EP0723577B1 - Compositions detergentes contenant des agents empechant le ternissement de l'argent - Google Patents

Compositions detergentes contenant des agents empechant le ternissement de l'argent Download PDF

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Publication number
EP0723577B1
EP0723577B1 EP94928878A EP94928878A EP0723577B1 EP 0723577 B1 EP0723577 B1 EP 0723577B1 EP 94928878 A EP94928878 A EP 94928878A EP 94928878 A EP94928878 A EP 94928878A EP 0723577 B1 EP0723577 B1 EP 0723577B1
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EP
European Patent Office
Prior art keywords
tarnishing
silver
nitrogen
composition according
compositions
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EP94928878A
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German (de)
English (en)
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EP0723577A1 (fr
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Petrus Adrianus J. M. Angevaare
Richard Gerald Gary
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Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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Priority claimed from US08/136,787 external-priority patent/US5374369A/en
Priority claimed from US08/301,459 external-priority patent/US5480576A/en
Priority claimed from US08/302,284 external-priority patent/US5468410A/en
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP0723577A1 publication Critical patent/EP0723577A1/fr
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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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • 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
    • C11D3/16—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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3947—Liquid 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
    • C11D3/395—Bleaching agents
    • C11D3/3951—Bleaching agents combined with specific additives
    • 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
    • C11D3/395—Bleaching agents
    • C11D3/3956—Liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom

Definitions

  • This invention relates to bleaching detergent compositions which include silver anti-tarnishing agents. More particularly, the invention relates to detergent compositions based on peroxygen and/or hypohalite bleaching agents and which include one or more particular organic heterocyclic species as a silver anti-tarnishing agent.
  • Silver is chemically the most reactive element among the noble metals and tarnishes readily on exposure to sulphur bearing atmospheres. Because of its electronic state, silver exhibits a drastically different chemical behaviour from, for instance, copper, although both metals are in the same group of the Periodic Table. Thus, silver tarnishing is very different from corrosion of other metals.
  • Tarnishing sometimes referred to as discolouring, is caused by a silver oxidation process in which sulphide is formed.
  • Food such as onions, mustard and eggs which contain organic sulphur compounds are also known to tarnish silver. See Singh et al., “Silver Tarnishing and its Prevention - A Review” Anti-corrosion Methods and Materials, Vol. 30 (July 1983), pp. 4-8.
  • Silver tarnishing is also known to occur when an oxygen bleaching agent used in detergent compositions oxidizes the silver to silver oxide. This oxidation process causes surface-blackening of the silver, leaving undesirable tarnishing of silverware when machine-dishwashed, for example.
  • U.S. Patents Nos. 2,618,606 (Procter & Gamble) and 2,618,608 (Procter & Gamble) disclose the use of derivatives of triazole, including 1,2,3-triazole, imidazole and pyrazole, as discolouration inhibitors used in detergent compositions for non-ferrous metals, such as copper and brass.
  • the detergents described do not, however, contain a bleaching agent which complicates silver tarnish inhibition.
  • the patents further state that a mixture of copper inhibitors are required to prevent tarnishing over a broad pH range.
  • Conventional detergents are generally formulated with chlorine bleaching agents in a high alkaline pH range.
  • chlorine bleaches e.g. chloroisocyanurate
  • Detergent compositions are, however, increasingly being based on peroxygen bleaching agents and are being formulated to be milder to produce more environmentally-friendly products. The problem of tarnishing of silver and silver-plated articles has thus become more severe.
  • Another object of the invention is to provide a method for washing silver or silver-plated articles without discolouring them.
  • a further object of the invention is to protect a silver or silver-plated article against tarnishing from organic foodstuffs with which it comes into contact.
  • Silver anti-tarnishing bleaching detergent compositions formulated for use in automatic dishwashing machines or fabric washing machines which are stable in a variety of physical forms, including liquid, powder and flakes is another object of the invention.
  • the present invention provides a bleaching detergent composition comprising:
  • the invention provides a method of washing a silver or silver-plated article whilst preventing or inhibiting tarnishing thereof during or as a result of the washing process, the method comprising washing the said article with a bleaching detergent composition according to the first aspect of the invention defined above.
  • the invention provides the use of a compound selected from any of (i) to (iv) defined above in accordance with the first aspect of the invention, as a silver anti-tarnishing agent in a peroxygen- and/or hypohalite based bleaching detergent composition having a pH value in a 1% aqueous solution in the range from 7 to 13, and wherein the anti-tarnishing agent has a pK a value at least 1 unit below the pH value of a 1% aqueous solution of the composition.
  • the silver anti-tarnishing agent of compositions of the invention is a compound or a mixture of two or more compounds selected from any of the following:
  • the pK a value of the anti-tarnishing compound(s) is at least 2 and up to 6 units below the pH value of the aqueous solution of the composition.
  • pK a means a pH value at which 50% of the heterocyclic ring moieties of the compound (particularly the five-membered rings in the case of the purine class compounds) are in ionic form.
  • purine class compound includes not only compounds of formula (I) above, but also tautomeric forms of these compounds.
  • Preferred compounds of formula (I) include those wherein X 1 is nitrogen and Y 1 is C-R 4 and R 1 , R 2 and R 4 are each independently hydrogen, hydroxy, alkoxy, alkylthio, amine, amido or lower alkyl having from 1 to 6 carbon atoms, wherein R 1 may additionally be SH when R 2 is hydrogen, X 1 is nitrogen and Y 1 is CH.
  • Especially preferred compounds of formula (I) include purine, adenine, guanine, 6-mercaptopurine, xanthine, hypoxanthine, uric acid, and allopurinol.
  • cyanuric acid means 1,3,5-triazine-2,4,6(1H,3H,5H)-trione, normal cyanuric acid, sym triazinetriol, 2,4,6-trihydroxy-1,3,5-triazine, tricyanic acid or trihydroxycyanidine.
  • isocyanuric acid as used herein, and within the scope of both terms are salts thereof.
  • the cyanuric acid or isocyanuric acid, or a salt thereof, as an anti-tarnishing agent in the present invention is an unsubstituted such species.
  • Cyanuric acid is available commercially, for example also from Aldrich Chemical Co. of Milwaukee, Wisconsin, USA.
  • Preferred 1,3-N azole compounds of formula (II) above include those wherein X 2 is C-R 7 , X 2 is nitrogen provided Y 2 is nitrogen, Y 2 is C-R 6 and R 5 and R 6 taken together form an aryl or a substituted aryl group.
  • Other preferred compounds of formula (II) include those wherein Y 2 is C-R 6 and R 5 and R 6 are each independently hydrogen, amine, amido, straight or branched chain alkyl having from 1 to 6 carbon atoms, alkoxy, alkylthio, hydroxy, alkenyl or an amino- or carboxylic-containing moiety.
  • Especially useful compounds of formula (II) include imidazole, benzimidazole, tetrazole, 4-aminotetrazole, 1,2,4-triazole, 3-amino-1,2,4-triazole and histidine.
  • 1,3-N azole compounds of formula (II) above useful in the invention are commercially available, for example also from Aldrich Chemical Co. of Milwaukee, Wisconsin, USA.
  • a group defined as being "alkyl” preferably means a group having from 1 to 20 carbon atoms, more preferably from 1 to 6 carbon atoms, most preferably from 1 to 4 carbon atoms.
  • those defined groups which are substituted alkyl groups preferably have an alkyl chain length of from 1 to 5 carbon atoms, more preferably from 1 to 3 carbon atoms.
  • aryl includes aryl groups containing one or more heteroatoms such as S, N or O, preferably N.
  • substituted aryl includes an aryl group substituted with one or more of the following groups: straight or branched chain alkyl having from 1 to 20 carbon atoms, hydroxy, alkoxy or alkenyl.
  • compositions containing certain 1-N azoles e.g. pyrrole
  • 1,2-N azoles e.g. indazole, pyrazole
  • pyrimidine e.g. indazole, pyrazole
  • the compounds used in the present invention form a complex with the silver molecules at the surface of the article to form a protective film which prevents or diminishes its tendency to tarnish in an oxidative environment.
  • the one or more compounds forming the anti-tarnishing agent are present in a (total) amount of from 0.05 to 10% by weight, preferably from 0.25 to 2.5% by weight, most preferably from 0.75 to 2% by weight.
  • the pH of a 1% aqueous solution of the compositions in accordance with the invention should be from 7 to 13, more preferably from 7 to 11, most preferably from 7 or 8 to 10.
  • Peroxygen or peroxygen-yielding bleaching agents for use in the compositions of the invention include organic peroxy acids and diacylperoxides.
  • Typical monoperoxy acids useful herein include alkyl peroxy acids and aryl peroxy acids such as:
  • Typical diperoxy acids useful herein include alkyl diperoxy acids and aryldiperoxy acids, such as:
  • a typical diacylperoxide useful herein includes dibenzoylperoxide.
  • Inorganic peroxygen compounds are also suitable for use in the present invention.
  • useful materials include salts of monopersulphate, perborate monohydrate, perborate tetrahydrate, and percarbonate.
  • Preferred organic oxygen bleaching agents include epsilon-phthalimidoperoxyhexanoic acid, o-carboxybenzamidoperoxy hexanoic acid, and mixtures thereof.
  • an oxygen bleaching agent is used as the bleaching agent in compositions of the invention, it is present therein in an amount from 1 to 20% by weight, preferably from 1 to 15% by weight, most preferably from 2 to 10% by weight.
  • the oxygen bleaching agent may be incorporated directly into the formulation or may be encapsulated by any suitable encapsulation technique known in the art to produce stable capsules in alkaline liquid formulations.
  • a preferred encapsulation method is described in U.S. Patent No. 5,200,236 (Lang et al).
  • the bleaching agent is encapsulated as a core in a paraffin wax material having a melting point from 40°C to 50°C.
  • the wax coating has a thickness of from 100 to 1500 microns.
  • Oxygen bleaching agent systems which may be employed in the present invention may if desired or if necessary employ one or more peroxyacid bleach precursors.
  • Suitable peroxygen peracid precursors for peroxy bleach compounds have been amply described in the literature, including United Kingdom Patents Nos. 836,988; 855,735; 907,356; 907,358; 907,950; 1,003,310 and 1,246,339; and U.S. Patents Nos. 3,332,882 and 4,128,494.
  • Typical examples of precursors are polyacylated alkylene diamines, such as N,N,N',N'-tetraacetylethylene diamine (TAED) and N,N,N',N'-tetraacetylmethylene diamine (TAMD); acylated glycolurils, such as tetraacetylglycoluril (TAGU); triacetylcyanurate, sodium sulphophyl ethyl carbonic acid ester, sodium acetyloxybenzene sulphonate (SABS), sodium nonanoyloxybenzene sulphonate (SNOBS) and choline sulphophenyl carbonate.
  • SABS sodium acetyloxybenzene sulphonate
  • SNOBS sodium nonanoyloxybenzene sulphonate
  • choline sulphophenyl carbonate choline sulphophenyl carbonate.
  • Peroxybenzoic acid precursors are known in the art, e.g., as described in GB-A-836,988. Examples of suitable precursors are phenylbenzoate; phenyl p-nitrobenzoate; o-nitrophenyl benzoate; o-carboxyphenyl benzoate; p-bromo-phenylbenzoate; sodium or potassium benzoyloxy benzenesulphonate; and benzoic anhydride.
  • Preferred peroxygen bleach precursors are sodium p-benzoyloxybenzene sulphonate, N,N,N',N'-tetraacetylethylene diamine, sodium nonanoyloxybenzene sulphonate and choline sulphophenyl carbonate.
  • Hypohalite or hypohalite-yielding bleaching agents for use in the compositions of the invention include hypohalite salts per se or compounds which yield hypohalite anions in aqueous alkaline conditions. Such materials are preferably incorporated into compositions of the invention in the form of dry, particulate, water-soluble anhydrous inorganic salts.
  • hypohalite salts for use in the invention include lithium, sodium or calcium hypochlorite and hypobromite, and halogenated (e.g. with chlorine or bromine) trisodium phosphate.
  • halogenated e.g. with chlorine or bromine
  • Sodium hypochlorite is particularly preferred for liquid compositions in accordance with the invention.
  • Hypohalite-yielding compounds suitable for use in the invention include, for example, chloramines, chloramides, chlorimines, chlorosulphonamides, and chlorohydantoins (though preferably not N-chloro imides which are harsher and less environmentally friendly than oxygen bleaching agents and other hypohalite bleaching agents such as those above), and active halogen compounds corresponding to any of these but which contain bromine instead of chlorine, or contain a mixture of chlorine and bromine.
  • halogenated isocyanuric acids such as trichloroisocyanuric acid, dichloroisocyanuric acid, and salts thereof, especially the sodium salts.
  • commercial sources of chlorinated isocyanuric acids include, for example, ACL-59 (trade mark) supplied by Mansanto Company, and Clearon CDB-56 (trade mark) supplied by Olin Corporation.
  • halogen-based bleaching agent such as those described above is used as the bleaching agent in compositions of the invention, it is present therein in a similar amount to that when an oxygen-based bleaching agent is used, namely in an amount of from about 1 to about 20% by weight, preferably from 1 to 15% by weight, most preferably from 2 to 10% by weight.
  • each component is used in an appropriate amount, such that the total amount of bleaching agent present also falls within the essential and preferred narrower ranges defined above with respect to each type of bleaching agent separately.
  • compositions of this invention may contain all manner of detergent builders commonly taught for use in automatic dishwashing or other cleaning compositions.
  • the builder component can include any of the conventional inorganic and organic water-soluble builder salts or mixtures thereof and, when present, is included in the composition preferably in an amount of from 1 to about 75% by weight, preferably from about 5 to 70% by weight.
  • phosphorus-containing inorganic builders include water-soluble (especially alkali metal) pyrophosphates, orthophosphates and polyphosphates.
  • specific examples of inorganic phosphate builders include sodium and potassium tripolyphosphates, phosphates, pyrophosphates and hexametaphosphates.
  • non-phosphorus-containing inorganic builders include water-soluble (especially alkali metal) carbonates, bicarbonates, sesquicarbonates, borates, silicates, metasilicates, and crystalline and amorphous aluminosilicates.
  • water-soluble carbonates especially alkali metal
  • bicarbonates especially alkali metal
  • sesquicarbonates especially bicarbonates
  • borates especially silicates, metasilicates, and crystalline and amorphous aluminosilicates.
  • Specific examples include sodium carbonates (with or without calcite seeds), potassium carbonate, sodium and potassium bicarbonates, silicates and zeolites.
  • Particularly preferred inorganic builders may be selected from the group consisting of sodium tripolyphosphate, potassium pyrophosphate, sodium carbonate, potassium carbonate, sodium bicarbonate, sodium silicate and mixtures thereof.
  • sodium tripolyphosphate builder concentrations may range from 2 to 40% by weight, preferably from 5 to 30% by weight of the composition.
  • Sodium carbonate and bicarbonate, when present, may range from 5 to 50% by weight, preferably from 10 to 30% by weight of the composition.
  • Sodium tripolyphosphate and potassium pyrophosphate are preferred builders in gel formulations, where they may be used in an amount of from 3 to 30% by weight, preferably from 10 to 20% by weight.
  • Organic detergent builders may also be used in the compositions of the invention.
  • organic builders include alkali metal citrates, succinates, malonates, fatty acid sulphates, fatty acid carboxylates, nitrilotriacetates, phytates, phosphonates, alkanehydroxyphosphonates, oxydisuccinates, alkyl and alkenyl disuccinates, oxydiacetates, carboxymethyloxy succinates, ethylenediamine tetraacetates, tartrate monosuccinates, tartrate disuccinates, tartrate monoacetates, tartrate diacetates, oxidized starches, oxidized heteropolymeric polysaccharides, polyhydroxysulphonates, polycarboxylates such as polyacrylates, polymaleates, polyacetates, polyhydroxyacrylates, polyacrylate/polymaleate and polyacrylate/polymethacrylate copolymers, aminopolycarboxylates and polyacetal carboxylates such as
  • Alkali metal citrates, oxydisuccinates, polyphosphonates and acrylate/maleate copolymers are especially preferred organic builders. When present, they are preferably included in an amount of from 1 to 35% by weight of the composition.
  • detergent builders are intended to illustrate by way of example only, and not to limit, the types of builders which may be employed in the compositions of the present invention.
  • compositions of this invention may contain one or more surfactant materials.
  • useful surfactants include anionic, nonionic, cationic, amphoteric and zwitterionic types, and mixtures thereof.
  • Such surfactants are well known in the detergent art and are described at length in "Surface Active Agents and Detergents", Vol. II, by Schwartz, Perry & Birch, Interscience Publishers, Inc. 1959.
  • Anionic synthetic detergents can be broadly described as surface-active compounds with one or more negatively charged functional groups. Soaps are included within this category.
  • a soap is a C 8 -C 22 alkyl fatty acid salt of an alkali metal, alkaline earth metal, ammonium, alkylsubstituted ammonium or alkanolammonium salt. Sodium salts of tallow and coconut fatty acids and mixtures thereof are most common.
  • Another important class of anionic compounds are the water-soluble salts, particularly the alkali metal salts, of organic sulphur reaction products having in their molecular structure an alkyl radical containing from 8 to 22 carbon atoms and a radical selected from the group consisting of sulphonic and sulphuric acid ester radicals.
  • Organic sulphur-based anionic surfactants include the salts of C 10 -C 16 alkylbenzene sulphonates, C 10 -C 22 alkane sulphonates, C 10 -C 22 alkyl ether sulphates, C 10 -C 22 alkyl sulphates, C 4 -C 10 dialkylsulphosuccinates, C 10 -C 22 acyl isethionates, alkyl diphenyloxide sulphonates, alkyl napthalene sulphonates, and 2-acetamido hexadecane sulphonates.
  • Organic phosphate-based anionic surfactants include organic phosphate esters such as complex mono- or diester phosphates of hydroxyl- terminated alkoxide condensates, or salts thereof. Included in the organic phosphate esters are phosphate ester derivatives of polyoxyalkylated alkylaryl phosphate esters of ethoxylated linear alcohols and ethoxylates of phenol. Also included are nonionic alkoxylates having a sodium alkylenecarboxylate moiety linked to a terminal hydroxyl group of the nonionic through an ether bond. Counterions to the salts of all the foregoing may be those of alkali metal (especially sodium), alkaline earth metal, ammonium, alkanolammonium and alkylammonium types.
  • Nonionic surfactants can be broadly defined as surface-active compounds with one or more uncharged hydrophilic substituents.
  • a major class of nonionic surfactants are those compounds produced by the condensation of alkylene oxide groups with an organic hydrophobic material which may be aliphatic or alkyl aromatic in nature.
  • the length of the hydrophilic or polyoxyalkylene radical which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
  • Illustrative, but not limiting, examples of various suitable nonionic surfactant types are:
  • Amphoteric synthetic detergents can be broadly described as derivatives of aliphatic and tertiary amines, in which the aliphatic radical may be straight or branched chain and wherein one of the aliphatic substituents contain from 8 to 18 carbons and one contains an anionic water-solubilizing group, i.e., carboxy, sulpho, sulphato, phosphato or phosphono.
  • an anionic water-solubilizing group i.e., carboxy, sulpho, sulphato, phosphato or phosphono.
  • Examples of compounds falling within this definition are sodium 3-dodecylamino propionate and sodium 2-dodecylamino propane sulphonate.
  • Zwitterionic synthetic detergents can be broadly described as derivatives of aliphatic quaternary ammonium, phosphonium and sulphonium compounds in which the aliphatic radical may be straight or branched chain, and wherein one of the aliphatic substituents contains from 8 to 18 carbon atoms and one contains an anionic water-solubilizing group, e.g., carboxy, sulpho, sulphato, phosphato or phosphono. These compounds are frequently referred to as betaines. Besides alkyl betaines, alkyl amino and alkyl amido betaines are encompassed herewithin.
  • the one or more surface active materials forming the surfactant component of compositions of the invention when present, constitute from 0.01 to 40% by weight of the composition.
  • the amount of surfactant, if present, will generally be within this range, but the actual amount used may depend upon the type of surfactant(s) employed.
  • anionic and/or nonionic surfactants making up the total surfactant concentration may typically be present in an amount of from about 1 to 40% by weight of the composition, more preferably from 2 to 35% by weight, even more preferably from 5 to 30% by weight.
  • Alkyl polyglycosides as the surfactant component may typically be present in lower concentrations, such as in an amount from 0.01 to 20% by weight, preferably from 0.5 to 10% by weight, optimally between 1 and 5% by weight of the composition.
  • compositions of this invention may optionally contain sodium or potassium silicate in an amount of from 1 to 40%, preferably from 1 to 20% by weight of the composition.
  • this material is employed as a cleaning ingredient, source of alkalinity, metal corrosion inhibitor and protector of glaze on china tableware.
  • sodium silicate having a ratio of SiO 2 :Na 2 O of from 1.0 to 3.3, preferably from 2 to 3.2. Some of the silicate may be in solid form.
  • An inert particulate filler material which is water-soluble may optionally also be present in the compositions of the invention which are in powder form. This material should not precipitate calcium or magnesium ions at the filler use level. Suitable for this purpose are organic or inorganic compounds.
  • Organic fillers include sucrose esters and urea.
  • Representative inorganic fillers include sodium sulphate, sodium chloride and potassium chloride.
  • a preferred filler is sodium sulphate. Its concentration may range from 0 to 60%, preferably from 10 to 30% by weight of the composition.
  • Thickeners are often desirable for inclusion in liquid cleaning compositions of the invention.
  • Thixotropic thickeners such as smectite clays including montmorillonite (bentonite), hectorite and saponite may be used to impart increased viscosity to such liquid bleaching detergent compositions.
  • Silica, silica gel, and aluminosilicate may also be used as thickeners.
  • Salts of polyacrylic acid (of molecular weight of from about 300,000 up to 6 million and higher), including polymers which are cross-linked, may also be used either alone or in combination with other thickeners.
  • Use of clay thickeners for automatic dishwashing compositions is disclosed, for example, in U.S. Patents Nos.
  • Synthetic smectite clays include Laponite (trade mark) supplied by Laporte Industries.
  • Commercially available bentonite clays include Korthix H and VWH ex Combustion Engineering, Inc.; Polargel T ex American Colloid Co.; and Gelwhite clays (particularly Gelwhite GP and H) ex English China Clay Co.
  • Polargel T is preferred as imparting a more intense white appearance to the composition than other clays.
  • the amount of clay thickener employed in the compositions, when it is present, is preferably from 0.1 to 10% by weight, preferably from 0.5 to 5% by weight.
  • Use of salts of polymeric carboxylic acids is disclosed, for example, in GB-A-2,164,350, and in U.S. Patents Nos. 4,859,358 and 4,836,948.
  • a chlorine-stable polymeric thickener is particularly useful for liquid formulations with a gel appearance and rheology, particularly if a clear gel is desired.
  • U.S. Patent No. 4,260,528 discloses natural gums and resins for use in clear autodishwashing detergent compositions, which are not chlorine-stable.
  • Cross-linked acrylic acid polymers manufactured by, for example, B.F.Goodrich and sold under the tradename "Carbopol” have been found to be effective for producing clear gels, and Carbopol 940 and 617, having a molecular weight of 4,000,000, are particularly preferred for maintaining high viscosity with excellent chlorine stability over extended periods.
  • Further suitable chlorine-stable polymeric thickeners are described in U.S. Patent No. 4,867,896.
  • the amount of thickener employed in the compositions of the invention is preferably from 0 to 5% by weight, preferably from 0.5 to 3% by weight.
  • Stabilizers and/or co-structurants such as long-chain calcium and sodium soaps and C 12 to C 18 sulphates which may optionally be incorporated in compositions of the invention are detailed in U.S. Patents Nos. 3,956,158 and 4,271,030 and the use of other metal salts of long-chain soaps is detailed in U.S. Patent No. 4,752,409.
  • Other co-structurants include Laponite (trade mark) and metal oxides and their salts, as described in U.S. 4,933,101.
  • the amount of stabilizer which may be used in liquid compositions of the invention is preferably from 0.01 to 5% by weight of the composition, preferably from 0.01 to 2% by weight. Such stabilizers are optional in gel formulations.
  • Co-structurants which are found especially suitable for gels include compounds containing trivalent metal ions which may be present in an amount of from 0.01 to 4% by weight of the composition, and Laponite and/or water-soluble structuring chelants, which may be present in an amount of from 1 to 60% by weight. These co-structurants are more fully described in EP-A-0323209.
  • Formulations of the cleaning composition of the invention comprising surfactant may further include a defoamer.
  • Suitable defoamers include mono- and distearyl acid phosphate, silicone oil and mineral oil. Even if the composition includes only defoaming surfactant, the defoamer may still assist in the minimizing of foam which food soils can generate. If a defoamer is present, the compositions may include from 0.02 to 2% by weight thereof, more preferably from 0.05 to 1.0% by weight thereof.
  • bleach scavengers including (but not limited to) sodium bisulphite, sodium perborate, reducing sugars, and short-chain alcohols; solvents and hydrotropes such as ethanol, isopropanol and xylene sulphonates; flow control agents (in granular forms of the composition); enzyme-stabilizing agents; soil-suspending agents; antiredeposition agents; anti-tarnish agents; anti-corrosion agents; colourants; other functional additives; perfumes.
  • bleach scavengers including (but not limited to) sodium bisulphite, sodium perborate, reducing sugars, and short-chain alcohols
  • solvents and hydrotropes such as ethanol, isopropanol and xylene sulphonates
  • flow control agents in granular forms of the composition
  • enzyme-stabilizing agents soil-suspending agents; antiredeposition agents; anti-tarnish agents; anti-corrosion agents; colourants; other functional additives; perfumes.
  • the pH of cleaning compositions of the invention may be adjusted as desired or as necessary by addition of strong acid or base.
  • alkalinity or buffering agents include, for example, sodium carbonate and sodium borate.
  • Enzymes capable of facilitating the removal of soils from a substrate may also optionally be present in compositions of the invention, preferably in an amount of from 0 to 10% by weight, preferably from 1 to 5% by weight.
  • Such enzymes include proteases (e.g., Alcalase (trade mark), Savinase (trade mark) and Esperase (trade mark) from Novo Industries A/S), amylases (e.g., Termamyl (trade mark) from Novo Industries A/S), lipases (e.g., Lipolase (trade mark) from Novo Industries A/S), oxidases, and mixtures thereof.
  • compositions a, b, c, d, e, f, and g were conducted with compositions a, b, c, d, e, f, and g at a product dosage of 40 grams per run in a European dishwasher, Bauknecht GSF 3162, with an intake of of 5 litres deionized water.
  • the wash program consisted of a pre-wash at 40°C, a mainwash at 55°C, two intermediate rinses, and a final rinse at 65°C.
  • the mainwash pH with these compositions was typically 8.7.
  • Silver-plated spoons (2 per run) were the monitors used in the test. The spoons were supplied by Oneida Silversmiths, USA. The monitors were washed in a commercially available hand dishwash liquid and rinsed with deionized water and acetone before use. In the dishwasher the monitors were kept apart from each other in the cutlery basket. At the end of a single-run machine program, the monitors were visually analyzed for the presence of colours and the loss of gloss.
  • composition a were unchanged after the dishwashing process, except for a few stain spots.
  • the stain spots were caused by deposition of non-volatile materials during the evaporation of undrained wash solution in the drying step of the machine program and were not related to a tarnishing (i.e. silver oxidation) process of the monitors.
  • compositions b, c, d, e, f, and g were increasingly tarnished as the levels of bleaching agent were increased.
  • the spoons washed with composition g were so heavily tarnished that they lost their gloss and were turned brown/black.
  • the set of spoons washed with the compositions a, b, c, d, e, f, and g were ranked from zero to six, respectively. This ranking of spoons was used as a reference scale for all subsequent Examples.
  • Machine dishwashing compositions were prepared as described in Example 1, except that the selected bleaching agent was epsilon-phthalimido peroxyhexanoic acid incorporated at 4% by weight.
  • the compound was supplied by Hoechst AG of Germany.
  • the compositions also contained various anti-tarnish agents incorporated in an amount of 1% by weight, as follows: SAMPLE ANTI-TARNISHING AGENT (1 wt.%) A None B Purine C Adenine D Guanine E 6-mercaptopurine F xanthine G uric acid H allopurinol
  • the anti-tarnishing agents were supplied by Aldrich Chemical Co.
  • Anti-tarnish scores ranging from 0 to 6 according to the level of tarnishing were obtained for samples A to H as follows: Composition Tarnish Score A 5 B 0 C 0.5 D 0 E 1 F 0 G 1 H 0
  • a detergent base was prepared having the following formula: Ingredient % by weight Sodium citrate (2H 2 O) 42 Sodium disilicate 2.0 35 Sodium perborate (H 2 O) 7 Sokalan CP5 5 TAED (80%) 4.2 Amylase 1.7 Protease 1.7 Laponite 1.7 Nonionic surfactant 1.7
  • tarnish monitoring tests were conducted with samples 1 to 5 using two silver-plated spoons as monitors. However, 1 gram/liter of sodium chloride was added to the deionized water used in the experiments. Additionally, 5 grams of egg yolk were dosed in the dishwasher immediately after water intake at the start of the main wash of each experiment. The main wash pH values were typically 9.8.
  • Silver-tarnishing scores on a scale of 0 to 6 were observed for samples 1 to 5 as follows: Sample Tarnish Score 1 3 2 1.5 3 1.5 4 0 5 1
  • control sample containing no anti-tarnishing agent gave rise to moderately heavy tarnishing. In contrast, samples 2 to 5 exhibited little to no tarnishing. Optimal anti-tarnishing performance was observed with sample 4 containing 0.25 wt.% adenine.
  • Sample Bleaching Agent (% by wt) (% by wt) A Peracetic acid (4.12%) 0% B Peracetic acid (4.12%) 1.0% C Epsilon-phthalimidoperoxy hexanoic acid (4.0%) 0% D Epsilon-phthalimidoperoxy hexanoic acid (4.0%) 1.0% E Sodium hypochlorite (8.23%) 0% F Sodium hypochlorite (8.23%) 1.0%
  • Tarnishing-monitoring experiments were conducted, using samples A, B, C, D, E, and F at a product dosage of 40 grams per run in a Bauknecht GSF 3162 dishwasher, with an intake of 5 litres water.
  • the mainwash pH values for compositions A and B were adjusted to 7.5; the mainwash pH values for compositions C and D were adjusted to 8.5.
  • Two experiments (each) were conducted, using compositions E and F; the mainwash pH values were adjusted to 9.0 and 10.5, respectively.
  • Silver-plated spoons, knives, and forks supplied by Oneida Silversmiths, USA), were used as monitors for all experiments.
  • the monitors were washed in a commercially available hand dishwashing liquid and rinsed with deionized water and acetone before use. At the end of the dishwashing machine program, the monitors were visually evaluated for the presence of colours and/or loss of shine, according to the reference scale described in Example 1.
  • the pK a of each compound was determined by preparing a 0.001M solution of inhibitor in deionized water. The pH of this solution was adjusted to 3.0 with H 2 SO 4 . The solution was then titrated with 1N NaOH to pH 11.0. A plot of mls. NaOH vs. pH for each sample was prepared. The pK a of the compound is that point where the maximum change in pH as a function of mls. NaOH is observed.
  • a comparison of anti-tarnishing performance of purine class compounds within the scope of the invention and azole compounds outside the invention was conducted.
  • the selected compounds were incorporated in an amount of 1 wt.% in a machine dishwashing composition containing 4 wt.% epsilon-phthalimido peroxyhexanoic acid as the bleaching agent.
  • the pH values of the compositions were adjusted by the addition of a 50% solution of sodium hydroxide or concentrated sulfuric acid, as necessary.
  • Silver plates were then held in each of the compositions for 25 minutes, removed, rinsed with deionized water and evaluated for silver tarnishing, and ranked as described in Example 1.
  • a tarnish score of 3 or less was considered effective as a silver anti-tarnishing compound. The observations were tabulated as presented below:
  • the compounds used in the invention must exhibit a pK a of more than 1 unit less than the pH of an aqueous solution of the composition in which they are incorporated.
  • Example 2 Three machine dishwashing compositions were prepared as described in Example 1, except that a chlorine bleaching agent and cyanuric acid as anti-tarnish agent were combined as follows: Sample Bleaching agent (% by wt.) Cyanuric acid (% by wt.) A Sodium dichloroisocyanurate (2.2%) 0% B Sodium hypochlorite (8.23%) 0% C Sodium hypochlorite (8.23%) 1%
  • compositions A, B and C The influence of the compositions A, B and C on silver tarnishing are shown in the following Table 12.
  • the anti-tarnish scale ranks from 0 to 6, according to the levels of tarnishing obtain with the compositions a to g of Example 1.
  • composition C containing 1% cyanuric acid
  • composition B in which hypochlorite was incorporated without cyanuric acid
  • Composition A containing sodium dichloroisocyanurate but no anti-tarnishing agent exhibited little silver tarnishing.
  • isocyanurate is formed during a wash in which sodium dichloroisocyanurate is used.
  • Isocyanurate can be formed upon dissociation of dicholoroisocyanurate, producing hypochlorite as the active bleaching species. This is also believed to explain why chloroisocyanurate bleach systems generally do not cause many problems in terms of silver tarnishing.
  • compositions were prepared as described in Example 1, except that the bleaching agent and anti-tarnish agent were varied as follows: Composition Bleaching Agent (% by wt.) Cyanuric Acid A Peracetic acid (4.12%) 0% B Peracetic acid (4.12%) 1.0% C Epsilon-phthalimidoperoxyhexanoic acid (4.0%) 0% D Epsilon-phthalimidoperoxyhexanoic acid (4.0%) 1.0% E Sodium hypochlorite (8.23%) 0% F Sodium hypochlorite (8.23%) 1.0%
  • Tarnish monitoring experiments were conducted using compositions A, B, C, D E and F at a product dosage of 40 grams per run in a Bauknecht GSF 3162 dishwasher, with an intake of 5 litres water.
  • the mainwash pH values for compositions A and B were adjusted to 7.5; the mainwash pH values for compositions C and D were adjusted to 8.5.
  • Two experiments were conducted using compositions E and F; the mainwash pH values were adjusted to 9.0 and 10.5, respectively.
  • Silver-plated spoons, knives, and forks supplied by Oneida Silversmiths, USA), were used as monitors for all experiments.
  • the monitors were washed in a commercially available dishwashing liquid and rinsed with deionized water and acetone before use. At the end of the dishwashing machine program, the monitors were visually evaluated for the presence of colours and/or loss of shine, according to the reference scale described in Example 1.
  • compositions A to E on silver tarnishing are shown in Table 15 below.
  • the anti-tarnish scale ranks from 0 to 6, according to the levels of tarnishing obtained with the compositions a to g of Example 1.
  • Tarnish monitoring experiments were conducted as described in Example 1, using two silver-plated spoons as monitors in each of the experiments.
  • the main wash pH in the experiments was between 8.8 and 8.5.
  • compositions B, C, D and J (outside the scope of the invention) exhibited heavy tarnishing on the washed spoons.
  • Tarnish monitoring experiments were conducted using compositions A, B, C, D, E and F at a product dosage of 40 grams per run in a Bauknecht GSF 3162 dishwasher, with an intake of 5 litres water.
  • the mainwash pH values for compositions A and B were adjusted to 7.5; the mainwash pH values for compositions C and D were adjusted to 8.5.
  • Two experiments were conducted using compositions E and F; the mainwash pH values were adjusted to 9.0 and 10.5. respectively.
  • Silver-plated spoons, knives and forks supplied by Oneida Silversmiths, USA), were used as monitors for all experiments.
  • the monitors were washed in a commercially available dishwashing liquid and rinsed with deionized water and acetone before use. At the end of the dishwashing machine program, the monitors were visually evaluated for the presence of colours and/or loss of shine, according to the reference scale described in Example 1.
  • 1,2,4-triazole reduced the level of tarnishing relative to the case where no anti-tarnishing agent was present. While tarnishing, inhibition due to 1,2,4-triazole occurred throughout the pH range described above, this effect was greater at higher alkalinity. At pH 7.5, the introduction of 1,2,4-triazole led to a reduction of 1.5 units of tarnishing; at pH 10.5 the reduction in tarnishing was 3.0 units. Furthermore, 1,2,4-triazole reduced tarnishing irrespective of the type of bleaching agent present in the composition; inhibition was noted for both chlorine and oxygen bleaches.
  • the anti-tarnish agent 1,2,4-triazole effectively reduced silver tarnishing.
  • Optimum performance of the agent was achieved at levels of 1 % by weight.
  • a comparison of anti-tarnishing performance of 1,3-N azole compounds within the scope of the invention and azole compounds outside the invention was conducted.
  • the selected compounds were incorporated in an amount of 1 wt.% in a machine dishwashing composition containing 4 wt.% epsilon-phthalimido peroxyhexanoic acid as the bleaching agent.
  • the pH values of the compositions were adjusted by the addition of a 50% solution of sodium hydroxide or concentrated sulfuric acid, as necessary.
  • the pK a of each compound was determined by preparing a 0.001M solution of inhibitor in deionized water. The pH of this solution was adjusted to 3.0 with H 2 SO 4 . The solution was then titrated with 1N NaOH to pH 11.0. A plot of mls. NaOH vs. pH for each sample was prepared. The pK a of the compound is that point where the maximum change in pH as a function of mls. NaOH is observed.
  • Silver plates were then held in each of the compositions for 25 minutes, removed, rinsed with deionized water and evaluated for silver tarnishing, and ranked as described in Example 1.
  • a tarnish score of 3 or less was considered effective as a silver anti-tarnishing compound. The observations were tabulated as presented below:
  • Tetrazole was not effective as a silver anti-tarnishing at a pH of 8.5 but was effective at a pH of 9.5 and greater. Tetrazole with a pK a of 8.4 is effective only in compositions having a pH of greater than 9.4. 5-aminotetrazole having a pK a of 8.1 was not effective at a pH of 8.8. The other compounds exhibited effective anti-tarnishing effects because their pK a values were more than 1 unit less than the pH of an aqueous solution of the composition in which they were incorporated.

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Claims (13)

  1. Composition détergente de blanchiment comprenant:
    (a) de 1 à 20 pourcent en poids d'un agent de blanchiment choisi parmi un composé peroxygéné ou un composé produisant un composé peroxygéné, un hypohalite ou un composé produisant un hypohalite, ou un sel de ceux-ci, ou leurs mélanges;
    (b) de 0,05 à 10% en poids d'un agent anti-ternissement choisi parmi:
    (i) un composé de la classe purine des formules (I) suivante et ses tautomères:
    Figure 00630001
       dans laquelle X1 représente un atome d'azote ou un groupe C-R3, Y1 représente un atome d'azote ou un groupe C-R4, et R1, R2, R3 et R4 représentent indépendamment un atome d'hydrogène, un groupe hydroxy, alcoxy, amine, alkyle à chaíne droite ou ramifiée possédant 1 à 20 atomes de carbone, amido, amidoalkyle, alkylthio, alcényle ou hydroxry-alkyle dans laquelle R1 peut de plus représenter SH lorsque R2 représente un atome d'hydrogène, X1 représente un atome d'azote, et Y1 représente un groupe CH
    (ii) de l'acide cyanurique ou de l'acide isocyanurique ou un sel de ceux-ci;
    (iii) un composé 1,3-N-azole de formule (II) suivante:
    Figure 00640001
       dans laquelle X2 représente un groupe C-R7 ou un atome d'azote à condition que Y2 soit également un atome d'azote, Y2 représente un atome d'azote ou un groupe C-R6, et R5, R6 et R7 représentent chacun indépendamment un atome d'hydrogène, un groupe amine, amido, alkyle à chaíne droite ou ramifiée possédant 1 à 20 atomes de carbone, une chaíne contenant un groupe amino ou carboxylique, alcoxy, alkylthio, hydroxy, hydroxyalkyle, alcényle, ou R5 et R6 pris ensemble forment un groupe aryle substitué ou non substitué; ou un sel de ceux-ci;
    (iv) un mélange de l'un quelconque des groupes (i), (ii), ou (iii);
    (c) éventuellement de 1 à 75% en poids d'un adjuvant de détergence; et
    (d) éventuellement, de 0,01 à 40% en poids d'un tensio-actif;
    dans lequel la composition présente une valeur de pH dans une solution aqueuse à 1% dans la gamme de 7 à 13, et dans laquelle l'agent anti-ternissement possède une valeur de pKa inférieure d'au moins une unité à la valeur du pH d'une solution aqueuse à 1% de la composition.
  2. Composition selon la revendication 1, dans laquelle l'agent anti-ternissement possède une valeur pKa inférieure de 2 à 6 unités à la valeur du pH d'une solution aqueuse à 1% de la composition.
  3. Composition selon la revendication 1 ou 2, dans laquelle l'agent anti-ternissement comprend un composé de formule (I) dans laquelle X1 représente un atome d'azote et Y1 représente un groupe C-R4 et R1, R2 et R4 représentent chacun indépendamment un atome d'hydrogène, un groupe hydroxy, alcoxy, alkylthio, amine, amido, un groupe alkyle inférieur possédant de 1 à 6 atomes de carbone, dans laquelle R1 peut de plus représenter SH, lorsque R2 représente un atome d'hydrogène, X1 représente un atome d'azote et Y1 représente CH.
  4. Composition selon la revendication 1 ou la revendication 2, dans laquelle le composé de formule (I) est choisi parmi la purine, l'adenine, la guanine, la 6-mercapto-purine, la xanthine, l'hypoxanthine, l'acide urique, et l'allopurinol.
  5. Composition selon la revendication 1 ou la revendication 2, dans laquelle l'agent anti-ternissement comprend un composé 1,3-N-azole de formule (II) dans lequel X2 représente un groupe C-R7, X2 représente un atome d'azote à condition que Y2 représente un atome d'azote, Y2 représente un groupe C-R6, et R5 et R6 pris ensembles forment un groupe aryle ou un groupe aryle substitué, ou un composé 1,3-N-azole de formule (II) dans lequel Y2 représente un groupe CR6 et R5 et R6 représentent chacun indépendamment un atome d'hydrogène, un groupe amine, amido, alkyle à chaíne droite ou ramifiée possédant de 1 à 6 atomes de carbone, alcoxy, alkylthio, hydroxy, alcényle ou une fraction contenant un groupe amino ou carboxylique.
  6. Composition selon la revendication 1 ou la revendication 2, dans laquelle l'agent anti-ternissement est choisi parmi l'imidazole, le benzimidazole, le 1,2,3,5-tetra-zole, le 4-amino-1,2,3,5-tétrazole, le 1,2,4-triazole, le 3-amino-1,2,4-triazole et l'histidine.
  7. Composition selon l'une quelconque des revendications précédentes, qui possède une valeur de pH de 7 à 11 en solution aqueuse à 1%.
  8. Composition selon l'une quelconque des revendications précédentes, dans laquelle l'agent de blanchiment comprend un composé peroxy choisi dans le groupe formé par: les mono- et di-peracides organiques; les diacylperoxydes organiques; et les sels inorganiques contenant un peroxy.
  9. Composition selon l'une quelconque des revendications précédentes, dans laquelle l'agent de blanchiment comprend un précurseur de blanchiment à base de peroxyacide.
  10. Composition selon l'une quelconque des revendications précédentes, dans laquelle l'agent de blanchiment comprend un composé contenant un halogène choisi dans le groupe formé par: les sels d'hypohalite: les composés contenant un halogène actif qui produisent des anions hypohalite dans des solutions alcalines aqueuses, et des acides isocyanuriques halogénés.
  11. Composition selon l'une quelconque des revendications précédentes, qui comprend de plus un ou plusieurs ingrédients supplémentaires choisis dans le groupe formé par les silicates; les matériaux de charge; les épaississants; les stabilisants et/ou les co-structurants; les agents anti-mousse, et les enzymes.
  12. Procédé de lavage d'un article en argent ou en plaqué argent tout en empêchant ou en inhibant son ternissement au cours ou en résultats du procédé de lavage, le procédé comprenant le lavage dudit article avec une composition détergente de blanchiment selon l'une quelconque des revendications 1 à 11.
  13. Utilisation d'un composé choisi parmi l'un quelconque de (i) à (iv) définis dans la revendication 1 en tant qu'agent anti-ternissement de l'argent dans un détergent de blanchiment à base de peroxygène et/ou hypohalite ayant une valeur de pH en solution aqueuse à 1% comprise entre 7 et 13, dans laquelle l'agent anti-ternissement possède une valeur de pKa inférieure d'au moins une unité à la valeur de pH d'une solution aqueuse à 1% de la composition.
EP94928878A 1993-10-14 1994-10-07 Compositions detergentes contenant des agents empechant le ternissement de l'argent Expired - Lifetime EP0723577B1 (fr)

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US302284 1981-09-15
US136629 1987-12-22
US13662993A 1993-10-14 1993-10-14
US13679193A 1993-10-14 1993-10-14
US136787 1993-10-14
US136791 1993-10-14
US08/136,787 US5374369A (en) 1993-10-14 1993-10-14 Silver anti-tarnishing detergent composition
US301459 1994-09-07
US08/301,459 US5480576A (en) 1993-10-14 1994-09-07 1,3-N azole containing detergent compositions
US08/302,284 US5468410A (en) 1993-10-14 1994-09-08 Purine class compounds in detergent compositions
PCT/EP1994/003322 WO1995010588A1 (fr) 1993-10-14 1994-10-07 Compositions detergentes contenant des agents empechant le ternissement de l'argent

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EP4314231A1 (fr) 2021-03-26 2024-02-07 Unilever IP Holdings B.V. Produit pour lave-vaisselle sous la forme d'une capsule à compartiments multiples
WO2024089079A1 (fr) 2022-10-25 2024-05-02 Symrise Ag Composition de nettoyage de vaisselle et/ou de rinçage de vaisselle présentant des propriétés de finition améliorées

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ES2122336T3 (es) 1998-12-16
WO1995010588A1 (fr) 1995-04-20
AU7812494A (en) 1995-05-04
CA2171312A1 (fr) 1995-04-20
EP0723577A1 (fr) 1996-07-31
BR9407809A (pt) 1997-05-06
DE69413051T2 (de) 1999-01-21
DE69413051D1 (de) 1998-10-08

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