EP0876465A1 - Agent detergent pour lave-vaisselle - Google Patents

Agent detergent pour lave-vaisselle

Info

Publication number
EP0876465A1
EP0876465A1 EP96934751A EP96934751A EP0876465A1 EP 0876465 A1 EP0876465 A1 EP 0876465A1 EP 96934751 A EP96934751 A EP 96934751A EP 96934751 A EP96934751 A EP 96934751A EP 0876465 A1 EP0876465 A1 EP 0876465A1
Authority
EP
European Patent Office
Prior art keywords
weight
water
soluble
inorganic
salts
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
EP96934751A
Other languages
German (de)
English (en)
Other versions
EP0876465B1 (fr
Inventor
Rainer Sorg
Willi Buchmeier
Peter Jeschke
Jürgen Härer
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
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0876465A1 publication Critical patent/EP0876465A1/fr
Application granted granted Critical
Publication of EP0876465B1 publication Critical patent/EP0876465B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • C11D3/02—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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0073—Anticorrosion compositions

Definitions

  • the invention is in the field of machine dishwashing detergents and relates to the use of an active ingredient combination for preventing tarnishing of silver or silver-plated washware.
  • Silver can react here to sulfur-containing substances that are dissolved or dispersed in the rinsing water, because when cleaning dishes in household dishwashers (HGSM) food residues and thus u. a. mustard, peas, egg and other sulfur-containing compounds such as mercaptoamino acid are also introduced into the washing liquor.
  • HGSM household dishwashers
  • the much higher temperatures during machine washing and the longer contact times with the sulfur-containing food residues also favor the tarnishing of silver compared to manual washing. Due to the intensive cleaning process in the dishwasher, the silver surface is also completely degreased and therefore more sensitive to chemical influences.
  • active chlorine-containing cleaners When using active chlorine-containing cleaners, tarnishing can be largely prevented by sulfur-containing compounds, since these compounds are converted into sulfones or sulfates by oxidation of the sulfidic functions in a secondary reaction. Furthermore, active chlorine-containing cleaners, due to their generally high pH of more than 12, cause less tarnishing of silver due to electrochemical reasons because of a passivation of the silver surface.
  • 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.
  • the low pH value results in a significantly lower passivation of the silver surface.
  • these agents release 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 the actual bleaching agent per (acetic) acid is formed even at low temperatures, thus achieving a good bleaching effect.
  • bleach activators so that the actual bleaching agent per (acetic) acid is formed even at low temperatures, thus achieving a good bleaching effect.
  • sulfidic deposits but preferably oxidic deposits on the silver surfaces due to the oxidizing attack of the intermediately formed peroxides or the active oxygen, are formed in the presence of silver.
  • Chloride deposits can also form under high salt loads.
  • 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.
  • Additives such as benzotriazole and iron (III) chloride are recommended as tarnish preventers. PH values of preferably 7-11.5 are mentioned.
  • European patent specifications 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.
  • 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 therefore relates to the use of a combination of water-soluble, inorganic redox-active metal compounds and inorganic, water-soluble fluorine compounds in machine dishwashing detergents to prevent silver corrosion and discoloration of the decor.
  • corrosion is to be interpreted in its broadest meaning in chemistry.
  • corrosion should stand for every visually just noticeable change in a metal surface, here silver, be it for example a selective discoloration, be it e.g. B. a large start-up.
  • corrosion relates only to the corrosion of metals, not to the corrosion of surfaces which have arisen from molten silicates. Such areas are generally not attacked by lower alkaline agents.
  • 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.
  • metal salts and / or metal complexes are particularly suitable.
  • the use of metal salts and / or metal complexes is preferably selected from the group of transition elements of the periodic table, in particular manganese, titanium, zirconium, hafnium, vanadium, cobalt and cerium salts and / or complexes to prevent silver corrosion, the metals being in one of the oxidation states II, III, IV, V or VI.
  • the common definition for "oxidation level” in chemistry is given, for example, in "Römpp Chemie Lexikon, Georg Thieme Verlag Stuttgart / New York, 9th edition, 1991, page 3168".
  • 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.
  • metal complexes are compounds which consist of a central atom and one or more ligands.
  • the central atom is one of the above Metals in one of the above Oxidation levels.
  • the ligands are neutral molecules or anions that are monodentate or multidentate; the term "ligand” in the sense of the invention is e.g. in "Römpp Chemie Lexikon, Georg Thieme Verlag Stuttgart / New York, 9th edition, 1990, page 2507" explained in more detail. If the charge of the central atom and the charge of the ligand (s) do not add up to zero in a metal complex, then depending on whether there is a cationic or an anionic excess charge, either one or more of the abovementioned.
  • Anions or one or more cations e.g. B. sodium, potassium, ammonium ions for the charge compensation.
  • Suitable complexing agents are e.g. Citrate, acetylacetonate or 1-hydroxyethane-1,1-diphosphonate.
  • metal salts and / or metal complexes are selected from the group MnSO 4, Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [l-hydroxyethane-l, l diphosphonate], salts of acids of vanadium, based on V2O5, V2O4, VO2 (here: called vanadates), Ti0S04, C0SO4, Co (N03) 2, Ce (N03) 3 and mixtures thereof.
  • MnS04 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 S03 production (contact process) is suitable, as well as the titanyl sulfate, T1OSO4, formed by diluting a Ti (S ⁇ 4) 2 * solution.
  • the inorganic redox-active substances are preferably coated, i.e. 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.
  • 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 to the material to be coated in a molten state, e.g.
  • 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 ideally be in the range between 45 ° C. and 65 ° C. and preferably in the range 50 ° C. to 60 ° C. for most applications.
  • Inorganic, water-soluble, ionic fluorine compounds from the class of salts or complex salts which release fluoride ions under the conditions of automatic dishwashing can be used as fluorine compounds.
  • Salts of hydrofluoric acid or hexafluorosilicic acid or mono-, di- or pentafluorophosphoric acid are particularly suitable.
  • the fluorides of the alkali salts such as sodium or potassium, ammonium fluoride, magnesium fluoride and complex fluorides such as magnesium hexafluorosilicate, sodium hexafluorosilicate, potassium hexafluorosilicate, sodium hexafluorosilicate, ammonium hexafluorosilicate.
  • Fluorophosphates of alkali metals or ammonium are also suitable.
  • Preferred among these compounds are the hexafluorosilicate, in particular sodium or magnesium hexafluorosilicate. It is also possible Use of aluminum hexafluoride or tin tetrafluoride. However, these are
  • Quantities of 0.1 to 6% by weight are used, preferably 0.1 to 5 and in particular 0.2 to 2.5% by weight, based on the total mixture.
  • 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- (Cj-Ci2) acyl group-containing bleach activator, 0.1 to 5 wt .-%, preferably 0.5 to 2.5 wt .-% of an enzyme, in each case based on the total agent, and Silver corrosion protection agent, an inorganic redox-active substance being contained as the silver corrosion protection agent.
  • metal salts and / or metal complexes selected from the group consisting of manganese, titanium, zirconium, hafnium, vanadium, cobalt, cerium salts and / or complexes, the metals being in one of the oxidation states II, III , IV, V or VI are present.
  • 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 -C-Ci2 acyl group, preferably the acetyl group, to which a 0 or N atom contained in the substance is bound, and the perhydrolysis of which gives C 1 -C 2 -alkanoic acids, preferably peracetic acid.
  • polymeric alkali metal phosphates which may be in the form of their alkaline neutral or acidic sodium or potassium salts. Examples 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. German patent application P 4228786.3) and polyamino acids such as polyglutamic acid or polyaspartic acid and NTA and their derivatives.
  • 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.
  • citric acid may also be present.
  • Sodium perborate mono- and tetrahydrate or sodium percarbonate are primarily considered as oxygen-based bleaches. The oxygen-based bleach is therefore preferably a percarbonate salt, especially sodium percarbonate.
  • bleach activators are used to activate it in the dishwasher.
  • Organic, 0- or N- (-C-Ci2) acyl group-containing bleach activators, such as PAG (pentaacetylglucose), DADHT (1,5-diacetyl-2,4-dioxo-hexa- hydro-l, 3,5-triazine) are used as bleach activators ) and ISA (isatoic anhydride), but preferably N, N, N ', N'-tetraacetylethylene diamine (TAED).
  • TAED tetraacetylethylene diamine
  • the addition of small amounts of known bleach stabilizers such as, for example, phosphonates, borates or metaborates and metasilicates and magnesium salts such as magnesium sulfate 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; Optimase ( R ) -M-440, Optimase ( R ) -M-330, Opticlean ( R ) -M-375, Opticlean ( R ) -M-250 from Solvay Enzymes; Maxacal ( R )
  • the dishwashing agents preferably contain proteases and / or amylases.
  • the agents according to the invention additionally contain the alkali carriers contained in customary low-alkaline machine dishwashing detergents, such as. B. alkali silicates, alkali carbonates and / or alkali hydrogen carbonates.
  • Alkali silicates can be used in amounts of up to 30% by weight. -%, based on the total Means to be included. The use of the highly alkaline metasilicates as alkali carriers is preferably avoided.
  • the alkali carrier system preferably used in the agents according to the invention is a mixture of essentially carbonate and bicarbonate, preferably sodium carbonate and bicarbonate, in an amount of up to 60% by weight, preferably 10 to 40% by weight. , based on the total agent, is included.
  • the ratio of the carbonate used and the hydrogen carbonate used varies depending on which pH value is ultimately desired or set; 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 C12-C18 alkyl polyethylene glycol polypropylene glycol ethers, each containing up to 8 moles of ethylene oxide and propylene oxide units in the molecule.
  • nonionic surfactants known as low-foam, such as.
  • APG ( R ) 225 and APG ( R ) 600 from Henkel e.g. APG ( R ) 225 and APG ( R ) 600 from Henkel
  • a bleached quality should be used, since otherwise brown granules are formed.
  • 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.
  • 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 • 10 * - * Pa up 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 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 constituents of the dishwasher detergent, 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 Decay 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 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 inorganic 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 3 to 6 g / 1.
  • the washing program of a household dishwasher is generally supplemented and ended by a few intermediate rinsing cycles with clear water and a rinsing cycle with a common rinse aid following the cleaning cycle. After drying you get not only a completely clean and hygienically perfect tableware, but above all also bright silver cutlery items.
  • a low-alkaline cleaner for household dishwashers was produced, the weight percent solution of which in distilled water has a pH of 9.5. They were used for this
  • the base product obtained in this way was disassembled into a dishwashing detergent in the following manner: 81% by weight base product 12% by weight sodium percarbonate
  • Decorative glasses were used as washware, which were printed on the one hand with high-bleach, low-melting colors or on the other hand with lead-free colors based on bismuth. The print showed red, blue, yellow, green and white color patches.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention vise à empêcher des décolorations des motifs de décoration et des articles en matière plastique lorsqu'on utilise des composés métalliques rédox inorganiques solubles dans l'eau, comme agents pour protéger l'argent contre la corrosion dans des produits détergents pour lave-vaisselle. Ce but est atteint grâce à l'utilisation des composés fluorés ioniques inorganiques solubles dans l'eau.
EP96934751A 1995-10-27 1996-10-18 Agent detergent pour lave-vaisselle Expired - Lifetime EP0876465B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19540087 1995-10-27
DE19540087A DE19540087A1 (de) 1995-10-27 1995-10-27 Geschirrspülmittel
PCT/EP1996/004542 WO1997016520A1 (fr) 1995-10-27 1996-10-18 Agent detergent pour lave-vaisselle

Publications (2)

Publication Number Publication Date
EP0876465A1 true EP0876465A1 (fr) 1998-11-11
EP0876465B1 EP0876465B1 (fr) 2000-04-12

Family

ID=7775977

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96934751A Expired - Lifetime EP0876465B1 (fr) 1995-10-27 1996-10-18 Agent detergent pour lave-vaisselle

Country Status (4)

Country Link
EP (1) EP0876465B1 (fr)
DE (2) DE19540087A1 (fr)
ES (1) ES2146417T3 (fr)
WO (1) WO1997016520A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9138393B2 (en) 2013-02-08 2015-09-22 The Procter & Gamble Company Cosmetic compositions containing substituted azole and methods for improving the appearance of aging skin
US9144538B2 (en) 2013-02-08 2015-09-29 The Procter & Gamble Company Cosmetic compositions containing substituted azole and methods for alleviating the signs of photoaged skin

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10114980A1 (de) * 2001-03-27 2002-10-17 Henkel Kgaa Haftvermittler für Lacke und Klebstoffe auf Metallen
JP2008531829A (ja) 2005-03-04 2008-08-14 ザ プロクター アンド ギャンブル カンパニー 腐食防止剤を有する自動食器洗浄用組成物

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3714451A1 (de) * 1987-04-30 1988-11-10 Hoechst Ag Mittel zur verhinderung von korrosion an keramischen oberflaechen
WO1994019445A1 (fr) * 1993-02-22 1994-09-01 Unilever N.V. Composition de lavage pour lave-vaisselle
CZ286401B6 (en) * 1993-05-08 2000-04-12 Henkel Kgaa Use of inorganic redox-active substances
DE4344215A1 (de) * 1993-12-23 1995-06-29 Cognis Bio Umwelt Silberkorrosionsschutzmittelhaltige Enzymzubereitung

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9716520A1 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9138393B2 (en) 2013-02-08 2015-09-22 The Procter & Gamble Company Cosmetic compositions containing substituted azole and methods for improving the appearance of aging skin
US9144538B2 (en) 2013-02-08 2015-09-29 The Procter & Gamble Company Cosmetic compositions containing substituted azole and methods for alleviating the signs of photoaged skin

Also Published As

Publication number Publication date
WO1997016520A1 (fr) 1997-05-09
EP0876465B1 (fr) 2000-04-12
DE19540087A1 (de) 1997-04-30
DE59604975D1 (de) 2000-05-18
ES2146417T3 (es) 2000-08-01

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