzt werden. Weitere fakultative Zusatzstoffe sind z. B. Parfümöle.If 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.
Die erfindungsgemäßen- Geschirrspülmittel liegen vorzugsweise als pulverförmige, granulare oder tablettenförmige Präparate vor, die in an sich üblicher Weise, beispielsweise durch Mischen, Granulieren, Walzenkompaktieren und/oder durch Sprühtrocknung hergestellt werden können.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.
Zur Herstellung von erfindungsgemäßen Reinigungsmitteln in Tablettenform geht man vorzugsweise derart vor, daß man alle Bestandteile in einem Mischer miteinander vermischt und das Gemisch mittels herkömmlicher Tablettenpressen, beispielsweise Exzenterpressen oder Rundläuferpressen, mit Preßdrucken im Bereich von 200 · 105 Pa bis 1 500 · 105 Pa verpresst. Man erhält so problemlos bruchfeste und dennoch unter Anwendungsbedingungen ausreichend schnell lösliche Tabletten mit Biegefestigkeit von normalerweise über 150 N. Vorzugsweise weist eine derart hergestellte Tablette ein Gewicht von 15 g bis 40 g, insbesondere von 20 g bis 30 g auf, bei einem Durchmesser von 35 mm bis 40 mm.For the preparation of cleaning agents according to the invention in tablet form, 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. In this way, break-proof tablets with a flexural strength of normally more than 150 N that are sufficiently quickly soluble under the conditions of use are obtained without problems. 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.
Die Herstellung der Maschinengeschirrspülmittel in Form von nicht staubenden, lagerstabil rieselfähigen Pulvern und/oder Granulaten mit hohen Schüttdichten im Bereich von 750 bis 1000 g/l kennzeichnet sich dadurch, daß man in einer ersten Verfahrensteilstufe die Builder-Komponenten mit wenigstens einem Anteil flüssiger Mischungskomponenten unter Erhöhung der Schüttdichte dieses Vorgemisches vermischt und nachfolgend - gewünschtenfalls nach einer Zwischentrocknung - die weiteren Bestandteile des Maschinengeschirrspülmittels, darunter die anorganischen redoxaktiven Substanzen mit dem so gewonnenen Vorgemisch vereinigt.The production of 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.
Da ein eventueller Alkalicarbonat-Gehalt die Alkalität des Produktes stark beeinflußt, muß die Zwischentrocknung so durchgeführt werden, daß der Zerfall des Natriumbicarbonats zu Natriumcarbonat möglichst gering (oder zumindest möglichst konstant) ist. Ein zusätzlich durch die Trocknung entstehender Natriumcarbonat-Anteil müßte nämlich bei der Formulierung der Granulat-Rezeptur berücksichtigt werden. Niedrige Trocknungstemperaturen wirken dabei nicht nur dem Natriumbicarbonat-Zerfall entgegen, sondern erhöhen auch die Löslichkeit des granulierten Reinigungsmittels bei der Anwendung. Vorteilhaft ist daher beim Trocknen eine Zulufttemperatur, die einerseits zur Vermeidung des Bicarbonat-Zerfalls so gering wie möglich sein sollte und die andererseits so hoch wie nötig sein muß, um ein Produkt mit guten Lagereigenschaften zu erhalten. Bevorzugt ist beim Trocknen eine Zulufttemperatur von ca. 80°C. Das Granulat selbst sollte nicht auf Temperaturen über etwa 60°C erhitzt werden. In der ersten Teilstufe des Mischverfahrens wird der Builder in der Regel in Abmischung mit wenigstens einer weiteren Komponente des Geschirrspülmittels mit den Flüssigkomponenten beaufschlagt. In Betracht kommt hier beispielsweise eine Vorstufe, in der die Builder-Komponente in Abmischung mit Perborat mit den flüssigen nichtionischen Tensiden und/oder der Lösung der Duftstoffe beaufschlagt und innig vermischt wird. Nachfolgend werden die restlichen Komponenten zugegeben und das Gesamtgemisch in der Mischvorrichtung durchgearbeitet und homogenisiert. Die Mitverwendung zusätzlicher Flüssigkeitsmengen, insbesondere also der Einsatz von zusätzlichem Wasser, ist hier in der Regel nicht erforderlich. Das angefallene Stoffgemisch liegt dann als rieselfähiges nicht staubendes Pulver der gewünschten hohen Schüttdichte etwa im Bereich von 750 bis 1000 g/l vor.As a possible alkali carbonate content the alkalinity of the product strongly influenced, 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 granules themselves shouldn't be on Temperatures above about 60 ° C are heated. In the first part of the The builder is usually mixed with at least a mixing process another component of the dishwashing detergent with the liquid components acted upon. For example, 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. Below are 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.
Die Vorgranulate werden dann mit den noch fehlenden Komponenten des Geschirrspülmittels, darunter anorganische redoxaktive Substanzen, zum Fertigprodukt abgemischt. Die Mischzeit liegt in allen hier dargestellten Fällen sowohl in der Vorstufe der verdichtenden Abmischung unter Einfluß von Flüssigkomponenten wie in der nachfolgenden Endabmischung mit den weiteren Komponenten im Bereich weniger Minuten, beispielsweise im Bereich von 1 bis 5 Minuten.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.
In einer besonderen Ausführungsform kann es bei der Herstellung von feinen Granulatkörnern zweckmäßig sein, durch Abpudern der Oberfläche des gebildeten Granulatkorns eine weiterführende Stabilisierung und Egalisierung einzustellen. Geeignet sind hierzu insbesondere geringe Anteile an Wasserglaspulver bzw. pulverförmigem Alkalicarbonat.In a particular embodiment, 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.
Die zu verwendenden Mittel können sowohl in Haushaltsgeschirrspülmaschinen wie in gewerblichen Spülmaschinen eingesetzt werden. Die Zugabe erfolgt von Hand oder mittels geeigneten Dosiervorrichtungen. Die Anwendungskonzentrationen in der Reinigungsflotte betragen etwa 2 bis 8 g/l, vorzugsweise 2 bis 5 g/l.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.
Das Spülprogramm wird im allgemeinen durch einige auf den Reinigungsgang folgende Zwischenspülgänge mit klarem Wasser und einem Klarspülgang mit einem gebräuchlichem Klarspülmittel ergänzt und beendet. Nach dem Trocknen erhält man nicht nur ein völlig sauberes und in hygienischer Hinsicht einwandfreies Geschirr, sondern vor allem auch hellglänzende Silberbesteckteile. 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.
Silberlöffel (Typ WMF, Hotelbesteck, Form Berlin) wurden mit einem Silberreiniger
gereinigt, mit Benzin entfettet und getrocknet. Jeweils drei
Löffel wurden dann in den Besteckkorb einer Haushaltsgeschirrspülmaschine
(HGSM) Typ Bosch S 712 gegeben. Das Reinigungsprogramm (65°C, 16°dH) wurde
nun gestartet und dem Reinigungsgang 50 g einer Anschmutzung (1) sowie 30
g des Reinigers direkt in die Maschine dosiert. Nach Beendigung des Spül-
und Trocknungsvorganges wurden die HGSM für 10 Minuten geöffnet, die Maschine
wieder geschlossen und erneut in der gleichen Weise gespült. Nach
dem 10. Spülgang wurden die Löffel entnommen und bewertet. Dazu wurden die
Anlauffarben im Bereich von 0 bis 4 bewertet:
(0 = kein Anlaufen, 1 = ganz/leichte Gelbfärbung, 2 = stärkere Gelbfärbung,
3 = ganzflächige Gold- bis Braunfärbung, 4 = Violett- bis Schwarzfärbung
der Löffel; Werte im oberen linken Teil der Tabelle 1).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. For this purpose, the tarnishing colors were rated in the range from 0 to 4:
(0 = no tarnishing, 1 = whole / light yellow coloring, 2 = stronger yellow coloring, 3 = all-over gold to brown coloring, 4 = violet to black coloring of the spoons; values in the upper left part of table 1).
Gleichzeitig wurde die Entfernung von Teeanschmutzung auf Porzellangut beurteilt. Hier lag die Benotung zwischen 0 und 10 mit 0 = keine Tee-Entfernung und 10 = vollständige Tee-Entfernung; Werte im unteren rechten Teil der Tabelle 1. At the same time, the removal of tea stains on porcelain judged. Here the rating was between 0 and 10 with 0 = no tea removal and 10 = complete tea removal; Values in the lower right Part of table 1.
In einem Wasseraufbereitungskessel werden 16 1 kaltes Stadtwasser (16°d)
kurz zum Sieden erhitzt. Man läßt 96 g Schwarzen Tee im Nylonnetz bei geschlossenem
Deckel für 5 Minuten ziehen und überführt den Tee in eine
Tauchapparatur mit Heizung und Rührwerk.
60 Teetassen werden 25 mal im Ein-Minuten-Takt bei 70°C in den vorbereiteten
Teesud getaucht. Anschließend werden die Tassen abgehängt und mit
der Öffnung nach unten zum Trocknen auf ein Blech gelegt.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.
Zuerst wurde folgendes niederalkalisches Grundprodukt hergestellt, dessen
1 Gew.-%ige Lösung in destilliertem Wasser einen pH-Wert von 9,5 ergab:
Mit diesem Grundprodukt wurden die mit der nachfolgenden Rezeptur vorgegebenen
Testvariationen durchgeführt. Die Ergebnisse sind Tabelle 1 zu
entnehmen.
Desweiteren wurden maschinelle Geschirrspülmittel der folgenden Zusammensetzungen
hergestellt (siehe Tabelle 2). Als Silberkorrosionsschutzmittel
wurden dabei die Verbindungen A - D eingesetzt:
Die Silberlöffel wurden durchweg mit 0 bis 1, d.h. "kein bis sehr schwaches Anlaufen", bewertet. Darüberhinaus zeigten die Zusammensetzungen 1 bis 20 gegenüber bleichbaren Anschmutzungen wie z. B. Tee hervorragende Reinigungsleistungen.The silver spoons were consistently rated 0 to 1, i.e. "no to very weak Tarnishing ", evaluated. In addition, the compositions 1 up to 20 against bleachable stains such as B. Excellent tea Cleaning services.
Identische Zusammensetzungen, jedoch jeweils ohne Silberkorrosionsschutzmittel A - D wirkten zwar ebenfalls sehr gut gegen bleichbare Anschmutzungen, verursachten jedoch auf Silberlöffeln Gelb- bis Violettfärbungen (Bewertung: 2 bis 4).Identical compositions, but without silver corrosion protection A - D also worked very well against bleachable soiling, however, caused yellow to violet tints on silver spoons (Rating: 2 to 4).
Für die Untersuchungen wurde als Probenmaterial anstelle von Silberbesteck Silberdraht (d = 2 mm, 99,99 %ig) verwendet. Von diesem Silberdraht wurden jeweils ca. 10 cm lange Stücke abgeschnitten und der in die Meßlösung eintauchende Teil der Probe mit SiC-Schleifpapier (600er Körnung) geschliffen. Anschließend wurden die Proben gut mit bidestilliertem Wasser gepült und evtl. anhaftende Schleifreste mit einem fusselfreien Tuch abgewischt. Dieser Vorgang wurde gegebenenfalls mehrfach wiederholt, bis die Probe optisch einen einwandfreien Eindruck hinterließ. Nach dem Schleifen der Proben wurden diese sofort für die Messung verwendet, um einer Reaktion des metallischen Silbers mit der Laborluft zuvorzukommen. Die effektive, in die Lösung eingetauchte Probenoberfläche betrug 0,70 cm2.For the investigations, silver wire (d = 2 mm, 99.99%) was used as the sample material instead of silver cutlery. Approximately 10 cm long pieces were cut from this silver wire and the part of the sample immersed in the measuring solution was ground with SiC abrasive paper (600 grit). The samples were then rinsed well with double-distilled water and any adhering grinding residues were wiped off with a lint-free cloth. This process was repeated several times, if necessary, until the sample optically left a perfect impression. After grinding the samples, they were used immediately for the measurement in order to pre-empt a reaction of the metallic silver with the laboratory air. The effective sample surface immersed in the solution was 0.70 cm 2 .
Die Experimente wurden in einer Duran-Glaszelle durchgeführt. Als Meßelektroden dienten die erwähnten Silberdrähte (A = 0,70 cm2). Die Gegenelektrode bestand aus einem Goldblech (99,99 %ig) mit einer Fläche von 1 cm2. Als Bezugselektrode wurde auf Grund der alkalischen Elektrolytlösungen eine Hg/Hg0/0,1 m NaOH-Elektrode gewählt, die über eine Haber-Luggin-Kapillare mit den Elektrolyten verbunden war. Die Messungen wurden mit 5 g/l Reiniger in Leitungswasser von 16°d und einer Salzbelastung von ca. 600 mg (Trockenrückstand) durchgeführt. The experiments were carried out in a Duran glass cell. The silver wires mentioned (A = 0.70 cm 2 ) served as measuring electrodes. 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).
Beim Ansetzen der Reinigerlösungen wurde zunächst das niederalkalische Grundprodukt (siehe oben) gelöst und die Lösung auf 65°C erhitzt. Direkt vor der Messung wurden das Bleichmittel und der Bleichmittelaktivator und/oder das Silberkorrosionsschutzmittel zugegeben. Danach erfolgte die elektrochemische Messung. Während der elektrochemischen Experimente wurden die Elektrolytlösungen auf 65°C temperiert und mit Luft gespült.When preparing the cleaning solutions, 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.
Zur Aufnahme der Stromspannungskurven wurde das Elektrodenpotential ausgehend von - 0,62, V bezogen auf die Standardwasserstoffelektrode (SHE), mit einer konstanten Geschwindigkeit erhöht. Nach einer Erhöhung von insgesamt 1,1 V wurde das Potential anschließend mit gleicher Geschwindigkeit erniedrigt. Hierzu diente ein Standardpotentiostat bestehend aus Mitkopplungsverstärker, Differenzverstärker, Addierer und Impedanzwandler, sowie ein Funktionsgenerator (Prodis 16 der Firma Intelligent Controls CLZ GmbH).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. 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).
Die Charakterisierung des Korrosionsverhaltens erfolgte an Hand von Stromspannungskurven.
Wesentliche Informationen kommen dabei aus dem Nulldurchgang
der Stromspannungskurve (Ruhepotential, das sich auch ohne äußere
Potentialbeeinflußung von selbst einstellt) und der Steigung der Kurve am
Nulldurchgang (reziproker Polarisationswiderstand) E. Heitz, R. Henkhaus,
A. Rahmel, "Korrosionskunde im Experiment" Verlag Chemie (1983), Seiten 31
ff; H. Kaesche, "Die Korrosion der Metalle", 2. Auflage, Springer Verlag
(1979), Seiten 117 ff. Dabei verschiebt sich durch den Zusatz des Silberkorrosionsschutzmittels
das Potential des Nulldurchgangs zu niedrigeren
Werten und die Steigung nimmt ab. Also wird die Silberkorrosion durch den
Zusatz der Silberkorrosionsschutzmittel auch elektrochemisch meßbar erheblich
reduziert.
Claims (15)
- The use of inorganic redox-active substances in dishwashing detergents as corrosion inhibitors for silver, characterized in that the inorganic redox-active substances are at least partly water-soluble 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 are present in one of the oxidation stages II, III, IV, V or VI.
- The use claimed in claim 1, characterized in that the metal salts and/or metal complexes are selected from the group consisting of MnSO4, Mn(ll) citrate, Mn(ll) stearate, Mn(ll) acetyl acetonate, Mn(ll) [1-hydroxyethane-1,1-diphosphonate], V2O5, V2O4, VO2, TiOSO4, K2TiF6, K2ZrF6, CoSO4, Co(NO3)2, Ce(NO3)3.
- The use claimed in claim 2, characterized in that the metal salt is MnSO4.
- A low alkali machine dishwashing detergent of which 1% by weight solutions have a pH value of 8 to 11.5 and preferably 9 to 10.5 and which contain 15 to 60% by weight and preferably 30 to 50% by weight of a water-soluble builder component, 5 to 25% by weight and preferably 10 to 15% by weight of an oxygen-based bleaching agent, 1 to 10% by weight and preferably 2 to 6% by weight of an organic bleach activator containing O- or N-(C1-12)-acyl groups, 0.1 to 5% by weight and preferably 0.5 to 2.5% by weight of an enzyme, based on the detergent as a whole, and silver corrosion inhibitors, characterized in that at least partly water-soluble metal salts and/or metal complexes selected from the group of manganese, titanium, zirconium, hafnium, vanadium, cobalt, cerium salts and/or complexes, of which the metals are present in one of the oxidation stages II, III, IV, V or VI, are present in a quantity of 0.05 to 6% by weight as the silver corrosion inhibitors.
- A detergent as claimed in claim 4, characterized in that the metal salts and/or metal complexes are selected from the group consisting of MnSO4, Mn(ll) citrate, Mn(ll) stearate, Mn(ll) acetyl acetonate, Mn(ll) [1-hydroxyethane-1,1-diphosphonate], V2O5, V2O4, VO2, TiOSO4, K2TiF6, K2ZrF6, CoSO4, Co(NO3)2, Ce(NO3)3.
- A detergent as claimed in claim 5, characterized in that the metal salt is MnSO4.
- A detergent as claimed in claims 4 to 6, characterized in that the silver corrosion inhibitors are present in a quantity of 0.2 to 2.5% by weight, based on the detergent as a whole.
- A detergent as claimed in claims 4 to 7, characterized in that the water-soluble builder component is a salt of citric acid, preferably sodium citrate.
- A detergent as claimed in claims 4 to 8, characterized in that the oxygen-based bleaching agent is a percarbonate salt, preferably sodium percarbonate.
- A detergent as claimed in claims 4 to 9, characterized in that the organic bleach activator containing O- or N-(C1-12)-acyl groups is N,N,N',N'-tetraacetyl ethylenediamine (TAED).
- A detergent as claimed in claims 4 to 10, characterized in that the enzyme is an amylase and/or protease.
- A detergent as claimed in claims 4 to 11, characterized in that it additionally contains up to 60% by weight and preferably 10 to 40% by weight, based on the detergent as a whole, of an alkali carrier system consisting essentially of carbonate and hydrogen carbonate, preferably sodium carbonate and sodium hydrogen carbonate.
- A detergent as claimed in claims 4 to 12, characterized in that it additionally contains up to 5% by weight and preferably up to 2% by weight, based on the detergent as a whole, of surfactants, preferably low-foaming nonionic surfactants.
- A detergent as claimed in claims 4 to 13, characterized in that it is present in tablet form and is obtainable by mixing all its ingredients in a mixer and tabletting the resulting mixture in a tabletting press under pressures of 2·107 Pa to 1.5·108 Pa.
- A detergent as claimed in claims 4 to 14, characterized in that it is present in the form of a powder or granules and has an apparent density of 750 g/l to 1000 g/l.
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19934315397 DE4315397A1 (en) | 1993-05-08 | 1993-05-08 | Cleaning composition preventing tarnishing of table silver in dishwashing machines |
DE4315397 | 1993-05-08 | ||
DE19934325922 DE4325922A1 (en) | 1993-08-02 | 1993-08-02 | Silver corrosion protection agent I |
DE4325922 | 1993-08-02 | ||
PCT/EP1994/001386 WO1994026859A1 (en) | 1993-05-08 | 1994-05-02 | Silver-corrosion protection agent (i) |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0697035A1 EP0697035A1 (en) | 1996-02-21 |
EP0697035B1 true EP0697035B1 (en) | 1998-02-11 |
Family
ID=25925737
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP94916181A Expired - Lifetime EP0697035B1 (en) | 1993-05-08 | 1994-05-02 | Silver-corrosion protection agent (i) |
Country Status (10)
Country | Link |
---|---|
EP (1) | EP0697035B1 (en) |
JP (1) | JPH08509777A (en) |
AT (1) | ATE163191T1 (en) |
CA (1) | CA2162460A1 (en) |
CZ (1) | CZ286401B6 (en) |
DE (1) | DE59405259D1 (en) |
DK (1) | DK0697035T3 (en) |
ES (1) | ES2112542T3 (en) |
PL (1) | PL177936B1 (en) |
WO (1) | WO1994026859A1 (en) |
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WO2008075084A1 (en) * | 2006-12-21 | 2008-06-26 | Reckitt Benckiser N.V. | Detergent composition |
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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 (en) * | 1991-03-15 | 1993-06-07 | Cleantabs As | PHOSPHATE-FREE MACHINE DISHWASH |
DK167364B1 (en) * | 1991-11-08 | 1993-10-18 | Cleantabs As | MACHINE DETERGENT |
-
1994
- 1994-05-02 CZ CZ19952348A patent/CZ286401B6/en not_active IP Right Cessation
- 1994-05-02 PL PL94311594A patent/PL177936B1/en unknown
- 1994-05-02 CA CA002162460A patent/CA2162460A1/en not_active Abandoned
- 1994-05-02 DE DE59405259T patent/DE59405259D1/en not_active Expired - Lifetime
- 1994-05-02 AT AT94916181T patent/ATE163191T1/en not_active IP Right Cessation
- 1994-05-02 WO PCT/EP1994/001386 patent/WO1994026859A1/en active IP Right Grant
- 1994-05-02 ES ES94916181T patent/ES2112542T3/en not_active Expired - Lifetime
- 1994-05-02 DK DK94916181T patent/DK0697035T3/en active
- 1994-05-02 EP EP94916181A patent/EP0697035B1/en not_active Expired - Lifetime
- 1994-05-02 JP JP6524887A patent/JPH08509777A/en active Pending
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008075084A1 (en) * | 2006-12-21 | 2008-06-26 | Reckitt Benckiser N.V. | Detergent composition |
Also Published As
Publication number | Publication date |
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ATE163191T1 (en) | 1998-02-15 |
WO1994026859A1 (en) | 1994-11-24 |
CA2162460A1 (en) | 1994-11-24 |
CZ234895A3 (en) | 1996-01-17 |
EP0697035A1 (en) | 1996-02-21 |
DE59405259D1 (en) | 1998-03-19 |
ES2112542T3 (en) | 1998-04-01 |
DK0697035T3 (en) | 1998-09-28 |
PL177936B1 (en) | 2000-01-31 |
CZ286401B6 (en) | 2000-04-12 |
PL311594A1 (en) | 1996-02-19 |
JPH08509777A (en) | 1996-10-15 |
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