WO1994026859A1 - Silver-corrosion protection agent (i) - Google Patents

Silver-corrosion protection agent (i) Download PDF

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Publication number
WO1994026859A1
WO1994026859A1 PCT/EP1994/001386 EP9401386W WO9426859A1 WO 1994026859 A1 WO1994026859 A1 WO 1994026859A1 EP 9401386 W EP9401386 W EP 9401386W WO 9426859 A1 WO9426859 A1 WO 9426859A1
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Prior art keywords
wt
characterized
preferably
ii
composition according
Prior art date
Application number
PCT/EP1994/001386
Other languages
German (de)
French (fr)
Inventor
Jürgen Härer
Helmut Blum
Birgit Burg
Thomas Holderbaum
Willi Buchmeier
Peter Jeschke
Horst-Dieter Speckmann
Frank Wiechmann
Christian Nitsch
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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Publication date
Priority to DE19934315397 priority Critical patent/DE4315397A1/en
Priority to DEP4315397.6 priority
Priority to DE19934325922 priority patent/DE4325922A1/en
Priority to DEP4325922.7 priority
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority claimed from DE1994505259 external-priority patent/DE59405259D1/en
Publication of WO1994026859A1 publication Critical patent/WO1994026859A1/en

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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/046Salts
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    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials characterised by their shape or physical properties
    • C11D17/0039Coated compositions or coated components in the compositions, (micro)capsules
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials characterised by their shape or physical properties
    • C11D17/0047Detergents in the form of bars or tablets
    • C11D17/0065Solid detergents containing builders
    • C11D17/0073Tablets
    • C11D17/0091Dishwashing tablets
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    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials characterised by their shape or physical properties
    • C11D17/06Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065High-density particulate detergent compositions
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    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/0042Reducing agents
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/0073Anticorrosion compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/046Salts
    • C11D3/048Nitrates, nitrites
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/12Water-insoluble compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/12Water-insoluble compounds
    • C11D3/1213Oxides, hydroxides, e.g. Al2O3, TiO2, CaO, Ca(OH)2
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/12Water-insoluble compounds
    • C11D3/122Sulfur-containing, e.g. sulfates, sulfites, gypsum
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2072Aldehydes-ketones
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    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2075Carboxylic acids-salts thereof
    • C11D3/2079Monocarboxylic acids-salts thereof
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    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2075Carboxylic acids-salts thereof
    • C11D3/2086Hydroxy carboxylic acids-salts thereof
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    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/34Organic compounds containing sulfur
    • C11D3/349Organic compounds containing sulfur additionally containing nitrogen atoms, e.g. nitro, nitroso, amino, imino, nitrilo, nitrile groups containing compounds or their derivatives, thio urea
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    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/36Organic compounds containing phosphorus
    • C11D3/361Phosphonates, phosphinates, phosphonites
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    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2003Alcohols; Phenols
    • C11D3/2041Dihydric alcohols
    • C11D3/2058Dihydric alcohols aromatic
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    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/34Organic compounds containing sulfur
    • C11D3/3472Organic compounds containing sulfur additionally containing -COOH groups or derivatives thereof

Abstract

The invention concerns the use of inorganic redox compounds, in particular salts and/or complexes of metals selected from the group comprising Mn, Ti, Zr, Hf, V, Co, and Ce, as silver-corrosion protection agents in dishwasher washing-up agents, in particular low-alkali dishwasher washing-up agents.

Description

"S lberkorrosionsschutzmittel I"

It is a well known fact that silver, even if it is not in use, "starts". It's just a matter of time before it gets dark, brownish, bluish to blue-black spots or discoloration total, making it "started" in common parlance.

Even with the mechanical cleaning of silverware occur in practice always problems in the form of tarnishing and discoloration of surfaces Silberober¬ on. Silver can react to sulfur-containing substances that are dissolved water in Spül¬ or dispersed here because (DDWM) in the cleaning of dishes in domestic dishwashing machines leftovers and including mustard, peas, egg and other sulfur containing Verbin¬ be so applications such as mercapto amino acid introduced into the wash liquor. The wäh¬ rend the machine dishwashing much higher temperatures and longer contact times with the sulfur-containing food remains in favor comparatively with manual dishwashing the tarnishing of silver. Due to the intensive cleaning process in the dishwasher the Silberoberfl che is completely degreased and thereby influences sensitive to chemical Ein¬.

In the application of active chlorine detergent tarnishing can be largely prevented by sulfur-containing compounds, as these compounds are reacted Ver¬ by oxidation of the sulfidic functions in secondary reaction to Sulfönen or sulfates.

The problem of the south but was re currently lberanlaufens, sodium or sodium were used as alterna¬ tive to the active chlorine compounds active oxygen compounds, such as for example, pin residues to eliminate bleachable stains such as tea stains / tea coatings, coffee residues, dyes from vegetables, Lippen¬ and the like are used.

These active oxygen compounds are used primarily in modern niederal¬ maniacal machine detergents of the new generation cleaner with bleach activators. These modern means consist are generally employed of the following functional components: builder component (complexing agents / dispersant), alkali carriers, bleaching system (bleach + bleach activator), enzymes, and wetting agents (surfactants).

the silver surfaces react generally more sensitive to the changing recipe parameters of the new active chlorine free Reini¬ gergeneration with lowered pH values ​​and activated oxygen bleach. During the machine dishwashing these means release the actual bleaching agent hydrogen peroxide or active oxygen in the wash cycle. The blei¬ sponding effect of detergents containing active oxygen is strengthened by vatoren Bleichakti¬, so that even at low temperatures, a good bleaching effect is obtained. In the presence of bleach activators formed as a reactive intermediate peracetic acid. Under these verän¬ derten flushing not only sul¬ fidische but by the oxidizing effect of the intermediate gebilde¬ th peroxides or the active oxygen preferred oxide deposits on the silver surfaces are formed in the presence of silver. Under high salt concentrations can also arise chloridi¬ specific coverings. tarnishing of the silver is amplified further by higher residual water hardness during the cleaning cycle.

Avoiding the silver corrosion, ie the formation of sulfidic, oxidi¬ shear or chloridic coatings on silver is the subject of numerous publications Ver¬. The corrosion of silver is prevented in these descriptions, especially by so-called silver protectants.

From the British Patent GB 1,131,738 Geschirr¬ alkaline detergent are known which contain as a corrosion inhibitor for silver benzotriazoles. In the American patent US 3,549,539 strongly alkaline machine dishwashing compositions are described which may contain as oxidants, inter alia, perborate with an organic bleach activator. To prevent tarnishing additives are suggested, inter alia, likewise if benzotriazole and iron (III) chloride. Here are a pH of preferably 7 - called 11.5. In European Patent¬ EP 135,226 and EP 135,227 writing weakly alkaline machine dishwashing will be described with a content of peroxy compounds and activators, which can contain as silver protection agents, inter alia benzotriazoles and fatty acids. Finally, from the German disclosure supply application DE 41 28 672 known that peroxy compounds, which are activated by set Zu¬ known organic bleach activators, prevent the tarnishing of silver in highly alkaline cleaning compositions.

We have found that inorganic redox-active substances, in particular the salts or complex compounds of certain bis¬ ago is not described as a silver anticorrosive metals, the corrosion of silver in automatic dishwashers effective verhin¬ countries.

The invention relates to the use of inorganic redox-active substances in dishwashing compositions as Silberkorrosionsschutzmit¬ tel.

The word "corrosion" is to be interpreted in its broadest commonly used in the chemical importance, especially to here "corrosion" for any visually just discernible change a metal surface, here are silver, it was for. As a selective discoloration, whether such. As a großflä¬ chiges tarnishing.

"Inorganic redox-active substances" are zen such inorganic Substan¬, which are amenable to easy running reversible oxidation and / or reduction. So fall, for example, oxides, hydroxides or halides Halo¬ of ammonium salts or of alkali or alkaline earth metals excluded from this definition. As "inorganic redox-active substances" include those based on different oxidation states of sulfur substances Na2S2Ü3 (sodium thiosulfate), Na2S2Ü4 (Natriu dithionite) or a2S2Ü5 (sodium metabisulfite) to name.

Especially, however, the salts or complex compounds of certain metals are suitable. the use of metal salts and / or complex Metall¬ is preferably selected from the group of manganese, titanium, zirconium, Haf¬ nium-, vanadium, cobalt and cerium salts and / or complexes to Verhinde¬ tion of silver corrosion, wherein the metals are present in one of the oxidation stages II, III, IV, V or VI.

The customary in chemistry definition of "oxidation state" is shown for example in "Römpp Chemie Lexikon, Georg Thieme Verlag, Stuttgart / New York, 9th edition, 1991, page 3168".

The metal salts or metal complexes used should be at least partially soluble in water. The suitable salt-forming counterions include all conventional one-, two-, or three-fold negatively charged inorganic anions, such. B. oxide, sulfate, nitrate, fluoride, but also organic anions such. B. stearate.

Metal complexes according to the invention are compounds which consist of a central atom and one or more ligands. The Zentralato is one of the abovementioned metals in one of the aforementioned oxidation states. The ligands are neutral molecules or anions which are mono- or polydentate; the term "ligand" within the meaning of the invention is nä¬ described for example in "Römpp Chemie Lexikon, Georg Thieme Verlag, Stuttgart / New York, 9th edition, 1990, page 2507" here. the charge of the Zen¬ complement tralatoms in a metal complex and the charge of the ligand / not, provides to zero, depending on whether a cationic or an anionic charge excess is vor¬, either one or more of the abovementioned anions or one or more cations such. For example, sodium, potassium, Ammoniu ions for charge balancing. Suitable complexing agents are, for example, citrate, acetylacetonate or 1-hydroxyethane-l, 1-diphosphonate.

Particularly preferred metal salts and / or metal complexes are selected from the group MnSOj, Mn (II) citrate, Mn stearate (II), Mn (II) -acetylaceto- nat, Mn (II) - [l-hydroxyethane-l, l diphosphonate], V2O5, V2O4, VO2, Ti0S04, K2TiFö, K2ZrF6, C0SO4, Co (N03) 2, Ce (N03) 3 and mixtures thereof. Insbe¬ sondere preferred MnSÜ4.

These metal salts or metal complexes are in allgemei¬ nen commercially available substances which are used for the purpose of silver corrosion protection according to the invention without prior purification nen kön¬. Thus, the S03 from the preparation (contact method) (VO2, V2O4 V2O5.) Is known, for example, mixture of pentavalent and tetravalent vanadium suitable, as are obtained by diluting a Ti (S04) 2 ~ solution resulting titanyl sulfate, Ti0S04.

The inorganic redox-active substances, in particular metal salts or metal complexes, are preferably coated, ie completely rial covered with a waterproof, but easily soluble in the cleaning temperatures Mate¬ to prevent their premature decomposition or oxidation at the La¬ delay. Preferred coating materials Telindus trie by known processes, such as melt coating method according Sandwik from the Lebensmit¬ be applied, are paraffins, microcrystalline waxes, waxes na¬-natural origin such as carnauba wax, candelilla wax, beeswax, hö¬ herschmelzende alcohols such as hexadecanol, soaps or fatty acids. Here, the solid at room temperature Coating material is applied to the material to be coated in ge schmolzenem state, for example, by fine-particle is thrown material to be coated in a continuous stream through a likewise continuously produced spray mist zone of the molten coating material. The melting point must be chosen so that the coating material during the subsequent use of the silver corrosion inhibitor in the dishwasher easily dissolves or rapidly melts. The melting point should therefore ideally be for most applications in the range between 45 ° C and 65 ° C and preferably in the range 50 ° C to 60 ° C.

In particular, however, the inorganic redox-active substances described above are suitable for preventing silver corrosion if they are included in nie¬ the alkaline cleaners for machine dishwashing. This is all the more surprising since this Silberkorrosionsschutzmit¬ tel are not impaired in their effect by the presence of usually contained in low-alkali bleaching agents based on oxygen.

A further subject of the invention are therefore free low means for machine cleaning of dishware, whose 1 wt .-% solutions 9 to 10.5 have a pH value of 8 to 11.5, preferably containing 15 to 60 wt .-%, preferably 30 to 50 wt .-% of a water-soluble builder component, 5 to 25 wt .-%, preferably 10 to 15 wt .-% of a bleaching agent based on oxygen, 1 to 10 parts by weight, preferably 2 to 6 wt .-% of an organic, 0- or N- (Cι ~ Ci2) -acylgruppenhaltigen Bleich¬ mittelaktivators, 0.1 to 5 wt .-%, preferably 0.5 to 2.5 wt .-% of an enzyme, based on the total composition, and silver corrosion ¬ protection agents, wherein a silver corrosion protection agent is an inorganic redox-active substance is contained. In particular, metal salts and / or metal complexes selected from the group of manganese, titanium, zirconium, hafnium, vanadium, cobalt, cerium salts and / or complexes suitable, the metals being in one of the oxidation stages II, III are present IV, V or VI.

Preferred dishwashing detergents contain metal salts or metal complexes selected from the group nS04, Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [l-hydroxyethane-l, 1- diphosphonate], V2O5, V2O4, VO2, T1OSO4, K2TiF6, K2ZrF6, C0SO4, Co (N03) 2, Ce (NÜ3) 3, and mixtures thereof. In particular MnS04 is preferred. Preferably, the inorganic redox-active substances, in particular metal salts and / or metal complexes in the inventive compositions in a total amount of 0.05 to 6 wt .-%, preferably 0.2 to 2.5 wt .-%, based on the total composition , contain.

Organic, 0- or N- (Cι-Ci2 -) - acylgruppenhaltige Bleichmittelaktivato¬ ren are substances in which at least one Cj-C ^ acyl group, preferred wise the acetyl group, contained in the substance to a 0- or N- Ato is bound, and their perhydrolysis Cι-Ci2-Alkanpersäuren, preferred wise peracetic acid provides.

Water-soluble builder components in principle all builders used customarily in maschi¬ tional dishwashing detergents come into consideration for. B. polymeric alkali metal phosphates, which may be in the form of their alkaline neu¬ tral or acidic sodium or potassium salts. Examples include tetrasodium diphosphate, disodium dihydrogen diphosphate, pen tanatriumtriphosphat, zen so-called sodium hexametaphosphate and the ent speaking potassium salts or mixtures of sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium and Kaliumsal¬. The amounts of phosphate are in the range of up to about 30 wt .-%, based on the total composition; preferably, however, compositions of the invention are free of such phosphates. Other possible water-soluble builder components are,. B. organic polymers of native occurring or synthetic origin rule, above all polycarboxylates which act in particular in Hartwas¬ water systems as co-builders. In example, polyacrylic acids and copolymers of maleic anhydride and acrylic acid come so¬ as the sodium salts of these polymer acids. Commercial products are, for example, Sokalan (R) CP 5 and PA 30 of BASF, Alcosperse (R) 175 or 177 of Alco, LMW (R) 45 N and SP02 N of Norsohaas. ge to the native polymers, for example, oxidized starch hear (z. B. German Patent Application P 4228786.3) and polyamino acids like polyglutamic acid or Polyaspara- ginsäure, z. As the Cygnus and SRCHEM. Other possible builder components are naturally occurring hydroxycarboxylic acids such. B. mono-, dihydroxysuccinic acid, α-Hydroxypropion¬ acid and gluconic acid. Preferred builder components are the salts of citric acid, especially sodium citrate. The sodium was¬ serfreies trisodium citrate and preferably trisodium citrate come. Trisodium citrate dihydrate may be used as a fine or coarse crystalline powder. Depending on the ultimately set in the inventive compositions, the pH corresponding to citrate acids may be present.

As a bleaching agent based on oxygen are primarily Natriumperbo- ratmono- and tetrahydrate or sodium into consideration. The use of sodium has advantages, since this particularly favorable effect on the corrosion behavior of glasses. The bleaching agents Sauer¬ material base is therefore preferably a percarbonate salt, in particular sodium percarbonate. Since active oxygen only develops its full effect at elevated temperatures, so-called bleach activators are used to activate it in the dishwasher. As bleach activators are organic, 0- or N- (Cι-Ci2) -acylgruppen- containing bleach activators such as PAG (pentaacetyl glucose), DADHT (l, 5-diacetyl-2,4-dioxo-hexahydro-l, 3,5-triazine ) and ISA (Isatosäureanhy- drid), but preferably N, N, N ', N'-tetraacetylethylenediamine (TAED). Moreover, the addition may be small amounts of known Bleichmittelsta¬ bilisatoren such as phosphonates, borates or metabolites and metasilicates and magnesium salts such as magnesium sulfate be useful.

The separation of protein, fat or starch-containing food residues dishwashing compositions of the invention contain enzymes such as proteases, amylases, lipases, and cellulases, for example proteases such as BLAP (R) 140 from Henkel; 0ptimase (R) -M-440, 0ptimase (R) -M-330, Opticlean (R) -M-375, Opticlean (R) -M-250 from Solvay Enzy it; 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 Ibis company and amylases such as Termamyl (R) 60 T, 90 T Novo; Amylase-LT (R) from Solvay Enzymes or Maxamyl (R) P 5000, CXT 5000 or CXT 2900 from Ibis company; Lipases such as Lipolase (R) 30 T Firm of Novo; Cellulases as Celluzym (R) 0.7 T from Novo Nordisk. Preferably, the medium Geschirreinigungs¬ contain proteases and / or amylases.

Preferably, the inventive compositions additionally comprise alkali carriers contained in the union üb¬ low-alkali machine dishwashing detergents such. drogencarbonate as alkali silicates, alkali and / or Alkalihy-. Among the alkali carriers typically used include carbonates, bicarbonates and alkali metal silicates with a molar ratio SiO 2 / 2O (M = alkali metal atom) of from 1.5: 1 to 2.5: 1. Alkali metal silicates may be present in amounts of up to 30 wt .-%, based be included on the total agent. To the use of the highly alkaline metasilicates as Al¬ kaliträger is preferably omitted. The alkali carrier system preferably used in the inventive compositions is a mixture consisting essentially of carbonate and hydrogen carbonate, preferably Natriu carbonate and hydrogen carbonate, which, in an amount of up to 60 wt .-%, vorzugs¬ 10 to 40 wt .-%, based on is included the total agent. Depending on which is ultimately desired pH or adjusted, the ratio of carbonate and inserted employed Hydro¬ varies bicarbonate; However, typically, an excess of sodium hydrogencarbonate is used, so that the weight ratio between Hydrogencar¬ carbonate and carbonate generally from 1: 1 to 15: 1.

The agents of the invention more particularly low-foaming nonionic surfactants may also optionally, surfactants may be added to the improve the removal of greasy food residues, fleet as a wetting agent, as granulation or as a dispersing aid to improve, homoge¬ NEN distribution of the aforementioned silver corrosion protection agent in the Spül¬ and serve silver surfaces. Their amount is then up to 5 wt .-%, preferably up to 2 wt .-%. Extremely low-foaming compounds are used. These include preferably Ci2 ~ _ CL8 alkyl polyethylene glycol polypropylene glycol ethers containing up-to 8 moles of ethylene oxide and propylene oxide units in the molecule. But you can also an¬ particular, used as foaming known nonionic surfactants such. B. Ci2-CI8 alkyl polyethylene glycol polybutylene each having up to 8 moles of ethylene oxide and butylene oxide units in the molecule, endgruppenverschlos- sene Alkylpolyalkylenglykolmischether and although foaming, but ecologically attractive C8-Ci4 alkyl polyglucosides with a degree of about polymerize approximately 1 - 4 ( for example, APG (R) 225 and APG (R) 600 from Hen¬ kel) and / or Ci2-Ci4-alkyl polyethylene glycols with 3 -. 8 ethylene oxide units in the molecule. It should be used a bleached quality, otherwise a brown granules are formed. Also suitable are surfactants from the family of the glucamides such as alkyl-N-methyl glucamides (alkyl = fatty alcohol having a carbon chain length C6-C14). It is partially advantageous if the surfactants described be used as mixtures, eg. For example, the mixture of alkyl polyglycoside with fatty alcohol ethoxylates or glucamide with alkyl polyglycosides etc.

If the detergents foam too vigorously in the application, they may contain up to 6 wt .-%, preferably about 0.5 to 4 wt .-% of a foam-suppressing compound, preferably from the group of silicone oils, mixtures of silicone oil and hydrophobicized silica, paraffin oil / Guerbet betalkohole, paraffins, hydrophobicized silica, the Bisstearinsäure- a ide and other known commercially available commercially defoamers. Other optional additives such. As perfume oils.

The erfindungsgemäßen- dishwashing detergents are preferably present as powder, granular or tablet-form preparations which animals in a customary per se, for example by mixing, granulating, Walzenkompak¬ and / or can be prepared by spray-drying.

For the preparation of the inventive cleaning compositions in tablet form is preferably such procedure is to shear-mixing all ingredients in a Mi¬ together and the mixture using conventional Tablet¬ tenpressen, for example eccentric presses or rotary presses with press pressures in the range of 200 • IO 5 Pa to 1 500 10 ^ Pa pressed. Is obtained so easily break-proof, yet under conditions of use sufficiently fast soluble tablets having bending strength of normaler¬ example the 150 N. Preferably, a tablet produced a weight of 15 g to 40 g, especially from 20 g to 30 g, with a diameter from 35 mm to 40 mm.

The production of the machine dishwashing detergent in the form of non stau¬ reproduced, storage stable free-flowing powders and / or granules with high apparent densities in the range of 750 to 1000 g / 1 is characterized in that the builder components is liquid in a first process partial step with at least a portion blend components while increasing the bulk density of this premix, and subsequently - gewünschten- appropriate after an intermediate drying - united schinengeschirrspül eans, including punch the inorganic redox-active Sub¬ the other components of the ma- with the thus obtained premix.

As a possible alkali content greatly influences the alkalinity of the product, the intermediate drying must be performed so that the decomposition of the sodium bicarbonate is as low as possible (or at least as constant as possible) to sodium carbonate. An additional emerging through the drying sodium carbonate content should in fact be taken into consideration in the formulation of the granular formulation. Low drying temperatures have not only the decomposition of sodium bicarbonate contrary, but also increase the solubility of the granulated cleaning agent in the application. It is therefore advantageous when drying a supply air temperature, which should be as low as possible to avoid the disintegration bicarbonate one hand and the other hand, must be as high as necessary to a domestic product Pro¬ obtain with good storage properties. during drying is preferably an inlet air temperature of about 80 ° C. The granules themselves should not be heated to temperatures above about 60 ° C. In the first part stage of the mixing process, the builder is usually applied components in admixture with at least one other component of the dishwashing agent with the Flüssigkompo¬. Into consideration, for example, is here a precursor, in which the builder component is applied in admixture with perborate with the liquid nonionic surfactants and / or the solution of fragrances and intimately mixed. Subsequently, the remaining components are added and worked through the total mixture in the mixing apparatus and homogenized. The use of additional amounts of liquid, ie in particular the use of additional water here is not usually required. The resulted mixture is then present as a free-flowing non-dusting powder of the desired high bulk density approximately in the range of 750 to 1000 g /. 1

The pregranules then schirrspülmittels with the missing components of the Ge, including inorganic redox-active substances, mixed tigprodukt to Fer¬. The mixing time is in all cases illustrated here, both in the preliminary stage of compacting mixing under the influence of liquid components such as in the following final mixing with the other components in the region of a few minutes, for example in the range of 1 to 5 minutes.

In a particular embodiment, it may be expedient in the production of fine granules, set by powdering the surface of the granule gebil¬ Deten a further stabilization and equalization. this are particularly suitable small amounts of Was¬ serglaspulver or powdery alkali.

The agent to be used can be used both in domestic dishwashing machines and in commercial dishwashers. The addition is carried out by hand or by suitable metering devices. The Anwendungskon¬ concentrations in the wash liquor are from about 2 to 8 g / 1, preferred wise 2 to 5 g /. 1

The wash program is generally augmented by some of the main wash cycle Zwischenspülgänge with clear water and a rinse cycle with a conventional rinse aid and terminated. After drying, not only completely clean and hygienically respect dishes, but also bright shiny Silberbe¬ plug parts. EXAMPLES

Silver spoons (type WMF, hotel cutlery, form Berlin) were purified berreiniger with a Sil¬, degreased with petrol and dried. Three spoons were placed 712 then in the cutlery basket of a domestic dishwasher (DDWM) Bosch type S. The cleaning program (65 ° C, 16 ° dH) was then started and the washing cycle 50 grams of a stain (• ■ •) and 30 g of the cleaner dosed directly into the machine. Upon completion of the rinsing and drying, the DDWM were open for 10 minutes, the machine Ma¬ closed again and again rinsed in the same way. After the 10th rinse the spoons were taken and evaluated. For this, the temper colors were evaluated in the range of 0 to 4:

(0 = no tarnish, 1 = whole / slight yellowing, advertising 2 = greater Gelbfär¬, 3 = • entire surface gold to brown staining, 4 = violet dye to Schwarz¬ the spoon; values ​​in the upper left part of Table 1).

(1) Composition of the Anschmutzuno:

Ketchup: 25g

Mustard (extra hot) 25 g

Gravy: 25 g

Potato starch: 5 g

Benzoic acid: ig

Egg yolks: 3 pieces

Milk: 1/2 1

Margarine: 92 g

City water: 608 ml

At the same time the removal of tea stain was evaluated in Porzellangut. Here the grading ranged from 0 to 10 with 0 = no tea Ent fernung and 10 = complete tea-distance; Values ​​in the lower right part of the table 1. Preparation of the tea soil

In a water treatment tank 16 1 of cold tap water (16 ° d) are heated briefly to boiling. It is allowed 96 grams of black tea in nylon mesh draw at ge schlossenem lid for 5 minutes and transferred to the tea into a diving apparatus with heating and stirring.

60 teacups are immersed 25 times at one-minute intervals at 70 ° C in the vorberei¬ Teesud ended. Subsequently, the cups are disconnected and placed with the opening downwards to dry on a sheet.

Reiniqerzusammensetzunq

First, the following low-alkali basic product was prepared, whose

1 wt .-% solution in distilled water a pH of 9.5 showed:

56.0% trisodium citrate dihydrate

36.1% sodium bicarbonate 6.1% Sodium carbonate anhydrous

1.8% mixture of nonionic surfactants from APG 225 (C8-Cιo-Alkyloligoglu- Cosid) (and Dehydol) LS2 (Ci2-Ci4-fatty alcohol 2E0 ethoxylate) (1: 1)

With this basic product, the vorge passed with the following recipe test variations were carried out. The results are shown in Table 1 below.

81-86 wt .-% Primary Product

12 wt .-% of sodium percarbonate

0 - 10 wt .-% TAED

0-2 wt .-%, coated with paraffin manganese sulfate monohydrate

1 wt .-% protease, 1 wt .-% A ylase Table 1 Teereinioung / silver corrosion

Machine: Bosch S 712 tea: 1 no cleaning

Dosage: 30 g 10 optimal cleaning

Program: 65 ° C Universal Silver: 0 no startup

Water hardness: 16 ° dH 4 strong start

Figure imgf000017_0001

TAED Furthermore, machine dishwashing detergents of the following Zusammen¬ ratios were prepared (see Table 2). while compounds A were as silver corrosion inhibitors - E used:

V2O4 / V2O5 TiOSθ4 C0SO4 Ce (N0 3) 3 x 5H2O Na2S2θ3

Continued Table 2 (all figures in wt .-%)

11 12 13 14 15 16 17 18 19 20

Soda 26 8 to 25.5 8-26 7-26

Na-bicarbonate - 30 - - 29 - - 29 - -

Na-disilicate 19.5 to 34 19 to 34 18.5 to 34 18.5

Trisodium citrate dihydrate 25 43 38 25 43 38 24 43 38 24

polycarboxylate

(Sokalan CP5 from BASF.) 10-10 10-10 10-9 10

Na percarbonate 10 10 - 10 10 - 10 10 - 10

Na perborate monohydrate - - 7 - - 7 - - 7 -

TAED 3 2 2 3 2 2 3 2 2 3

Fatty alcohol ethoxylate 0.75 1 1 0.75 1 1 0.75 1 1 0.75 (Dehydol LS2 of Messrs. Henkel)

Alkyl oligoglucoside (APG 225 of Messrs. Henkel) 0.75 1 1 0.75 1 1 0.75 1 1 0.75

Protease 1 1 1.5 1 1 1.5 1 1 1.5 1

A lase 1 1 1.5 1 1 1.5 1 1 1.5 1

SiIberkorrosionsschutzmittel AE (A) (B) (C) (D) (E) (A) (B) (C) (D) (E) 3 3 4 4 4 4 5 5 5 5 pH of a l% aqueous 11 9.5 10.5 11 9.5 10.5 11 9.5 10.5 11 solution

Table 2 (all figures in wt .-%)

Figure imgf000020_0001

Figure imgf000020_0002

The silver spoons were consistently by 0 to 1, that "no to very schwa¬ ches start" evaluated. In addition, the compositions showed 1 to 20 against bleachable stains such. As tea excellent cleaning performance.

Identical compositions, but each without Silberkorrosionsschutz¬ medium A - D likewise worked very well against bleachable Anschmut¬ tongues, but caused on silver spoons yellow to violet staining (Rating: 2 to 4).

Electrochemical measurements

Sample preparation:

For the experiments as the sample material instead of silver cutlery silver wire was (d = 2 mm, 99.99% pure) was used. From this silver wire each about 10 cm long pieces were cut and in the test sample ein¬ submersible portion of the sample with SiC abrasive paper (600 grit) fen geschlif¬. The samples were well gepult with bidestiliiertem water and wiped off any adhering sanding residue with a lint-free cloth. This operation was optionally repeated several times, until the sample optically left a perfect impression. After grinding, the samples were immediately used for the measurement in order to forestall a reaction of the metallic silver with the laboratory air. The effective, dipped in the solution sample surface was 0.70 cm2.

Electrolytes and electrodes:

The experiments were conducted in a Duran glass cell. trodes as Meßelek¬ were mentioned silver wires (A = 0.70 cm2). The Gegenelek¬ trode consisted of a gold plate (99.99% pure) with an area of ​​1 cm. As a reference electrode, a Hg / HgO / 0.1 M NaOH electrode was selected on the basis of the alkaline electrolytic solutions pillare a Haber-Luggin Ka was associated with the electrolyte. The measurements were d with 5 g / 1 detergent in tap water of 16 ° and a salt content of approximately 600 mg (dry residue) is performed. When preparing the cleaning solutions, the low-alkali basic product was first (see above) and the solution heated to 65 ° C. Directly in front of the measurement, the bleach and the bleach activator and / or silver corrosion protection agents have been added. After that, the electrochemical measurement was carried out. During the electrochemical experiments, the electrolyte solutions were heated to 65 ° C and purged with air.

Apparatus and recording of the measurement curves:

For receiving the current-voltage curves, the electrode potential was aus¬ continuously from - 0.62 V relative to the standard hydrogen electrode (SHE), increased at a constant speed. After an increase of ins¬ total 1.1 V, the potential was lowered subsequently at the same speed. For this purpose a Standardpotentiostat served consisting of lung amplifier Mitkopp¬, differential amplifier, adder, and an impedance converter, and a function generator (Prodis 16 from Intelligent Controls CLZ GmbH).

Results:

The characterization of the corrosion behavior was voltage curves with reference to Strom¬. Essential information come of it from the Nulldurch¬ transition of the current-voltage curve (rest potential that is established without external Potentialbeeinflußung by itself) and the slope of the curve at the zero crossing (reciprocal polarization resistance) E. Heitz, R. Henkhaus, A. Rahmel, "Corrosion Studies experiment "Verlag Chemie (1983), pages 31 et seq; H. Kaesche, "The Corrosion of Metals", 2nd edition, Springer Verlag (1979), pages 117 et seq. In this case moves through the addition of Silber¬ corrosion protection by means of the potential of the zero crossing toward lower values ​​and the slope decreases. So the silver corrosion is measurable erheb¬ Lich reduced electrochemically by the addition of silver corrosion inhibitor. Composition capable zero crossing slope in

Cleaner E (mV) (SHE) zero crossing di / dE (mA / V)

Base product (87%) 435 25

+ 12% percarbonate

+ 1% TAED

Base product (87%) 360 0.3

+ 12% percarbonate

+ 1% Silberkorrosions¬ retardant *)

Base product (86.5%) 405 7

+ 12% percarbonate

+ 1% TAED

+ O, 5% Silberkorrosions¬ retardant *)

Base product (86%) 375 0.6

+ 12% percarbonate

+ 1% TAED

+ 1% Silberkorrosions¬ retardant *)

) SiIberkorrosionsschutzmittel: manganese sulphate monohydrate

Claims

P atentanspr ü che
1. The use of inorganic redox-active substances in Geschirr¬ cleaner preparations as silver corrosion inhibitor.
2. Use according to claim 1, characterized in that the anorgani¬ specific redox-active substance and / or metal complex aus¬ selected from the group of manganese, titanium, zirconium, hafnium, Va¬ nadium- a metal salt, cobalt, and cerium salts and / or complexes and the metals are present in one of the oxidation stages II, III, IV, V or VI.
3. Use according to claim 2, characterized in that the Metall¬ salts and / or metal complexes are selected from the group MnSθ4, Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II ) - [l-hydroxyethane-l, l-diphosphonate], V2O5, V2O4, VO2, TiOSθ4, TiFß ^, ^ ZrF, C0SO4, Co (N0 3) 2, Ce (N0 3). 3
4. Use according to claim 3, characterized in that the metal salt is MnSθ4.
5. Low Alkaline composition for machine dishwashing, des¬ sen 1 wt .-% solution has a pH from 8 to 11.5, preferably 9 to 10.5, having containing 15 to 60 wt .-%, preferably 30 - 50 wt .-% of a water-soluble builder component, 5 to 25 wt .-%, vor¬ preferably 10-15 wt .-% of a bleaching agent based on oxygen, 1 to 10 wt .-%, preferably 2 to 6 wt .-% of a organic, 0- or N- (Cι-Ci2) -acylgruppenhaltigen bleach activator, 0.1 to 5 wt .-%, preferably 0.5 to 2.5 wt .-% of an enzyme, based on the total composition, and silver corrosion inhibitors characterized ge denotes that an inorganic redox-active substance is contained as a silver corrosion protection agent.
6. Low Alkaline composition for machine dishwashing according to claim 5, characterized in that the medium Silberkorrosionsschutz- metal salts and / or metal complexes selected from the group of manganese, titanium, zirconium, hafnium, vanadium, cobalt, cerium - salts and / or complexes are present, and that the metals are present in one of the oxidation stages II, III, IV, V or VI.
7. The composition according to claim 6, characterized in that the metal salts and / or metal complexes are selected from the group MnSÜ4, Mn (II) - citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [l-hydroxy-ethane-l, l-diphosphonate], V2O5, V2O4, VO2, Ti0S04, - ^ TiFe, K2ZrF6, C0SO4, Co (N0 3) 2, Ce (N0 3). 3
8. A composition according to claim 6, characterized in that the metal salt is MnS04 "
9. A composition according to claim 5 to 8, characterized in that the anorga¬ African redox-active substances to the entire in an amount of 0.05 to 6 wt .-%, preferably 0.2 to 2.5 wt .-%, based agents are keeping ent.
10. A composition according to claim 5 to 9, characterized in that the wasser¬ soluble builder component is a salt of citric acid, preferably sodium citrate.
11. A composition according to claim 5 to 10, characterized in that the bleaching agents based on oxygen, a percarbonate salt, preferably sodium percarbonate.
is 12. Composition according to claim 5 to 11, characterized in that the orga niche, 0- or N- (Cι-Ci2) -acylgruppenhaltige NNN'.N' bleach activator tetracetyl ethylenediamine (TAED).
13. Composition according to claim 5 to 12, characterized in that the enzyme is an amylase and / or a protease.
14. Composition according to claim 5 to 13, characterized in that it zusätz¬ Lich up to 60 wt .-%, preferably 10 to 40 wt .-%, based on the total composition, of an alkali carrier system consisting essentially of carbonate and hydrogen carbonate, preferably sodium carbonate and sodium bicarbonate, contains. 11
15. Composition according to claim 5 to 14, characterized in that it zusätz¬ Lich up to 5 wt .-%, preferably up to 2 wt .-% based on the total agent, surfactants, preferably contains low-foaming nonionic surfactants.
16. Composition according to claim 5 to 15, characterized in that it is present in blettenform Ta¬ and press by mixing all its constituents in a mixer and compressing the mixture by means of a Tabletten¬ under pressures of 2 10? Pa is available to 1.5 • 10 ^ Pa.
17. Composition according to claim 5 to 15, characterized in that it is present as powder or granules and has a bulk density of 750 g / 1 to 1000 g /. 1
PCT/EP1994/001386 1993-05-08 1994-05-02 Silver-corrosion protection agent (i) WO1994026859A1 (en)

Priority Applications (4)

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
DEP4315397.6 1993-05-08
DE19934325922 DE4325922A1 (en) 1993-08-02 1993-08-02 Silver corrosion protection agent I
DEP4325922.7 1993-08-02

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DK94916181T DK0697035T3 (en) 1993-05-08 1994-05-02 Silver protectant as with the corrosion in
JP52488794A JPH08509777A (en) 1993-05-08 1994-05-02 Silver corrosion protection agent (▲ i ▼)
PL94311594A PL177936B1 (en) 1993-05-08 1994-05-02 Agent for protecting silver i against corrosion
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WO1996037596A1 (en) * 1995-05-22 1996-11-28 Henkel Kommanditgesellschaft Auf Aktien Diswasher detergent with agents providing protection against the corrosion of silver
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EP0697035B1 (en) 1998-02-11
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JPH08509777A (en) 1996-10-15
DK697035T3 (en)
AT163191T (en) 1998-02-15
CZ234895A3 (en) 1996-01-17
DK0697035T3 (en) 1998-09-28
CA2162460A1 (en) 1994-11-24
PL177936B1 (en) 2000-01-31
PL311594A1 (en) 1996-02-19
EP0697035A1 (en) 1996-02-21

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