EP0697036A1 - Produits de protection de l'argent contre la corrosion ii - Google Patents

Produits de protection de l'argent contre la corrosion ii

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Publication number
EP0697036A1
EP0697036A1 EP94917579A EP94917579A EP0697036A1 EP 0697036 A1 EP0697036 A1 EP 0697036A1 EP 94917579 A EP94917579 A EP 94917579A EP 94917579 A EP94917579 A EP 94917579A EP 0697036 A1 EP0697036 A1 EP 0697036A1
Authority
EP
European Patent Office
Prior art keywords
weight
silver
composition according
alkyl
agent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP94917579A
Other languages
German (de)
English (en)
Other versions
EP0697036B1 (fr
Inventor
Jürgen Härer
Helmut Blum
Birgit Burg
Thomas Holderbaum
Willi Buchmeier
Peter Jeschke
Horst-Dieter Speckmann
Frank Wiechmann
Christian Nitsch
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE19934315397 external-priority patent/DE4315397A1/de
Priority claimed from DE19934338724 external-priority patent/DE4338724A1/de
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0697036A1 publication Critical patent/EP0697036A1/fr
Application granted granted Critical
Publication of EP0697036B1 publication Critical patent/EP0697036B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38609—Protease or amylase in solid compositions only
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0091—Dishwashing tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0042—Reducing agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0073—Anticorrosion compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • C11D3/048—Nitrates or nitrites
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/1213—Oxides or hydroxides, e.g. Al2O3, TiO2, CaO or Ca(OH)2
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/122—Sulfur-containing, e.g. sulfates, sulfites or gypsum
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2065—Polyhydric alcohols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2079—Monocarboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2096—Heterocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/28—Heterocyclic compounds containing nitrogen in the ring
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/30—Amines; Substituted amines ; Quaternized amines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/349—Organic compounds containing sulfur additionally containing nitrogen atoms, e.g. nitro, nitroso, amino, imino, nitrilo, nitrile groups containing compounds or their derivatives or thio urea
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/361—Phosphonates, phosphinates or phosphonites
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2041—Dihydric alcohols
    • C11D3/2058—Dihydric alcohols aromatic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/3472—Organic compounds containing sulfur additionally containing -COOH groups or derivatives thereof

Definitions

  • active oxygen compounds such as sodium perborate or sodium percarbonate, which are used to remove bleachable soiling, for example Tea stains / tea deposits, coffee residues, vegetable dyes, lipstick residues and the like are used.
  • active oxygen compounds are mainly used in modern low-alkaline machine dishwashing detergents of the new generation of detergents together with bleach activators.
  • These modern agents generally consist of the following functional components: builder component (complexing agent / dispersant), alkali carrier, bleaching system (bleach + bleach activator), enzymes and wetting agents (surfactants).
  • the silver surfaces are generally more sensitive to the changed recipe parameters of the new generation of active chlorine-free cleaners with lowered pH values and activated oxygen bleaching. During machine rinsing, these agents release the actual bleaching agent hydrogen peroxide or active oxygen in the cleaning cycle.
  • the bleaching effect of the active oxygen-containing cleaners is enhanced by bleach activators, so that a good bleaching effect is achieved even at low temperatures. In the presence of these bleach activators, peracetic acid forms as a reactive intermediate.
  • peracetic acid forms as a reactive intermediate.
  • silver in the presence of silver not only oxidic deposits, but preferably oxidic deposits on the silver surfaces due to the oxidizing attack of the intermediately formed peroxides or the active oxygen substance are formed. If the salt load is high, chloridic deposits can additionally develop.
  • the tarnishing of the silver is also reinforced by higher residual water hardness during the cleaning cycle.
  • alkaline dishwashing detergents which contain benzotriazoles as a corrosion inhibitor for silver.
  • machine-applicable dishwashing detergents which can contain, among other things, perborate with an organic bleach activator as the oxidizing agent.
  • Additions of benzotriazole and iron (III) chloride, among others, are recommended as anti-tarnish agents.
  • PH values of preferably 7-11.5 are mentioned.
  • EP 135 226 and EP 135 227 describe weakly alkaline, machine-usable dishwashing detergents containing peroxy compounds and activators, which may contain, among other things, benzotriazoles and fatty acids as silver preservatives.
  • peroxy compounds and activators which may contain, among other things, benzotriazoles and fatty acids as silver preservatives.
  • German Offenlegungsschrift DE 41 28 672 that peroxy compounds which are activated by addition of known organic bleach activators prevent silver parts from tarnishing in strongly alkaline cleaning agents.
  • organic redox-active substances in particular the coupler and / or developer compounds which are usually used in oxidation colorants and have not hitherto been described as silver corrosion inhibitors, effectively prevent the corrosion of silver in machine dishwashers.
  • the invention relates to the use of organic redox-active substances in dishwashing detergent preparations as silver corrosion protection agents.
  • corrosion is to be interpreted in its broadest use in chemistry. In particular, “corrosion” should stand for every visually just recognizable change in a metal surface, here silver. B. a selective discoloration, be it z. B. a large area tarnishing.
  • Organic redox-active substances are those organic substances which are accessible to easily reversible oxidation and / or reduction. For example, typical complexing agents such. B. EDTA or hydroxyethane diphosphonic acid and related compounds do not fall under this definition.
  • organic redox-active substances z. As ascorbic acid (vitamin C), indole, methionine ( ⁇ -amino-7-methyl-ercaptobutyric acid).
  • N-mono- (C 1 -C 4 -alkyl) glycines e.g. N-mono-methyl-glycine and N, N-di- (-C-C4-alkyl) -glycine, e.g. N, N-dimethylglycine and 2-phenylglycine.
  • Coupler and / or developer compounds known from oxidative dyeing are also particularly suitable.
  • the preferably used organic substances to prevent the corrosion of silver are coupler and / or developer compound chosen from the group of diaminopyridines, aminohydroxypyridines, Dihydroxypyri- dine, heterocycli Service hydrazones, aminohydroxypyrimidines, Dihydroxypyri i- dine, tetraaminopyrimidines, triaminohydroxypyrimidines, Diaminodihydroxy- pyrimidines Dihydroxynaphtaline, naphthols , Pyrazolones, hydroxyquinolines, aminoquinolines, the primary aromatic amines, which have a further free or substituted with C 1 -C 4 -alkyl or C2-C4 ⁇ hydroxyalkyl groups in the ortho, meta or para position, and the di or trihydroxybenzenes.
  • the developer and coupler compounds used according to the invention to prevent silver corrosion are the substances from the abovementioned groups that are usually used in oxidation dyeing agents. Examples of such developer and coupler compounds can be found, for example, in "Venkataraman, The Che istry of synthetic dyes, Vol. V, Academic Press New York / London, 1971, pages 478-495", and in the literature cited there.
  • the developer or coupler compounds selected from the group p-hydroxyphenylglycine, 2,4-diaminophenol, 5-chloro-2,3-pyridinediol, 1- (p-aminophenyl) morpholine are particularly suitable for preventing silver corrosion , Hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, pyrogallol.
  • the organic redox-active substances are preferably coated, ie completely covered with a waterproof material which is easily soluble at the cleaning temperatures, in order to prevent their premature decomposition or oxidation during storage.
  • Preferred coating materials which are applied by known processes are paraffins, micro waxes, waxes of natural origin such as carnauba wax, candell law wax, beeswax, higher-melting alcohols such as hexadecanol, soaps or fatty acids.
  • the coating material which is solid at room temperature, is applied in a molten state to the material to be coated, for example by spinning finely divided material to be coated in a continuous stream through a spray zone of the molten coating material, which is also continuously generated.
  • the melting point must be selected so that the coating material easily dissolves or quickly melts in the dishwasher during the subsequent use of the silver corrosion protection agents.
  • the melting point should therefore ideally be in the range between 45 ° C and 65 ° C and preferably in the range 50 ° C to 60 ° C for most applications.
  • the organic redox-active substances described above are particularly suitable for preventing silver corrosion if they are contained in alkaline cleaners for the automatic cleaning of dishes. This is all the more surprising since the effectiveness of these silver corrosion protection agents is not impaired by the presence of oxygen-based bleaching agents usually present in lower-alkaline cleaners.
  • Another subject of the invention is 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.
  • an organic 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 corrosion inhibitor, an organic redox-active substance being contained as the silver corrosion inhibitor.
  • ascorbic acid, indole, methionine, N-mono- (-C-C4-alkyl) -glycine, N, N * -Di- (-C-C4-alkyl) -glycine and 2-phenylglycine but especially coupler and / or developing agents selected from the group of slide inopyri- dine, aminohydroxypyridines, dihydroxypyridines, heterocycTischen hydrazones, aminohydroxypyrimidines, dihydroxypyrimidines, tetraaminopyrimidines, tri- aminohydroxypyrimidines, Diaminodihydroxypyri idine, Dihydroxynaphtaline, naphthols, pyrazolones, hydroxyquinolines, aminoquinolines, primary aro ⁇ matic amines, which have in the ortho, meta or para position a further free or with C-C4-alkyl or C2-C4-hydroxyalkyl groups substituted hydroxy or amino group and the di
  • Preferred dishwashing detergents contain coupler and / or developer compounds selected from the group p-hydroxyphenylglycine, 2,4-diaminophenol, 5-chloro-2,3-pyridine, l- (p-aminophenyl) morpholine, hydroquinone , Pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, pyrogallol and mixtures thereof.
  • the organic redox-active substances are preferably present in the compositions according to the invention in a total amount of 0.05 to 6% by weight, preferably 0.2 to 2.5% by weight, based on the total composition.
  • 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.
  • Bu lder components are such.
  • polyacrylic acids and copolymers of maleic anhydride and acrylic acid as well as 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 (eg German patent application P 4228786.3) and polyamino acids such as polyglutanic acid or polyaspartic acid, e.g. B. from the companies Cygnus and SRCHEM.
  • builder components are naturally occurring hydroxy carboxylic acids such as. B. mono-, dihydroxysuccinic acid, ⁇ -hydroxypropionic acid and gluconic acid.
  • Preferred builder components are the salts of citric acid, especially sodium citrate.
  • Water-free trisodium citrate or preferably trisodium citrate dihydrate are suitable as sodium citrate.
  • Trisodium citrate dihydrate can be used as a fine or coarse crystalline powder.
  • the acids corresponding to citrate can also be present.
  • Sodium perborate ono- and tetrahydrate or sodium percarbonate are primarily considered as bleaching agents based on oxygen.
  • 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, in particular 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.
  • PAG penentaacetylglucose
  • DADHT l, 5-diacetyl-2,4-dioxo-hexahydro-l, 3,5-triazine
  • ISA isato acid
  • N, N, N ', N'-tetraacetylethylene diamine TAED
  • bleach stabilizers such as, for example, phosphonates, borates or metaborates and metasilicates and magnesium salts such as magnesium sulfate can 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; 0ptimase ( R ) -M-440, 0ptimase ( R ) -M-330, 0 ⁇ ticlean ( R ) -M-375, 0pticlean ( 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 TermamyH) 60 T, 90 T from Novo; Amylase-LT ( R ) from Solvay Enzymes or Maxamyl ( R ) P 5000, C
  • proteases such as BLAP ( R ) 140 from Hen
  • the agents according to the invention preferably additionally contain the alkali carriers contained in conventional low-alkaline machine dishwashing detergents, such as. B. alkali silicates, alkali carbonates and / or alkali hydrogen carbonates.
  • Alkali silicates can be present in amounts of up to 30% by weight all the means.
  • the use of the highly alkaline metasilicates as alkali carriers is preferably dispensed with.
  • 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 Means, is included.
  • the ratio of carbonate and hydrocarbon used varies. gene carbonate; 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 improve the detachment of 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 serve.
  • 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 Ci2-Cl8 _ alkyl polyethylene glycol polypropylene glycol ether, each containing up to 8 moles of ethylene oxide and propylene oxide units in the molecule.
  • nonionic surfactants known as low-foam, such as.
  • B C ⁇ 2-Ci8-alkylpolyethylene glycol-polybutylene glycol ether, each with up to 8 moles of ethylene oxide and butylene oxide units in the molecule, end-capped alkylpolyalkylene glycol mixed ethers and the foaming but ecologically attractive C8-Ci4-alkylpolyglucosides with a degree of polymerization of about 1 - 4 ( eg APG ( R ) 225 and APG ( R ) 600 from Henkel) and / or Ci2-Ci4-alkyl polyethylene glycols with 3 - 8 ethylene oxide units in the molecule.
  • the cleaning agents foam too much during use, they can still contain up to 6% by weight, preferably about 0.5 to 4% by weight, of a foam-suppressing compound, preferably from the group of silicone oils, mixtures of silicone oil and hydrophobized silica, Paraffin oil / Guerbet alcohols, paraffins, hydrophobized silica, the bisstearic acid amides and other other known commercially available defoamers can be added.
  • a foam-suppressing compound preferably from the group of silicone oils, mixtures of silicone oil and hydrophobized silica, Paraffin oil / Guerbet alcohols, paraffins, hydrophobized silica, the bisstearic acid amides and other other known commercially available defoamers can be added.
  • Other optional additives are e.g. B. Perfume oils.
  • the dishwashing detergents according to the invention are preferably in the form of powdery, granular or tablet-like preparations which can be prepared in a conventional manner, for example by mixing, granulating, roller compacting and / or by spray drying.
  • the procedure is preferably such that all constituents are mixed with one another in a mixer and the mixture is used by means of conventional tablet presses, for example eccentric presses or rotary presses, with pressures in the range from 200 • 10-5 Pa to 1 500 • 10 ⁇ 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 from 35 mm to 40 mm.
  • 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 is characterized in that in a first process stage, the builder components are at least partially liquid Mixing components mixed with increasing the bulk density of this premix and subsequently - if desired after an intermediate drying - the further components of the dishwasher detergent, including organic redox-active substances, combined with the premix obtained in this way.
  • the intermediate drying must be carried out so that the decomposition of the sodium bicarbonate to sodium carbonate is as low as possible (or at least as constant as possible).
  • An additional sodium carbonate portion resulting from the drying would have to be in the formulation of Granulate recipe are taken into account.
  • Low drying temperatures not only counteract sodium bicarbonate decay, but also increase the solubility of the granulated detergent during use. It is therefore advantageous for drying to have a supply air temperature which, on the one hand, should be as low as possible to avoid bicarbonate decomposition and, on the other hand, must be as high as necessary in order to obtain a product with good storage properties.
  • a supply air temperature of approximately 80 ° C. is preferred during drying.
  • the builder is generally charged with the liquid components in admixture with at least one further component of the dishwashing detergent.
  • a precursor may be considered in which the builder component, mixed with perborate, is acted upon by the liquid nonionic surfactants and / or the solution of the fragrances and mixed intimately.
  • the remaining components are then added and the entire mixture is worked through and homogenized in the mixing device.
  • additional amounts of liquid in particular the use of additional water, is generally not necessary here.
  • the mixture of substances obtained is then in the form of a free-flowing, dust-free powder of the desired high bulk density in the range from 750 to 1000 g / l.
  • the pre-granules are then mixed with the still missing components of the dishwashing detergent, including organic redox-active substances, to form the finished product.
  • the mixing time is both in the preliminary stage of the compacting mixture under the influence of liquid components and in the subsequent final mixture with the other components in the range of a few minutes, for example in the range of 1 to 5 minutes.
  • the agents to be used can be used both in household dishwashers and in commercial dishwashers. They are added by hand or using suitable dosing devices.
  • the application concentrations in the cleaning liquor are about 2 to 8 g / 1, preferably 2 to 5 g / 1.
  • the rinse program is generally supplemented and ended with a few intermediate rinse cycles with clear water and a rinse cycle with a common rinse aid following the cleaning cycle. After drying, not only are completely clean dishes which are an from a hygienic point of view, but above all also bright silver silver cutlery.
  • Silver spoons (type WMF, hotel cutlery, form Berlin) were cleaned with a silver cleaner, degreased with gasoline 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) was now started and 50 g of a soiling (-0 and 30 g of the detergent) were metered 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 cycle, 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 left to draw in the nylon net with the lid closed for 5 minutes and the tea is transferred to a dipping apparatus with heating and stirrer.
  • teacups are immersed 25 times in one-minute intervals at 70 ° C in the prepared tea infusion.
  • the cups are then removed and placed on a tray with the opening facing down to dry.
  • TAED Machine dishwashing detergents of the following compositions were also prepared (see Table 4).
  • the compounds A - M were used as silver corrosion inhibitors: A: p-hydroxyphenylglycine B: 2,4-diaminophenol C: 5-chloro-2,3-pyridinediol D: 1- (p-aminophenyl) morpholine E: ascorbic acid F: N-monomethylglycine G: N, N-dimethylglycine H: 2-hydroxy-4-aminopyrimidine I: 2,4-dihydroxy-5-methylpyrimidine K: indole L: methionine M: 2-phenylglycine
  • Ci2-Ci4-fatty alcohol ethoxylate (2E0) (Dehydol LS2 from Henkel) 1 0.75 1 1 0.75 1 1 0.75 1
  • Silver corrosion inhibitor AM (A) (B) (C) (0) (E) (F) (G) (H) (I) (K) 1 1 1 1 2 2 2 3 pH value of a 1% aqueous 10 , 5 11 9.5 10.5 11 9.5 10.5 11 9.5 10.5 solution
  • Trisodium citrate dihydrate 25 43 38 25 43 38 24 43 38 24
  • Silver corrosion protection agent AM (L) (M) (A) (B (C) (D) (E) (F) (G) (H) 3 3 4 4 4 4 5 5 5 5 pH value of a 1% aqueous solution 11 9.5 10.5 11 9.5 10.5 11 9.5 10.5 11 solution
  • the silver spoons were consistently rated 0 to 1, i.e. "no to very weak tarnishing", rated. Identical compositions, but without silver corrosion inhibitor A - D in each case caused yellow to violet colors on silver spoons (rating: 2 to 4).
  • Electrolytes and electrodes are Electrolytes and electrodes:
  • the experiments were carried out in a Duran glass cell.
  • the counterelectrode consisted of a gold plate (99.99% pure) with an area of 1 cm ⁇ .
  • a Hg / Hg0 / 0.1 m NaOH electrode was chosen as the reference electrode, which was connected to the electrolytes via a Haber-Luggin capillary.
  • the measurements were carried out with 5 g / 1 cleaner in tap water of 16 ° d and a salt load of approx. 600 mg (dry residue).
  • the low-alkaline basic product (see above) was first dissolved and the solution heated to 65 ° C.
  • the bleach and the bleach activator were used immediately before the measurement and / or the silver anticorrosive agent is added.
  • the electrochemical measurement was then carried out. During the electrochemical experiments, the electrolyte solutions were heated to 65 ° C and flushed with air.
  • the electrode potential was increased at a constant speed starting from -0.62, V based on the standard hydrogen electrode (SHE). After a total increase of 1.1 V, the potential was subsequently lowered at the same rate.
  • a standard potentiostat consisting of a positive feedback amplifier, differential amplifier, adder and impedance converter and a function generator (Prodis 16 from Intelligent Controls CLZ GmbH) were used for this purpose.
  • the corrosion behavior was characterized on the basis of 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. The silver corrosion is thus also considerably reduced by the addition of the silver corrosion protection agents.
EP94917579A 1993-05-08 1994-05-02 Produits de protection de l'argent contre la corrosion ii Expired - Lifetime EP0697036B1 (fr)

Applications Claiming Priority (5)

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

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EP0697036B1 EP0697036B1 (fr) 1999-07-28

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HU218008B (hu) 2000-05-28
HUT73028A (en) 1996-06-28
HU9503201D0 (en) 1995-12-28
PL311624A1 (en) 1996-03-04
WO1994026860A1 (fr) 1994-11-24
DK0697036T3 (da) 2000-01-31
CA2162459A1 (fr) 1994-11-24
ATE182615T1 (de) 1999-08-15
CZ262595A3 (en) 1996-02-14
JPH08509778A (ja) 1996-10-15
HU9503200D0 (en) 1996-01-29
HU218021B (hu) 2000-05-28
EP0697036B1 (fr) 1999-07-28
CZ287850B6 (en) 2001-02-14
HUT73025A (en) 1996-06-28
DE59408548D1 (de) 1999-09-02
PL177935B1 (pl) 2000-01-31
ES2134944T3 (es) 1999-10-16

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