EP0723577A1 - Compositions detergentes contenant des agents empechant le ternissement de l'argent - Google Patents

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

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Publication number
EP0723577A1
EP0723577A1 EP94928878A EP94928878A EP0723577A1 EP 0723577 A1 EP0723577 A1 EP 0723577A1 EP 94928878 A EP94928878 A EP 94928878A EP 94928878 A EP94928878 A EP 94928878A EP 0723577 A1 EP0723577 A1 EP 0723577A1
Authority
EP
European Patent Office
Prior art keywords
tarnishing
compound
silver
composition according
composition
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
EP94928878A
Other languages
German (de)
English (en)
Other versions
EP0723577B1 (fr
Inventor
Petrus Adrianus J. M. Angevaare
Richard Gerald Gary
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.)
Unilever PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from 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
Application granted granted Critical
Publication of EP0723577B1 publication Critical patent/EP0723577B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—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-tamishing 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.
  • the present invention provides a bleaching detergent composition comprising:
  • a bleaching agent selected from a peroxygen or peroxygen-yielding compound, a hypohalite or hypohalite-yielding compound, or a salt thereof, or mixtures thereof;
  • X 1 is nitrogen or C-R 3
  • Y 1 is nitrogen or C-R 4
  • R 1 , R 2 , R 3 and R 4 are each independently hydrogen, hydroxy, alkoxy, amine, straight or branched chain alkyl having 1 to 20 carbon atoms, amido, amidoalkyl, alkylthio, alkenyl or hydroxyalkyl;
  • X 2 is C-R 7 or nitrogen provided Y 2 is also nitrogen, Y 2 is nitrogen or C-R 6 , and R s , R 6 and R 7 are each independently hydrogen, amine, amido, straight or branched chain alkyl having from 1 to 20 carbon atoms, an amino- or carboxylic-containing chain, alkoxy, alkylthio, hydroxy, hydroxyalkyl, alkenyl, or R' and R 6 taken together form an unsubstituted or substituted aryl group; or a salt thereof;
  • composition exhibits a pH value in the range from about 7 to about 13, especially from about 7 to about 11, and wherein the anti-tarnishing agent has a pK a value below the pH value of an aqueous solution of the composition.
  • 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 the range from about 7 to about 13.
  • 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:
  • X 1 is nitrogen or C-R 3
  • Y 1 is nitrogen or C-R 4
  • R 1 , R 2 , R 3 and R 4 are each independently hydrogen, hydroxy, alkoxy, amine, straight or branched chain alkyl having 1 to 20 carbon atoms, amido, amidoalkyl, alkylthio, alkenyl or hydroxyalkyl;
  • X 2 is C-R 7 or nitrogen provided Y 2 is also nitrogen, Y 2 is nitrogen or C-R 6 , and R 5 , R 6 and R 7 are each independently hydrogen, amine, amido, straight or branched chain alkyl having from 1 to 20 carbon atoms, an amino- or carboxylic-containing chain, alkoxy, alkylthio, hydroxy, hydroxyalkyl, alkenyl, or R s and R 6 taken together form an unsubstituted or substituted aryl group; or a salt thereof;
  • the compound(s) have a pK a value which is below, preferably at least 1 unit below (especially in the case of the purine class compounds) , more preferably at least 2 units below, a pH value of an aqueous solution (preferably a 1% aqueous solution) of the composition in which the compound(s) is/are incorporated.
  • 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- embered rings in the case of the purine class compounds) are in anionic 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 , R 3 and R 4 are each independently hydrogen, hydroxy, alkoxy, oxygen, alkylthio, amine, amido or lower alkyl having from 1 to 6 carbon atoms.
  • 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 (IH, 3H, 5H) -trione, normal cyanuric acid, sym- triazinetriol, 2 , 4, 6-trihydroxy-l, 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 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, 5-aminotetrazole, 1, 2 ,4-triazole, 3-amino-l,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 about 6 carbon atoms, most preferably from 1 to about 4 carbon atoms.
  • those defined groups which are substituted alkyl groups preferably have an alkyl chain length of from 1 to about 5 carbon atoms, more preferably from 1 to about 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
  • This observation was particularly surprising in view of the fact that most of the 1-N and 1,2-N azole compounds did prevent copper tarnishing under similar conditions.
  • 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 about 0.05 to about 10% by weight, preferably from about 0.25 to about 2.5% by weight, most preferably from about 0.75 to about 2% by weight.
  • the pH of an aqueous solution (preferably a 1% solution) of the compositions in accordance with the invention should be from about 7 to about 13, more preferably from about 7 to about 11, most preferably from about 7 or 8 to about 10.
  • Peroxy bleaching agent 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: (i) peroxybenzoic acid and ring-substituted peroxybenzoic acids, e.g., peroxy-alpha-naphthoic acid, and magnesium monoperphthalate;
  • aliphatic and substituted aliphatic monoperoxy acids e.g., peroxylauric acid, peroxystearic acid, epsilon-phthalimido peroxyhexanoic acid, o-carboxybenzamido peroxyhexanoic acid, N-nonenylamidoperadipic acid and N- nonenylamidopersuccinic acid.
  • Typical diperoxy acids useful herein include alkyl diperoxy acids and aryldiperoxy acids, such as:
  • N,N-terephthaloyl-di(6-aminopercaproic acid) (vii) N,N-terephthaloyl-di(6-aminopercaproic acid) .
  • 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 about 1 to about 20% by weight, preferably from about 1 to about 15% by weight, most preferably from about 2 to about 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.
  • the bleaching agent is encapsulated as a core in a paraffin wax material having a melting point from about 40°C to about 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 chlorohydantoin ⁇ (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 about 1 to about 15% by weight, most preferably from about 2 to about 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 about 1 to about 75% by weight, preferably from about 5 to about 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 about 2 to about 40% by weight, preferably from about 5 to about 30% by weight of the composition.
  • Sodium carbonate and bicarbonate when present, may range from about 5 to about 50% by weight, preferably from about 10 to about 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 about 3 to about 30% by weight, preferably from about 10 to about 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 about 1 to about 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.
  • Surfactants 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, incorporated herein by reference.
  • 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, alkyl- substituted 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 about 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, 6 alkylbenzene sulphonates, C I0 -C 22 alkane sulphonates, C H) -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:
  • Suitable carboxylic acids include "coconut” fatty acids (derived from coconut oil) which contain an average of about 12 carbon atoms, "tallow” fatty acids (derived from tallow-class fats) which contain an average of about 18 carbon atoms, palmitic acid, myristic acid, stearic acid and lauric acid;
  • polyoxyethylene or polyoxypropylene condensates of aliphatic alcohols whether linear- or branched-chain and unsaturated or saturated, containing from about 6 to about 24 carbon atoms and incorporating from about 2 to about 50 ethylene oxide and/or propylene oxide units.
  • Suitable alcohols include coconut fatty alcohol, tallow fatty alcohol, lauryl alcohol, myristyl alcohol and oleyl alcohol.
  • Particularly preferred nonionic surfactant compounds in this category are the "Neodol"-type products, a registered trademark of the Shell Chemical Company.
  • nonionic surfactants having the following formula (III) :
  • R is a linear alkyl hydrocarbon radical having an average of 6 to 18 carbon atoms
  • R 1 and R 2 are each linear alkyl hydrocarbons of about 1 to about 4 carbon atoms
  • x is a integer of from 1 to 6
  • y is an integer of from 4 to 20
  • z is an integer from 4 to 25.
  • One preferred nonionic surfactant of formula I is Poly- Tergent SLF-18 (trade mark) , from the Olin Corporation, New Haven, Connecticut, USA, having a composition of the above formula where R is a C 6 -C K) linear alkyl mixture, R 1 and R 2 are methyl, x averages 3, y averages 12 and z averages 16. Also suitable are alkylated nonionics as are described in U.S. Patent No. 4,877,544 (Gabriel et al.), incorporated herein by reference.
  • nonionic surfactants included within this category are compounds of the following formula (IV) :
  • R 3 is a C 6 -C 24 linear or branched alkyl hydrocarbon radical and q is a number from 2 to 50; more preferably R 3 is a C 3 -C 18 linear alkyl mixture and q is a number from 2 to 15; (c) polyoxyethylene or polyoxypropylene condensates of alkyl phenols, whether linear- or branched- chain and unsaturated or saturated, containing from about 6 to 12 carbon atoms and incorporating from about 2 to about 25 moles of ethylene oxide and/or propylene oxide;
  • the preferred polyoxyethylene derivatives are of sorbitan monolaurate, sorbitan trilaurate, sorbitan monopalmitate, sorbitan tripalmitate, sorbitan monostearate, sorbitan monoisostearate, sorbitan tripalmitate, sorbitan monostearate, sorbitan monoisostearate, sorbitan tristearate, sorbitan monooleate, and sorbitan trioleate.
  • the polyoxyethylene chains may contain between about 4 and 30 ethylene oxide units, preferably about 20.
  • the sorbitan ester derivatives contain 1, 2 or 3 polyoxyethylene chains dependent upon whether they are mono-, di- or tri-acid esters;
  • a, b, c, d, e and f are integers from 1 to 350, reflecting the respective polyethylene oxide and polypropylene oxide blocks of said polymer.
  • the polyoxyethylene component of the block polymer constitutes at least about 10% of the block polymer.
  • the material preferably has a molecular weight of between about 1,000 and 15,000, more preferably from about 1,500 to about 6,000. These materials are well known in the art. They are commercially available for example under the trademarks "Pluronic” and "Pluronic R" from BASF corporation;
  • R 4 is a monovalent organic radical (e.g., a monovalent saturated aliphatic, unsaturated aliphatic or aromatic radical such as alkyl, hydroxyalkyl, alkenyl, hydroxyalkenyl, aryl, alkylaryl, hydroxyalkylaryl, arylalkyl, alkenylaryl, arylalkenyl, etc.) containing from about 6 to about 30 (preferably from about 8 to 18, more preferably from about 9 to about 13) carbon atoms; R 5 is a divalent hydrocarbon radical containing from 2 to about 4 carbon atoms such as ethylene, propylene or butylene (most preferably the unit (R 5 0) n represents repeating units of ethylene oxide, propylene oxide and/or random or block combinations thereof) ; n is a number having an average value of from 0 to about 12; Z 1 represents a moiety derived from a reducing saccharide containing 5 or 6 carbon atoms (most preferably a glucose unit)
  • Examples of commercially available materials from Henkel Kom andit GmbH Aktien of Dusseldorf, Germany include: APG (trade mark) 300, 325 and 350, with R 4 being C 9 -C ⁇ , n is 0 and p is 1.3, 1.6 and 1.8-2.2, respectively; APG 500 and 550 with R 4 is C,,-C 13 , n is 0 and p is 1.3 and 1.8-2.2, respectively; and APG 600 with R 4 being C 12 -C l4 , n is 0 and p is 1.3. Particularly preferred is APG 600; (g) Amine oxides having the following formula (VI II ) :
  • R 5 , R 6 and R 7 are saturated aliphatic radicals or substituted saturated aliphatic radicals.
  • Preferable amine oxides are those wherein R 5 is an alkyl chain of about 10 to about 20 carbon atoms and R° and R 7 are methyl or ethyl groups or both R 5 and R 6 are alkyl chains of about 6 to about 14 carbon atoms and R 7 is a methyl or ethyl group.
  • 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 about 8 to about 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 about 8 to about 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 about 0.01 to about 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 surfactan (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 about 40% by weight of the composition, more preferably from about 2 to about 35% by weight, even more preferably from about 5 to about 30% by weight.
  • Alkyl polyglycosides as the surfactant component may typically be present in lower concentrations, such as in an amount from about 0.01 to about 20% by weight, preferably from about 0.5 to about 10% by weight, optimally between about 1 and about 5% by weight of the composition.
  • compositions of this invention may optionally contain sodium or potassium silicate in an amount of from about 1 to about 40%, preferably from about 1 to about 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 Si0 2 :Na 2 0 of from about 1.0 to about 3.3, preferably from about 2 to about 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 about 60%, preferably from about 10 to about 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, saponite, and the like 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 about 0.1 to about 10% by weight, preferably from about 0.5 to about 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 about 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, incorporated herein by reference.
  • the amount of thickener employed in the compositions of the invention is preferably from 0 to about 5% by weight, preferably from about 0.5 to about 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, incorporated herein by reference.
  • the amount of stabilizer which may be used in liquid compositions of the invention is preferably from about 0.01 to about 5% by weight of the composition, preferably from about 0.01 to about 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 about 0.01 to about 4% by weight of the composition, and Laponite and/or water-soluble structuring chelants, which may be pre_ nt in an amount of from about 1 to about 60% by weight.
  • Formulations of the cleaning composition of the invertion comprising surfactant may further include a defoamer.
  • Suitable defoa ers 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 wnich food soils can generate. If a defoamer is present, the compositions may include from about 0.02 to about 2% by weight thereof, more preferably from about 0.05 to about 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; anti- redeposition 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; anti- redeposition 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 about 10% by weight, preferably from about 1 to about 5% by weight.
  • Such enzymes include proteases (e.g., Alcalase
  • Example 2 The following different levels of sodium perborate (H 2 0) and TAED (N,N,N ,N / -tetraacetylethylene diamine bleach activator) were used in Example 1:
  • Example 1 No anti-tarn sh agent was used n Example 1.
  • 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 about 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: Table 2
  • 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:
  • a detergent base was prepared having the following formula:
  • 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 about 9.8.
  • 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.
  • 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 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. 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 S0 4 . The solution was then titrated with IN NaOH to pH 11.0. A plot of mis. 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 mis. 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 claimed compounds 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.
  • machine dishwashing compositions having a pH of both 8.5 and 11 were prepared containing 4% by weight epsilon-phthalimido peroxyhexanoic acid as the bleaching agent and 1% by weight of three copper anti-tarnishing compounds listed below. Samples of the compositions were adjusted to both a pH of 8.5 and 11 by the addition of sodium hydroxide. Copper plates and silver plates were held in each of the compositions for 25 minutes, removed, rinsed with deionized water and evaluated for tarnishing. The following results were observed.
  • 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.
  • 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 43
  • 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 about 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 O.OOIM solution of inhibitor in deionized water. The pH of this solution was adjusted to 3.0 with H 2 S0 4 . The solution was then titrated with IN NaOH to pH 11.0. A plot of mis. NaOH vs. pH for each sample was prepared. The pK. of the compound is that point where the maximum change in pH as a function of mis. NaOH is observed.
  • 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.
  • machine dishwashing compositions having a pH of both 8.5 and 11 were prepared containing 4% by weight epsilon-phthalimido peroxyhexanoic acid as the bleaching agent and 1% by weight of three copper anti-tarnishing compounds listed below. Samples of the compositions were adjusted to both a pH of 8.5 and 11 by the addition of sodium hydroxide. Copper plates and silver plates were held in each of the compositions for 25 minutes, removed, rinsed with deionized water and evaluated for tarnishing. The following results were observed.

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Abstract

Une composition détergente de blanchiment qui empêche ou inhibe le ternissement de l'argent, comprend: (a) un agent de blanchiment choisi parmi un composé peroxygène ou à rendement peroxygène, un composé hypohalite ou à rendement hypohalite, ou un sel ou des mélanges de ces composés; (b) un agent contre le ternissement choisi parmi: (i) un composé de classe purine; (ii) un acide cyanurique ou isocyanurique ou un sel de l'un ou l'autre; (iii) un composé 1,3-N azole; (iv) un mélange de deux ou plusieurs des composés (i), (ii) ou (iii); (c) le cas échéant, un adjuvant; (d) le cas échéant, un tensioactif. Cette composition présente un pH s'échelonnant entre 7 et 13, et l'agent contre le ternissement a un pKa inférieur au pH d'une solution aqueuse 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)

Applications Claiming Priority (11)

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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
US08/136,787 US5374369A (en) 1993-10-14 1993-10-14 Silver anti-tarnishing detergent composition
US136787 1993-10-14
US136791 1993-10-14
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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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6463939B1 (en) 1999-02-05 2002-10-15 Unilever Home & Personal Care, Usa, Division Of Conopco, Inc. Dish washing process
WO2013092276A1 (fr) 2011-12-22 2013-06-27 Unilever N.V. Composition détergente comprenant du n,n-diacétate d'acide glutamique, de l'eau et un agent de blanchiment
WO2014198547A2 (fr) 2013-06-12 2014-12-18 Unilever N.V. Composition de détergent versable contenant des particules en suspension
WO2017148985A1 (fr) 2016-03-02 2017-09-08 Unilever N.V. Composition détergente fluide
WO2017148990A1 (fr) 2016-03-02 2017-09-08 Unilever N.V. Composition détergente se présentant sous la forme d'une suspension
WO2017148989A1 (fr) 2016-03-02 2017-09-08 Unilever N.V. Suspension de détergent pouvant être versée, comprenant une phase fluide colorée et des particules en suspension
WO2017153528A1 (fr) 2016-03-11 2017-09-14 Unilever N.V. Suspension de détergent fluide comprenant des granulés de catalyseur de blanchiment
WO2018206812A1 (fr) 2017-05-12 2018-11-15 Unilever N.V. Composition de détergent pour lave-vaisselle sans phosphate
WO2018206811A1 (fr) 2017-05-12 2018-11-15 Unilever N.V. Composition de détergent pour lave-vaisselle automatique
WO2021063560A1 (fr) 2019-09-30 2021-04-08 Unilever Ip Holdings B.V. Capsule pour lave-vaisselle à trois compartiments
WO2021170398A1 (fr) 2020-02-28 2021-09-02 Unilever Ip Holdings B.V. Produit détergent pour lave-vaisselle
WO2021170427A1 (fr) 2020-02-28 2021-09-02 Unilever Ip Holdings B.V. Produit détergent pour lave-vaisselle
WO2022161793A1 (fr) 2021-01-29 2022-08-04 Unilever Ip Holdings B.V. Liquide détergent pour lave-vaisselle professionnel
WO2022200053A1 (fr) 2021-03-26 2022-09-29 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

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19518693A1 (de) * 1995-05-22 1996-11-28 Henkel Kgaa Maschinelle Geschirrspülmittel mit Silberkorrosionsschutzmittel
AU1873297A (en) * 1996-02-29 1997-09-16 Unilever N.V. Machine dishwashing gel compositions
DE19631787C2 (de) * 1996-08-07 2000-06-29 Henkel Kgaa Benzotriazolhaltige, granulare Komponente für den Einsatz in Maschinengeschirrspülmitteln (MGSM) und Verfahren zu dessen Herstellung
EP0846757B1 (fr) * 1996-12-05 2005-01-26 Unilever N.V. Composition gélifiée pour lave-vaisselle
DE19701031C2 (de) * 1997-01-15 1998-12-10 Henkel Kgaa Verwendung von 3-Amino-5-alkyl-1,2,4-Triozolen als Silberschutzmittel
DE19716094A1 (de) * 1997-04-17 1998-10-22 Henkel Kgaa Spülmittel mit Korrosionsschutzwirkung
DE19758262A1 (de) * 1997-12-31 1999-07-08 Henkel Kgaa Alkylaminotriazolhaltige, granulare Komponente für den Einsatz in Maschinengeschirrspülmitteln (MGSM) und Verfahren zu dessen Herstellung
US7067467B2 (en) 2002-12-19 2006-06-27 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Aqueous perborate bleach composition
TWI453301B (zh) * 2007-11-08 2014-09-21 Enthone 浸鍍銀塗層上的自組分子

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE563877A (fr) * 1957-01-10
GB1372522A (en) * 1970-11-13 1974-10-30 Ciba Geigy Ag Detergent compositions
GB1347008A (en) * 1970-11-13 1974-02-13 Ciba Geigy Uk Ltd Detergent compositions
US4212937A (en) * 1977-12-23 1980-07-15 Asahi Kasei Kogyo Kabushiki Kaisha Heat developable photosensitive materials
US4321166A (en) * 1978-12-26 1982-03-23 The Procter & Gamble Company Liquid detergent compositions containing corrosion inhibiting system
CH673033A5 (en) * 1987-10-26 1990-01-31 Cosmina Ag Powder dishwashing agents for dishwashing machines - contg. combination of sodium citrate and sodium salt(s) of hydroxy-ethane di:phosphonic acid with sodium silicate

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9510588A1 *

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6463939B1 (en) 1999-02-05 2002-10-15 Unilever Home & Personal Care, Usa, Division Of Conopco, Inc. Dish washing process
WO2013092276A1 (fr) 2011-12-22 2013-06-27 Unilever N.V. Composition détergente comprenant du n,n-diacétate d'acide glutamique, de l'eau et un agent de blanchiment
WO2014198547A2 (fr) 2013-06-12 2014-12-18 Unilever N.V. Composition de détergent versable contenant des particules en suspension
WO2017148985A1 (fr) 2016-03-02 2017-09-08 Unilever N.V. Composition détergente fluide
WO2017148990A1 (fr) 2016-03-02 2017-09-08 Unilever N.V. Composition détergente se présentant sous la forme d'une suspension
WO2017148989A1 (fr) 2016-03-02 2017-09-08 Unilever N.V. Suspension de détergent pouvant être versée, comprenant une phase fluide colorée et des particules en suspension
WO2017153528A1 (fr) 2016-03-11 2017-09-14 Unilever N.V. Suspension de détergent fluide comprenant des granulés de catalyseur de blanchiment
WO2018206812A1 (fr) 2017-05-12 2018-11-15 Unilever N.V. Composition de détergent pour lave-vaisselle sans phosphate
WO2018206811A1 (fr) 2017-05-12 2018-11-15 Unilever N.V. Composition de détergent pour lave-vaisselle automatique
WO2021063560A1 (fr) 2019-09-30 2021-04-08 Unilever Ip Holdings B.V. Capsule pour lave-vaisselle à trois compartiments
WO2021170398A1 (fr) 2020-02-28 2021-09-02 Unilever Ip Holdings B.V. Produit détergent pour lave-vaisselle
WO2021170427A1 (fr) 2020-02-28 2021-09-02 Unilever Ip Holdings B.V. Produit détergent pour lave-vaisselle
WO2022161793A1 (fr) 2021-01-29 2022-08-04 Unilever Ip Holdings B.V. Liquide détergent pour lave-vaisselle professionnel
WO2022200053A1 (fr) 2021-03-26 2022-09-29 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

Also Published As

Publication number Publication date
ES2122336T3 (es) 1998-12-16
DE69413051T2 (de) 1999-01-21
DE69413051D1 (de) 1998-10-08
EP0723577B1 (fr) 1998-09-02
AU7812494A (en) 1995-05-04
WO1995010588A1 (fr) 1995-04-20
BR9407809A (pt) 1997-05-06
CA2171312A1 (fr) 1995-04-20

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