WO1994026859A1 - Silver-corrosion protection agent (i) - Google Patents
Silver-corrosion protection agent (i) Download PDFInfo
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- 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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- 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 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).
- 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.
- the invention relates to the use of inorganic 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 noticeable change in a metal surface, here silver. B. a selective discoloration, be it z. B. a large area tarnishing.
- “Inorganic redox-active substances” are those inorganic substances which are amenable to easy reversible oxidation and / or reduction.
- the oxides, hydroxides or halides of ammonium salts or of alkali or alkaline earth metals do not fall under this definition.
- Examples of “inorganic redox-active substances” are the substances Na2S2Ü3 (sodium thiosulfate), Na2S2Ü4 (sodium dithionite) or a2S2Ü5 (sodium disulfite), which are based on various oxidation levels of the sulfur.
- the salts or complex compounds of certain metals are particularly suitable. It is preferred to use metal salts and / or metal complexes selected from the group consisting of manganese, titanium, zirconium, hafnium, vanadium, cobalt and cerium salts and / or complexes for preventing the Silver corrosion, the metals being in one of the oxidation states II, III, IV, V or VI.
- the metal salts or metal complexes used are said to be at least partially soluble in water.
- the counterions suitable for salt formation include all customary one, two or three times negatively charged inorganic anions, e.g. B. oxide, sulfate, nitrate, fluoride, but also organic anions such. B. stearate.
- Suitable complexing agents are, for example, citrate, acetylacetonate or 1-hydroxyethane-l, 1-diphosphonate.
- metal salts and / or metal complexes are selected from the group MnSOj, Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [l-hydroxyethane-l, l -diphosphonate], V2O5, V2O4, VO2, Ti0S04, K2TiFö, K2ZrF6, C0SO4, Co (N03) 2, Ce (N03) 3 and their mixtures.
- MnSÜ4 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 (V2O5. VO2, V2O4) known from the S03 production (contact process) is suitable, as is the titanyl sulfate, Ti0S04, formed by diluting a Ti (S04) 2 ⁇ solution.
- the inorganic redox-active substances are preferably coated, ie completely coated 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, microwaxes, waxes of natural origin such as carnauba wax, candella wax, beeswax, higher-melting alcohols such as hexadecanol, soaps or fats acids.
- the coating material which is solid at room temperature, is applied in the 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 dissolves easily or quickly melts during the subsequent use of the silver corrosion inhibitor in the dishwasher. The melting point should therefore be for most Applications are ideally in the range between 45 ° C and 65 ° C and preferably in the range 50 ° C to 60 ° C.
- the inorganic redox-active substances described above are 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 of an organic, 0- or N- (-C ⁇ Ci2) acyl group-containing bleach activator, 0.1 to 5 wt .-%, preferably 0.5 to 2.5 wt .-% of an enzyme, each based on the total agent, and silver corrosion ⁇ protectant, which contains an inorganic redox-active substance as a silver corrosion inhibitor.
- Metal salts and / or metal complexes selected from the group consisting of manganese, titanium, zirconium, hafnium, vanadium, cobalt, cerium salts and / or complexes are particularly suitable, the metals being in one of the oxidation states II, III , IV, V or VI are present.
- Preferred dish 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 their mixtures.
- MnS04 is particularly preferred.
- the inorganic redox-active substances are preferably present in the agents 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 agent , contain.
- Organic, 0- or N- (-C-Ci2 -) - acyl group-containing bleach activators are substances in which at least one Cj-C ⁇ -acyl group, preferably the acetyl group, is attached to a 0- or N- Ato is bound, and their perhydrolysis C 1 -C 2 -alkanoic acids, preferably peracetic acid, provides.
- polymeric alkali metal phosphates which may be in the form of their alkaline neutral or acidic sodium or potassium salts. Examples of these are: 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 co-builders.
- 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 (e.g.
- 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, 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.
- Organic bleach activators containing 0- or N- (C 1 -C 12) -acyl groups serve as bleach activators, e.g.
- 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, Opticlean ( R ) -M-375, Opticlean ( R ) -M-250 from Solvay Enzy es; 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 the company Ibis and amylases such as Termamyl ( R ) 60 T, 90 T from Novo; Amylase-LT ( R ) from Solvay Enzymes or Maxamyl ( R ) P 5000,
- 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 include preferably Ci2 ⁇ _ CL8 alkyl polyethylene glycol polypropylene glycol ethers containing up-to 8 mol Ethylene oxide and propylene oxide units in the molecule.
- 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 manufacture 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 are mixed while increasing the bulk density of this premix and subsequently - if desired after an intermediate drying - the further components of the dishwasher, including the inorganic redox-active substances, are 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 taken into account when formulating the granule formulation.
- 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 comes into consideration, in which the builder component in admixture with perborate with the liquid nonionic surfactants and / or the solution of the fragrances is applied and intimately mixed.
- 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.
- 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.
- Alkyl oligoglucoside (APG 225 from Henkel) 0.75 1 1 0.75 1 1 0.75 1 1 0.75
- the silver spoons were consistently rated 0 to 1, i.e. "no to very weak tarnishing", rated.
- the compositions showed 1 to 20 against bleachable stains such.
- 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%) with an area of 1 cm.
- a Hg / HgO / 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 / 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 and / or the silver corrosion inhibitor were added directly before the measurement.
- 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.
- Anti-corrosion agent Manganese sulfate monohydrate
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Detergent Compositions (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Paints Or Removers (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE59405259T DE59405259D1 (en) | 1993-05-08 | 1994-05-02 | SILVER CORROSION PROTECTANT I |
EP94916181A EP0697035B1 (en) | 1993-05-08 | 1994-05-02 | Silver-corrosion protection agent (i) |
JP6524887A JPH08509777A (en) | 1993-05-08 | 1994-05-02 | Silver corrosion protector (▲ I ▼) |
PL94311594A PL177936B1 (en) | 1993-05-08 | 1994-05-02 | Agent for protecting silver i against corrosion |
DK94916181T DK0697035T3 (en) | 1993-05-08 | 1994-05-02 | Silver preservative with corrosion I |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEP4315397.6 | 1993-05-08 | ||
DE19934315397 DE4315397A1 (en) | 1993-05-08 | 1993-05-08 | Cleaning composition preventing tarnishing of table silver in dishwashing machines |
DE19934325922 DE4325922A1 (en) | 1993-08-02 | 1993-08-02 | Silver corrosion protection agent I |
DEP4325922.7 | 1993-08-02 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1994026859A1 true WO1994026859A1 (en) | 1994-11-24 |
Family
ID=25925737
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1994/001386 WO1994026859A1 (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) |
Cited By (167)
Publication number | Priority date | Publication date | Assignee | Title |
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Also Published As
Publication number | Publication date |
---|---|
EP0697035A1 (en) | 1996-02-21 |
CZ234895A3 (en) | 1996-01-17 |
ATE163191T1 (en) | 1998-02-15 |
JPH08509777A (en) | 1996-10-15 |
PL311594A1 (en) | 1996-02-19 |
CZ286401B6 (en) | 2000-04-12 |
DK0697035T3 (en) | 1998-09-28 |
ES2112542T3 (en) | 1998-04-01 |
EP0697035B1 (en) | 1998-02-11 |
DE59405259D1 (en) | 1998-03-19 |
CA2162460A1 (en) | 1994-11-24 |
PL177936B1 (en) | 2000-01-31 |
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