EP0948593A1 - Compositions pour lavage de vaisselle en machine - Google Patents

Compositions pour lavage de vaisselle en machine

Info

Publication number
EP0948593A1
EP0948593A1 EP97905571A EP97905571A EP0948593A1 EP 0948593 A1 EP0948593 A1 EP 0948593A1 EP 97905571 A EP97905571 A EP 97905571A EP 97905571 A EP97905571 A EP 97905571A EP 0948593 A1 EP0948593 A1 EP 0948593A1
Authority
EP
European Patent Office
Prior art keywords
bismuth
diphosphonate
acid
compound
solution
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.)
Withdrawn
Application number
EP97905571A
Other languages
German (de)
English (en)
Other versions
EP0948593A4 (fr
Inventor
Alison Moyra Smith
John Scott Park
Harold Emmerson
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.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Publication of EP0948593A1 publication Critical patent/EP0948593A1/fr
Publication of EP0948593A4 publication Critical patent/EP0948593A4/xx
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/94—Bismuth compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
    • C07F9/3839—Polyphosphonic acids
    • C07F9/386—Polyphosphonic acids containing hydroxy substituents in the hydrocarbon radicals
    • 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
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/361—Phosphonates, phosphinates or phosphonites
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3932—Inorganic compounds or complexes

Definitions

  • the present invention relates to bismuth diphosphonate compounds and methods of making such compounds and their use in oxygen-bleach containing compositions, adapted for use in machine dishwashing, which exhibit good bleachable stain removal and reduced silver-tarnishing properties.
  • compositions designed for use in automatic dishwasher machines are well known, and a consistent effort has been made by detergent manufacturers to improve the cleaning and/or rinsing efficiency of said compositions on chinaware, glassware and silverware, as reflected by numerous patent publications.
  • a problem encountered with the use of oxygen bleaches is the tarnishing of any silverware components of the washload.
  • Chlorine bleaches can under certain circumstances give rise to silver tarnishing, but the problem is significantly less pronounced than that arising from the use of oxygen bleaches.
  • the level of tarnishing observed with oxygen bleaches can range from slight discolouration of the silverware to the formation of a dense black coating on the surface of the silverware.
  • the formulator thus faces the dual challenge of formulating an oxygen bleach containing product which maximises bleachable soil cleaning but minimises the occurrence of tarnishing of any silverware components of the washload.
  • the rate of release of the oxygen bleach is preferably also controlled.
  • the rate of release of oxygen bleach is preferably rapid enough to provide satisfactory cleaning, but not so rapid that tarnishing is enabled.
  • compositions having low alkalinity and in particular those having alkalinity systems including a minor proportion of a metasilicate component are preferred, as are compositions having a pH which is not unduly high.
  • UK Patent Specification No. 1,586,067 in the name of the Procter and Gamble Company discloses automatic dishwashing compositions containing bismuth salts to provide protection to china overglaze without any negative glassware irridescence effects.
  • Bismuth diphosphonate compounds are not explicitly described. It is taught therein that chlorine bleaching agents are preferable components of these compositions and specific examples of chlorine containing compositions are given. The use of oxygen bleaches in such compositions is not disclosed. The problem of silver tarnishing is not addressed by this document, nor is any teaching provided of the use of bismuth salts as silver tarnish inhibition agents.
  • bismuth diphosphonate compound wherein the molar ratio of bismuth to diphosphonate components is from 1 :0.7 to 1 :7.
  • the amount of bismuth to diphosphonate species corresponds to a molar ratio of from 1 :0.7 to 1 :7.
  • Said bismuth diphosphonate solution can be sprayed onto a bleaching composition to form a bleaching product.
  • the bleaching composition also contains detergent components.
  • bleaching and detergent compositions adapted for use in machine dishwashing methods, containing an oxygen-releasing bleaching system and bismuth diphosphonate compound.
  • the detergent compositions contain no phosphate builder compound.
  • a bismuth diphosphonate compound wherein the molar ratio of bismuth to diphosphonate components is from 1:0.7 to 1:7, preferably from 1: 1 to 1:6, more preferably from 1:2 to 1 :5.
  • the bismuth diphosphonate compound may be essentially any salt or complex of bismuth with essentially any organic diphosphonic acid.
  • organo diphosphonic acid it is meant herein an organo diphosphonic acid which does not contain nitrogen as part of its chemical structure. This definition therefore excludes the organo aminophosphonates, which however may be included in any compositions in accord with the invention as heavy metal ion sequestrant components.
  • the organo diphosphonic acid is preferably a C1-C4 diphosphonic acid, more preferably a C2 diphosphonic acid, such as ethylene diphosphonic acid, or most preferably ethane 1 -hydroxy- 1 ,1 -diphosphonic acid (HEDP) and may be present in partially or fully ionized form, particularly as a salt or complex.
  • HEDP ethane 1 -hydroxy- 1 ,1 -diphosphonic acid
  • the compound containing bismuth and HEDP at a 1 :3.5 molar ratio is most preferred.
  • a step-wise process for making a bismuth diphosphonate solution involving sequentially the formation of an alkaline solution containing a diphosphonate species followed by addition of a solution containing bismuth ions.
  • This solution has been found to be both storage and transport stable, and may be employed in the making of bleaching and/or detergent compositions, as described hereinafter.
  • the advantage provided by the step-wise process versus a process in which both steps take place concurrently is that, in the latter case, a heavy yellow essentially insoluble precipitate, believed to be bismuth hydroxide, is formed. This precipitate impedes the further processing of the solution, and limits its usefulness in the making of bleaching and/or detergent compositions.
  • the process comprises as a first step the formation of an alkaline solution containing a diphosphonate species.
  • the alkaline solution may for example, be formed by direct addition, preferably with agitation, of a diphosphonic acid to an aqueous alkaline solution, such as NaOH solution.
  • said addition is continuous, but carried out at a relatively slow rate such as to avoid excess generation of heat from the neutralization reaction.
  • the process has as a second step the agitative addition of a solution containing bismuth ions to the alkaline solution containing the diphosphonate species.
  • agitative addition it is meant addition in the presence of some means of agitation, such as may be provided by carrying out the addition in a mixer apparatus.
  • the solution containing bismuth ions may comprise a solution of any suitable salt or complex of bismuth with essentially any inorganic or organic counter anion.
  • Preferred inorganic bismuth salts for use in making up the solution are selected from the bismuth trihalides, bismuth nitrate and bismuth phosphate.
  • Bismuth acetate and citrate are preferred salts with an organic counter anion.
  • the amount of alkaline diphosphonate and bismuth ion solutions employed in this process aspect is adjusted such as to result in the formation of a bismuth diphosphonate solution having a molar ratio of bismuth to diphosphonate species of from 1 :0.7 to 1 :7.
  • the bismuth diphosphonate solution can be sprayed onto a bleaching composition to form a bleaching product.
  • the bleaching composition also contains detergent components, and the bismuth diphosphonate solution is thus sprayed onto both bleaching and detergent components.
  • a process for making a bismuth disphosphonate-containing particle by agglomeration of an inorganic salt with an alkaline bismuth diphosphonate solution preferably obtained by the process described hereinabove.
  • the inorganic salt comprises an anion capable of forming a salt, especially an insoluble salt, with bismuth.
  • the alkaline diphosphonate solution preferably has a pH of at least 9.0, more preferably at least 10.0.
  • the inorganic salt may be essentially any salt of an inorganic anion capable also of forming a bismuth salt, such as sulfates, carbonates and phosphates with any counter cation, including the alkali and alkaline earth metals.
  • Preferred salts are selected from the sulfates of the alkali and alkaline earth metals, particularly sodium sulfate.
  • the weight ratio of the inorganic salt to bismuth diphosphonate compound in the particle is preferably from 200: 1 to 2: 1 , more preferably from 100: 1 to 5: 1, most preferably from 50: 1 to 10: 1.
  • the particle comprises an organic binder material.
  • the organic binder material is preferably selected from any of the organic polymeric compounds described in detail hereinafter, and any mixtures thereof.
  • Other suitable binders include the C10-C20 alcohol ethoxylates containing from 5 - 100 moles of ethylene oxide per mole of alcohol and more preferably the C15-C20 primary alcohol ethoxylates containing from 20 - 100 moles of ethylene oxide per mole of alcohol.
  • Polyvinylpyrrolidones with an average molecular weight of from 12,000 to 700,000 and polyethylene glycols (PEG) with an average molecular weight of from 600 to 5 x IO 6 preferably 1000 to 400,000 most preferably 1000 to 10,000 are also suitable binders.
  • Cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, and homo- or co- polymeric polycarboxylic acids or their salts are other examples of binders suitable for use herein.
  • the agglomeration method employed can be any of those known in the art. Any conventional agglomerator/mixer may be used including, but not limited to pan, rotary drum and vertical blender types. Mixers sold by Schugi (tradename) and Lodige (tradename) for use in agglomeration methods are particularly suitable. Agglomeration processes employing 'in series' combinations of mixers are also envisaged.
  • the bismuth diphosphonate compounds and particles containing such compounds described hereinbefore may be inco ⁇ orated into compositions containing an oxygen-releasing bleaching system.
  • the bleaching system contains a hydrogen peroxide source and an organic peroxyacid bleach precursor compound.
  • the production of the organic peroxyacid occurs by an in situ reaction of the precursor with a source of hydrogen peroxide.
  • Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches.
  • a preformed organic peroxyacid is incorporated directly into the composition.
  • Compositions containing mixtures of a hydrogen peroxide source and organic peroxyacid precursor in combination with a preformed organic peroxyacid are also envisaged.
  • compositions in accord with the invention preferably include a hydrogen peroxide source, as an oxygen-releasing bleach.
  • Suitable hydrogen peroxide sources include the inorganic perhydrate salts.
  • the inorganic perhydrate salts are normally inco ⁇ orated in the form of the sodium salt at a level of from 1 % to 40% by weight, more preferably from 2% to 30% by weight and most preferably from 5 % to 25% by weight of the compositions.
  • inorganic perhydrate salts include perborate, percarbonate, pe ⁇ hosphate, persulfate and persilicate salts.
  • the inorganic perhydrate salts are normally the alkali metal salts.
  • the inorganic perhydrate salt may be included as the crystalline solid without additional protection.
  • the preferred executions of such granular compositions utilize a coated form of the material which provides better storage stability for the perhydrate salt in the granular product.
  • Sodium perborate can be in the form of the monohydrate of nominal formula NaB ⁇ 2H2 ⁇ 2 or the tetrahydrate NaB ⁇ 2H2 ⁇ 2-3H2 ⁇ .
  • Alkali metal percarbonates, particularly sodium percarbonate are preferred perhydrates for inclusion in compositions in accordance with the invention.
  • Sodium percarbonate is an addition compound having a formula corresponding to 2Na2C ⁇ 3.3H2 ⁇ 2, and is available commercially as a crystalline solid.
  • Sodium percarbonate, being a hydrogen peroxide addition compound tends on dissolution to release the hydrogen peroxide quite rapidly which can increase the tendency for localised high bleach concentrations to arise.
  • the percarbonate is most preferably inco ⁇ orated into such compositions in a coated form which provides in product stability.
  • a suitable coating material providing in product stability comprises mixed salt of a water soluble alkali metal sulphate and carbonate.
  • the weight ratio of the mixed salt coating material to percarbonate lies in the range from 1 : 200 to 1 : 4, more preferably from 1 : 99 to 1 : 9, and most preferably from 1 : 49 to 1 : 19.
  • the mixed salt is of sodium sulphate and sodium carbonate which has the general formula Na2SO n.Na2C ⁇ 3 wherein n is from 0.1 to 3, preferably n is from 0.3 to 1.0 and most preferably n is from 0.2 to 0.5.
  • coatings which contain silicate (alone or with borate salts or boric acids or other inorganics), waxes, oils, fatty soaps can also be used advantageously within the present invention.
  • Potassium peroxymonopersulfate is another inorganic perhydrate salt of utility in the compositions herein.
  • Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid.
  • peroxyacid bleach precursors may be represented as
  • L is a leaving group and X is essentially any functionality, such that on perhydroloysis the structure of the peroxyacid produced is
  • O X-C -OOH Peroxyacid bleach precursor compounds are preferably inco ⁇ orated at a level of from 0.5 % to 20% by weight, more preferably from 1 % to 10% by weight, most preferably from 1.5% to 5% by weight of the compositions.
  • Suitable peroxyacid bleach precursor compounds typically contain one or more N- or O-acyl groups, which precursors can be selected from a wide range of classes.
  • Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are disclosed in GB-A- 1586789. Suitable esters are disclosed in GB-A-836988, 864798, 1147871 , 2143231 and EP-A-0170386.
  • L group The leaving group, hereinafter L group, must be sufficiently reactive for the perhydrolysis reaction to occur within the optimum time frame (e.g., a wash cycle). However, if L is too reactive, this activator will be difficult to stabilize for use in a bleaching composition.
  • Preferred L groups are selected from the group consisting of:
  • R is an alkyl, aryl, or alkaryl group containing from 1 to 14 carbon atoms
  • R is an alkyl chain containing from 1 to 8 carbon atoms
  • R is H or R
  • Y is H or a solubilizing group.
  • Any of R , R and R may be substituted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammmonium groups
  • the preferred solubilizing groups are -SO ⁇ " M , -CO2 M , -SO M , -N + (R 3 ) 4 X " and 0 ⁇ N(R 3 ) 3 and most preferably -S0 3 " M + and -C ⁇ 2 ⁇ M wherein R is an alkyl chain containing from 1 to 4 carbon atoms, M is a cation which provides solubility to the bleach activator and X is an anion which provides solubility to the bleach activator.
  • M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred, and X is a halide, hydroxide, methylsulfate or acetate anion.
  • Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis.
  • Suitable O-acylated perbenzoic acid precursor compounds include the substituted and unsubstituted benzoyl oxybenzene sulfonates, including for example benzoyl oxybenzene sulfonate:
  • benzoylation products of sorbitol, glucose, and all saccharides with benzoylating agents including for example:
  • Perbenzoic acid precursor compounds of the imide type include N-benzoyl succinimide, tetrabenzoyl ethylene diamine and the N-benzoyl substituted ureas.
  • Suitable imidazole type perbenzoic acid precursors include N- benzoyl imidazole and N-benzoyl benzimidazole and other useful N-acyl group-containing perbenzoic acid precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.
  • perbenzoic acid precursors include the benzoyl diacyl peroxides, the benzoyl tetraacyl peroxides, and the compound having the formula:
  • Phthalic anhydride is another suitable perbenzoic acid precursor compound h hpe.rrpeiinn-:
  • Suitable N-acylated lactam perbenzoic acid precursors have the formula:
  • n is from 0 to 8, preferably from 0 to 2
  • R is a benzoyl group.
  • Perbenzoic acid derivative precursors provide substituted perbenzoic acids on perhydrolysis.
  • Suitable substituted perbenzoic acid derivative precursors include any of the herein disclosed perbenzoic precursors in which the benzoyl group is substituted by essentially any non-positively charged (ie; non-cationic) functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl and amide groups.
  • a preferred class of substituted perbenzoic acid precursor compounds are the amide substituted compounds of the following general formulae:
  • Rl is an aryl or alkaryl group with from 1 to 14 carbon atoms
  • R ⁇ is an arylene, or alkarylene group containing from 1 to 14 carbon atoms
  • R5 is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms and L can be essentially any leaving group.
  • Rl preferably contains from 6 to 12 carbon atoms.
  • R ⁇ preferably contains from 4 to 8 carbon atoms.
  • Rl may be aryl, substituted aryl or alkylaryl containing branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat. Analogous structural variations are permissible for R2.
  • substitution can include alkyl, aryl, halogen, nitrogen, sulphur and other typical substituent groups or organic compounds.
  • R ⁇ is preferably H or methyl.
  • Rl and R ⁇ should not contain more than 18 carbon atoms in total.
  • Amide substituted bleach activator compounds of this type are described in EP-A-0170386.
  • Cationic peroxyacid precursor compounds produce cationic peroxyacids on perhydrolysis.
  • cationic peroxyacid precursors are formed by substituting the peroxyacid part of a suitable peroxyacid precursor compound with a positively charged functional group, such as an ammonium or alkyl ammmonium group, preferably an ethyl or methyl ammonium group.
  • Cationic peroxyacid precursors are typically present in the compositions as a salt with a suitable anion, such as for example a halide ion or a methylsulfate ion.
  • the peroxyacid precursor compound to be so cationically substituted may be a perbenzoic acid, or substituted derivative thereof, precursor compound as described hereinbefore.
  • the peroxyacid precursor compound may be an alkyl percarboxylic acid precursor compound or an amide substituted alkyl peroxyacid precursor as described hereinafter
  • Cationic peroxyacid precursors are described in U.S. Patents 4,904,406; 4,751 ,015; 4,988,451 ; 4,397,757; 5,269,962; 5, 127,852; 5,093,022; 5,106,528; U.K. 1 ,382,594; EP 475,512, 458,396 and 284,292; and in JP 87-318,332.
  • Suitable cationic peroxyacid precursors include any of the ammonium or alkyl ammonium substituted alkyl or benzoyl oxybenzene sulfonates, N- acylated caprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides.
  • a preferred cationically substituted benzoyl oxybenzene sulfonate is the 4- (trimethyl ammonium) methyl derivative of benzoyl oxybenzene sulfonate:
  • a preferred cationically substituted alkyl oxybenzene sulfonate has the formula:
  • Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl ammonium methylene benzoyl caprolactams, particularly trimethyl ammonium methylene benzoyl caprolactam:
  • N-acylated caprolactam class examples include the trialkyl ammonium methylene alkyl caprolactams:
  • n is from 0 to 12, particularly from 1 to 5.
  • Another preferred cationic peroxyacid precursor is 2-(N,N,N-trimethyl ammonium) ethyl sodium 4-sulphophenyl carbonate chloride.
  • Alkyl percarboxylic acid bleach precursors form percarboxylic acids on perhydrolysis.
  • Preferred precursors of this type provide peracetic acid on perhydrolysis.
  • Preferred alkyl percarboxylic precursor compounds of the imide type include the N-,N,N N1 tetra acetylated alkylene diamines wherein the alkylene group contains from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1 , 2 and 6 carbon atoms. Tetraacetyl ethylene diamine (TAED) is particularly preferred.
  • TAED Tetraacetyl ethylene diamine
  • alkyl percarboxylic acid precursors include sodium 3,5,5- tri-methyl hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate (ABS) and pentaacetyl glucose.
  • Amide substituted alkyl peroxyacid precursor compounds are also suitable, including those of the following general formulae:
  • Rl is an alkyl group with from 1 to 14 carbon atoms
  • R ⁇ is an alkylene group containing from 1 to 14 carbon atoms
  • R ⁇ is H or an alkyl group containing 1 to 10 carbon atoms and L can be essentially any leaving group.
  • Rl preferably contains from 6 to 12 carbon atoms.
  • R ⁇ preferably contains from 4 to 8 carbon atoms.
  • Rl may be straight chain or branched alkyl containing branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat. Analogous structural variations are permissible for R2.
  • the substitution can include alkyl, halogen, nitrogen, sulphur and other typical substituent groups or organic compounds.
  • R ⁇ is preferably H or methyl.
  • Rl and R ⁇ should not contain more than 18 carbon atoms in total. Amide substituted bleach activator compounds of this type are described in EP-A-0170386.
  • precursor compounds of the benzoxazin-type as disclosed for example in EP-A-332,294 and EP-A-482,807, particularly those having the formula:
  • R j is H, alkyl, alkaryl, aryl, arylalkyl, and wherein R2, R3, R4, and R may be the same or different substituents selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxyl, amino, alkyl amino, COOR ⁇ (wherein Rzr is H or an alkyl group) and carbonyl functions.
  • An especially preferred precursor of the benzoxazin-type is:
  • the organic peroxyacid bleaching system may contain, in addition to, or as an alternative to, an organic peroxyacid bleach precursor compound, a preformed organic peroxyacid , typically at a level of from 0.5% to 25% by weight, more preferably from 1 % to 10% by weight of the composition.
  • a preferred class of organic peroxyacid compounds are the amide substituted compounds of the following general formulae:
  • Rl is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms
  • R2 is an alkylene, ary lene, and alkarylene group containing from 1 to 14 carbon atoms
  • R ⁇ is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms.
  • Rl preferably contains from 6 to 12 carbon atoms.
  • R ⁇ preferably contains from 4 to 8 carbon atoms.
  • Rl may be straight chain or branched alkyl, substituted aryl or alkylaryl containing branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat. Analogous structural variations are permissible for R ⁇ .
  • substitution can include alkyl, aryl, halogen, nitrogen, sulphur and other typical substituent groups or organic compounds.
  • R ⁇ is preferably H or methyl.
  • Rl and R5 should not contain more than 18 carbon atoms in total. Amide substituted organic peroxyacid compounds of this type are described in EP-A-0170386.
  • organic peroxyacids include diacyl and tetraacylperoxides, especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid, and diperoxyhexadecanedioc acid.
  • Dibenzoyl peroxide is a preferred organic peroxyacid herein.
  • Mono- and diperazelaic acid, mono- and diperbrassylic acid, and N-phthaloylaminoperoxicaproic acid are also suitable herein.
  • compositions may contain additional corrosion inhibitors preferably selected from organic silver coating agents, particularly paraffin, nitrogen- containing corrosion inhibitor compounds and Mn(II) compounds, particularly Mn(II) salts of organic ligands.
  • additional corrosion inhibitors preferably selected from organic silver coating agents, particularly paraffin, nitrogen- containing corrosion inhibitor compounds and Mn(II) compounds, particularly Mn(II) salts of organic ligands.
  • Organic silver coating agents are described in PCT Publication No. W094/ 16047 (attorney's docket no. CM497M) and copending UK Application No. UK 9413729.6 (attorney's docket no. CM750F).
  • Nitrogen- containing corrosion inhibitor compounds are disclosed in copending European Application no. EP 93202095.1 (attorney's docket no. CM571F).
  • Mn(II) compounds for use in corrosion inhibition are described in copending UK Application No. 9418567.5 (attorney's docket no. CM719FM).
  • Organic silver coating agent may be inco ⁇ orated at a level of from 0.05 % to 10% , preferably from 0.1 % to 5% by weight of the total composition.
  • the functional role of the silver coating agent is to form 'in use' a protective coating layer on any silverware components of the washload to which the compositions of the invention are being applied.
  • the silver coating agent should hence have a high affinity for attachment to solid silver surfaces, particularly when present in as a component of an aqueous washing and bleaching solution with which the solid silver surfaces are being treated.
  • Suitable organic silver coating agents herein include fatty esters of mono- or polyhydric alcohols having from 1 to about 40 carbon atoms in the hydrocarbon chain.
  • the fatty acid portion of the fatty ester can be obtained from mono- or poly-carboxylic acids having from 1 to about 40 carbon atoms in the hydrocarbon chain.
  • monocarboxylic fatty acids include behenic acid, stearic acid, oleic acid, palmitic acid, myristic acid, lauric acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, lactic acid, gly colic acid and ⁇ , ⁇ '- dihydroxy isobutyric acid.
  • suitable polycarboxylic acids include: n-butyl-malonic acid, isocitric acid, citric acid, maleic acid, malic acid and succinic acid.
  • the fatty alcohol radical in the fatty ester can be represented by mono- or polyhydric alcohols having from 1 to 40 carbon atoms in the hydrocarbon chain.
  • suitable fatty alcohols include; behenyl, arachidyl, cocoyl, oleyl and lauryl alcohol, ethylene glycol, glycerol, ethanol, isopropanol, vinyl alcohol, diglycerol, xylitol, sucrose, erythritol, pentaerythritol, sorbitol or sorbitan.
  • the fatty acid and/or fatty alcohol group of the fatty ester adjunct material have from 1 to 24 carbon atoms in the alkyl chain.
  • Preferred fatty esters herein are ethylene glycol, glycerol and sorbitan esters wherein the fatty acid portion of the ester normally comprises a species selected from behenic acid, stearic acid, oleic acid, palmitic acid or myristic acid.
  • glycerol esters are also highly preferred. These are the mono-, di- or tri-esters of glycerol and the fatty acids as defined above.
  • fatty alcohol esters for use herein include: stearyl acetate, palmityl di-lactate, cocoyl isobutyrate, oleyl maleate, oleyl dimaleate , and tallowy 1 proprionate.
  • Fatty acid esters useful herein include: xylitol monopalmitate, pentaerythritol monostearate, sucrose monostearate, glycerol monostearate, ethylene glycol monostearate, sorbitan esters.
  • Suitable sorbitan esters include sorbitan monostearate, sorbitan palmitate, sorbitan monolaurate, sorbitan monomyristate, sorbitan monobehenate, sorbitan mono-oleate, sorbitan dilaurate, sorbitan distearate, sorbitan dibehenate, sorbitan dioleate, and also mixed tallowalkyl sorbitan mono- and di-esters.
  • Glycerol monostearate glycerol mono-oleate, glycerol monopalmitate, glycerol monobehenate, and glycerol distearate are preferred glycerol esters herein.
  • Suitable organic silver coating agents include triglycerides, mono or diglycerides, and wholly or partially hydrogenated derivatives thereof, and any mixtures thereof.
  • Suitable sources of fatty acid esters include vegetable and fish oils and animal fats.
  • Suitable vegetable oils include soy bean oil, cotton seed oil, castor oil, olive oil, peanut oil, safflower oil, sunflower oil, rapeseed oil, grapeseed oil, palm oil and corn oil.
  • Waxes including microcrystalline waxes are suitable organic silver coating agents herein.
  • Preferred waxes have a melting point in the range from about 35 °C to about 110°C and comprise generally from 12 to 70 carbon atoms.
  • Preferred are petroleum waxes of the paraffin and microcrystalline type which are composed of long-chain saturated hydrocarbon compounds.
  • Alginates and gelatin are suitable organic silver coating agents herein.
  • Dialkyl amine oxides such as C12-C20 methylamine oxide, and dialkyl quaternary ammonium compounds and salts, such as the C12-C20 methylammonium halides are also suitable.
  • suitable organic silver coating agents include certain polymeric materials.
  • perfume materials particularly those demonstrating a high substantivity for metallic surfaces, are also useful as the organic silver coating agents herein.
  • Suitable polymeric soil release agents include those soil release agents having: (a) one or more nonionic hydrophile components consisting essentially of (i) polyoxyethylene segments with a degree of polymerization of at least 2, or (ii) oxypropylene or polyoxypropylene segments with a degree of polymerization of from 2 to 10, wherein said hydrophile segment does not encompass any oxypropylene unit unless it is bonded to adjacent moieties at each end by ether linkages, or (iii) a mixture of oxyalkylene units comprising oxy ethylene and from 1 to about 30 oxypropylene units, said hydrophile segments preferably comprising at least about 25 % oxyethylene units and more preferably, especially for such components having about 20 to 30 oxypropylene units, at least about 50% oxyethylene units; or (b) one or more hydrophobe components comprising (i) C3 oxyalkylene terephthalate segments, wherein, if said hydrophobe components also comprise oxyethylene terephthalate, the
  • the polyoxyethylene segments of (a)(i) will have a degree of polymerization of from about 200, although higher levels can be used, preferably from 3 to about 150, more preferably from 6 to about 100.
  • Suitable oxy C4-C6 alkylene hydrophobe segments include, but are not limited to, end-caps of polymeric soil release agents such as M ⁇ 3S(CH2) n OCH2CH2 ⁇ -, where M is sodium and n is an integer from 4-6, as disclosed in U.S. Patent 4,721 ,580, issued January 26, 1988 to Gosselink.
  • Polymeric soil release agents useful herein also include cellulosic derivatives such as hydroxyether cellulosic polymers, copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, and the like. Such agents are commercially available and include hydroxyethers of cellulose such as METHOCEL (Dow). Cellulosic soil release agents for use herein also include those selected from the group consisting of C1-C4 alkyl and C4 hydroxyalkyl cellulose; see U.S. Patent 4,000,093, issued December 28, 1976 to Nicol, et al.
  • Soil release agents characterized by poly(vinyl ester) hydrophobe segments include graft copolymers of poly(vinyl ester), e.g. , Ci-C vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkylene oxide backbones, such as polyethylene oxide backbones.
  • poly(vinyl ester) e.g. , Ci-C vinyl esters
  • poly(vinyl acetate) grafted onto polyalkylene oxide backbones such as polyethylene oxide backbones.
  • Another suitable soil release agent is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate.
  • the molecular weight of this polymeric soil release agent is in the range of from about 25,000 to about 55,000. See U.S. Patent 3,959,230 to Hays, issued May 25, 1976 and U.S. Patent 3,893,929 to Basadur issued July 8, 1975.
  • Another suitable polymeric soil release agent is a polyester with repeat units of ethylene terephthalate units contains 10-15 % by weight of ethylene terephthalate units together with 90-80% by weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol of average molecular weight 300-5,000.
  • Another suitable polymeric soil release agent is a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and terminal moieties covalently attached to the backbone.
  • These soil release agents are described fully in U.S. Patent 4,968,451 , issued November 6, 1990 to J.J. Scheibel and E.P. Gosselink.
  • Other suitable polymeric soil release agents include the terephthalate polyesters of U.S. Patent 4,711 ,730, issued December 8, 1 87 to Gosselink et al, the anionic end-capped oligomeric esters of U.S.
  • Patent 4,721,580 issued January 26, 1988 to Gosselink
  • block polyester oligomeric compounds of U.S. Patent 4,702,857 issued October 27, 1987 to Gosselink.
  • Other polymeric soil release agents also include the soil release agents of U.S. Patent 4,877,896, issued October 31 , 1989 to Maldonado et al, which discloses anionic, especially sulfoarolyl, end-capped terephthalate esters.
  • Another soil release agent is an oligomer with repeat units of terephthaloyl units, sulfoisoterephthaloyl units, oxyethyleneoxy and oxy-l ,2-propylene units.
  • the repeat units form the backbone of the oligomer and are preferably terminated with modified isethionate end-caps.
  • a particularly preferred soil release agent of this type comprises about one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-1 ,2- propyleneoxy units in a ratio of from about 1.7 to about 1.8, and two end- cap units of sodium 2-(2-hydro xy ethoxy )-ethanesulfonate.
  • a preferred organic silver coating agent is a paraffin oil, typically a predominantly branched aliphatic hydrocarbon having a number of carbon atoms in the range of from 20 to 50; preferred paraffin oil selected from predominantly branched C25-45 species with a ratio of cyclic to noncyclic hydrocarbons of from 1 :10 to 2:1 , preferably from 1 :5 to 1 : 1.
  • Suitable nitrogen-containing corrosion inhibitor compounds include imidazole and derivatives thereof such as benzimidazole, 2- heptadecyl imidazole and those imidazole derivatives described in Czech Patent No. 139, 279 and British Patent GB-A-1, 137,741 , which also discloses a method for making imidazole compounds.
  • nitrogen-containing corrosion inhibitor compounds are pyrazole compounds and their derivatives, particularly those where the pyrazole is substituted in any of the 1 , 3, 4 or 5 positions by substituents R ⁇ , R3, R4 and R5 where R] is any of H, CH2OH, CONH3, or COCH3, R3 and R5 are any of C1-C20 alkyl or hydroxyl, and R4 is any of H, NH2 or N ⁇ 2-
  • nitrogen-containing corrosion inhibitor compounds include benzotriazole, 2-mercaptobenzothiazole, l-phenyl-5- mercapto-l ,2,3,4-tetrazole, thionalide, mo ⁇ holine, melamine, distearylamine, stearoyl stearamide, cyanuric acid, aminotriazole, aminotetrazole and indazole.
  • Nitrogen-containing compounds such as amines, especially distearylamine and ammonium compounds such as ammonium chloride, ammonium bromide, ammonium sulphate or diammonium hydrogen citrate are also suitable.
  • the compositions may contain an Mn(II) corrosion inhibitor compound.
  • the Mn(II) compound is preferably inco ⁇ orated at a level of from 0.005% to 5% by weight, more preferably from 0.01 % to 1 % , most preferably from 0.02% to 0.4% by weight of the compositions.
  • the Mn(II) compound is inco ⁇ orated at a level to provide from 0.1 ppm to 250 ppm, more preferably from 0.5 ppm to 50 ppm, most preferably from 1 ppm to 20 ppm by weight of Mn(II) ions in any bleaching solution.
  • the Mn (II) compound may be an inorganic salt in anhydrous, or any hydrated forms. Suitable salts include manganese sulphate, manganese carbonate, manganese phosphate, manganese nitrate, manganese acetate and manganese chloride.
  • the Mn(II) compound may be a salt or complex of an organic fatty acid such as manganese acetate or manganese stearate.
  • the Mn(II) compound may be a salt or complex of an organic ligand.
  • the organic ligand is a heavy metal ion sequestrant.
  • the organic ligand is a crystal growth inhibitor.
  • additional corrosion inhibitor compounds include, mercaptans and diols, especially mercaptans with 4 to 20 carbon atoms including lauryl mercaptan, thiophenol, thionapthol, thionalide and thioanthranol. Also suitable are saturated or unsaturated C10-C20 fatty acids, or their salts, especially aluminium tristearate. The C12-C20 hydroxy fatty acids, or their salts, are also suitable. Phosphonated octa- decane and other anti-oxidants such as betahydroxytoluene (BHT) are also suitable.
  • BHT betahydroxytoluene
  • Copolymers of butadiene and maleic acid particularly those supplied under the trade reference no. 07787 by Polysciences Inc have been found to be of particular utility as corrosion inhibitor compounds.
  • the level of available oxygen in the present compositions is preferably controlled; the level of available oxygen should hence preferably be in the range from 0.3% to 2.5% , preferably from 0.5% to 1.7% , more preferably from 0.6% to 1.5% , most preferably from 0.7% to 1.2% , measured according to the method described hereunder.
  • the rate of release of available oxygen is preferably also controlled; the rate of release of available oxygen from the compositions herein preferably should be such that, when using the method described hereinafter, the available oxygen is not completely released from the composition until after 3.5 minutes, preferably the available oxygen is released in a time interval of from 3.5 minutes to 10.0 minutes, more preferably from 4.0 minutes to 9.0 minutes, most preferably from 5.0 minutes to 8.5 minutes.
  • a beaker of water (typically 2L) is placed on a stirrer Hotplate, and the stirrer speed is selected to ensure that the product is evenly dispersed through the solution.
  • the detergent composition typically 8g of product which has been sampled down from a bulk supply using a Pascal sampler
  • the detergent composition is added and simultaneously a stop clock is started.
  • the temperature control should be adjusted so as to maintain a constant temperature of 20°C throughout the experiment.
  • the level of AvO, measured in units of % available oxygen by weight, for the sample at each time interval corresponds to the amount of titre according to the following equation
  • AvO level is plotted versus time to determine the maximum level of AvO, and the rate of release of AvO
  • Controlled rate of release - means
  • a means may be provided for controlling the rate of release of oxygen bleach to the wash solution.
  • Means for controlling the rate of release of the bleach may provide for controlled release of peroxide species to the wash solution.
  • Such means could, for example, include controlling the release of any inorganic perhydrate salt, acting as a hydrogen peroxide source, to the wash solution.
  • Suitable controlled release means can include coating any suitable component with a coating designed to provide the controlled release.
  • the coating may therefore, for example, comprise a poorly water soluble material, or be a coating of sufficient thickness that the kinetics of dissolution of the thick coating provide the controlled rate of release.
  • the coating material may be applied using various methods. Any coating material is typically present at a weight ratio of coating material to bleach of from 1:99 to 1:2, preferably from 1:49 to 1:9.
  • Suitable coating materials include triglycerides (e.g. partially) hydrogenated vegetable oil, soy bean oil, cotton seed oil) mono or diglycerides, microcrystalline waxes, gelatin, cellulose, fatty acids and any mixtures thereof.
  • suitable coating materials can comprise the alkali and alkaline earth metal sulphates, silicates and carbonates, including calcium carbonate and silicas.
  • a preferred coating material particularly for an inorganic perhydrate salt bleach source, comprises sodium silicate of Si ⁇ 2 : Na2 ⁇ ratio from 1.8 : 1 to 3.0 : 1 , preferably 1.8: 1 to 2.4:1 , and/or sodium metasilicate, preferably applied at a level of from 2% to 10% , (normally from 3 % to 5%) of Si ⁇ 2 by weight of the inorganic perhydrate salt.
  • Magnesium silicate can also be included in the coating.
  • Suitable means of providing the required controlled release include mechanical means for altering the physical characteristics of the bleach to control its solubility and rate of release. Suitable protocols could include compaction, mechanical injection, manual injection, and adjustment of the solubility of the bleach compound by selection of particle size of any particulate component.
  • particle size Whilst the choice of particle size will depend both on the composition of the particulate component, and the desire to meet the desired controlled release kinetics, it is desirable that the particle size should be more than 500 micrometers, preferably having an average particle diameter of from 800 to 1200 micrometers.
  • Additional protocols for providing the means of controlled release include the suitable choice of any other components of the detergent composition matrix such that when the composition is introduced to the wash solution the ionic strength environment therein provided enables the required controlled release kinetics to be achieved.
  • detergent compositions containing the bleaching compositions hereinbefore described and one or more detergent ingredients are provided.
  • the detergent ingredients are preferably selected from builder compounds, sources of alkalinity, surfactants, heavy metal ion sequestrants, crystal growth inhibitors, enzymes, organic polymeric compounds, and suds suppressors.
  • the binding constant for bismuth with organic diphosphonate ligands has, in general, been found to be high enough to ensure the stability of the salt or complex in a bleaching/detergent product, but weak enough such that on introduction of the product to a wash solution the bismuth ions are readily released from the compound to the wash solution.
  • the detergent compositions preferably contain the bismuth diphosphonate compound at a level of from 0.005 % to 20% , more preferably from 0.01 % to 5%, most preferably from 0.1 % to 1 % by weight of the detergent composition.
  • Preferred detergent compositions herein are adapted for use in a machine dishwashing method. Such compositions are formulated to enable the removal of, typically food based, soils and stains from soiled tableware under the conditions present in a machine dishwasher. Typically the compositions are low foaming, preferably containing only low levels of low-foaming surfactants.
  • a preferred detergent composition herein comprises a detergent component selected from the group consisting of a water soluble builder compound, a low foaming surfactant system and any mixtures thereof, and the hereinbefore described bleaching composition.
  • the detergent compositions of the present invention may contain as a highly preferred component a water-soluble builder compound, typically present at a level of from 1 % to 80% by weight, preferably from 10% to 70% by weight, most preferably from 20% to 60% by weight of the composition.
  • Suitable water-soluble builder compounds include the water soluble monomeric poly carboxylates, or their acid forms, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more that two carbon atoms, carbonates, bicarbonates, borates, phosphates, and mixtures of any of the foregoing.
  • the carboxylate or polycarboxylate builder can be monomeric or oligomeric in type although monomeric polycarboxylates are generally preferred for reasons of cost and performance.
  • Suitable carboxylates containing one carboxy group include the water soluble salts of lactic acid, gly colic acid and ether derivatives thereof.
  • Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic 34
  • Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxy methyloxysuccinates described in British Patent No. 1 ,379,241, lactoxysuccinates described in British Patent No.
  • Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829, 1,1 ,2,2-ethane tetracarboxylates, 1 , 1 ,3,3-propane tetracarboxylates and 1 ,1 ,2,3-propane tetracarboxylates.
  • Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1 ,398,421 and 1 ,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1 ,439,000.
  • Alicyclic and heterocyclic polycarboxylates include cyclopentane- cis,cis,cis-tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5- tetrahydrofuran - cis, cis, cis-tetracarboxylates, 2,5-tetrahydrofuran - cis - dicarboxylates, 2,2,5, 5 -tetrahydrofuran - tetracarboxylates, 1 ,2,3,4,5,6- hexane - hexacarboxylates and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol.
  • Aromatic polycarboxylates include mellitic acid, pyromellitic acid and the phthalic acid derivatives disclosed in British Patent No. 1 ,425,343.
  • the preferred polycarboxylates are hydro y carboxylates containing up to three carboxy groups per molecule, more particularly citrates.
  • the parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts e.g. citric acid or citrate/citric acid mixtures are also contemplated as useful builder components.
  • Borate builders, as well as builders containing borate-forming materials that can produce borate under detergent storage or wash conditions can also be used but are not preferred at wash conditions less that about 50°C, especially less than about 40°C.
  • carbonate builders are the alkaline earth and alkali metal carbonates, including sodium carbonate and sesqui-carbonate and mixtures thereof with ultra-fine calcium carbonate as disclosed in German Patent Application No. 2,321 ,001 published on November 15, 1973.
  • water-soluble phosphate builders are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta/phosphate in which the degree of polymerization ranges from about 6 to 21 , and salts of phytic acid.
  • Partially soluble or insoluble builder compound Partially soluble or insoluble builder compound
  • the detergent compositions of the present invention may less preferably contain a partially soluble or insoluble builder compound.
  • partially water soluble builders include the crystalline layered silicates as disclosed for example, in EP-A-0164514, DE-A-3417649 and DE-A- 3742043.
  • largely water insoluble builders include the sodium aluminosilicates, including Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite MAP, Zeolite HS and mixtures thereof.
  • the detergent compositions preferably contain an alkalinity system containing sodium silicate having an Si ⁇ 2 : Na2 ⁇ ratio of from 1.8 to 3.0, preferably from 1.8 to 2.4, most preferably 2.0, present preferably at a level of less than 20% , preferably from 1 % to 15% , most preferably from 3% to 12% by weight of Si ⁇ 2-
  • the alkali metal silicate may be in the form of either the anhydrous salt or a hydrated salt.
  • the alkalinity system also preferably contains sodium metasilicate, present at a level of at least 0.4% Si ⁇ 2 by weight.
  • Sodium metasilicate has a nominal Si ⁇ 2 : Na2 ⁇ ratio of 1.0.
  • the weight ratio of said sodium silicate to said sodium metasilicate, measured as Si ⁇ 2, is preferably from 50:1 to 5:4, more preferably from 15: 1 to 2: 1 , most preferably from 10: 1 to 5:2.
  • a highly preferred component of the detergent compositions of the invention is a surfactant system comprising surfactant selected from anionic, cationic, nonionic ampholytic and zwitterionic surfactants and mixtures thereof.
  • Automatic dishwashing machine products should be low foaming in character and thus the foaming of the surfactant system must be suppressed or more preferably be low foaming, typically nonionic in character.
  • the surfactant system is typically present at a level of from 0.2% to 30% by weight, more preferably from 0.5% to 10% by weight, most preferably from 1 % to 5% by weight of the compositions.
  • nonionic surfactants useful for detersive pu ⁇ oses can be included in the compositions.
  • Preferred, non-limiting classes of useful nonionic surfactants are listed below.
  • alkyl ethoxylate condensation products of aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide are suitable for use herein.
  • the alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms.
  • Particularly preferred are the condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms with from about 2 to about 10 moles of ethylene oxide per mole of alcohol.
  • the ethoxylated C -Cig fatty alcohols and Cg-Cig mixed ethoxylated/propoxylated fatty alcohols are suitable surfactants for use herein, particularly where water soluble.
  • the ethoxylated fatty alcohols are the C10-C18 ethoxylated fatty alcohols with a degree of ethoxylation of from 3 to 50, most preferably these are the C12-C18 ethoxylated fatty alcohols with a degree of ethoxylation from 3 to 40.
  • the mixed ethoxylated/propoxylated fatty alcohols have an alkyl chain length of from 10 to 18 carbon atoms, a degree of ethoxylation of from 3 to 30 and a degree of propoxylation of from 1 to 10.
  • the condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are suitable for use herein.
  • the hydrophobic portion of these compounds preferably has a molecular weight of from about 1500 to about 1800 and exhibits water insolubility.
  • Examples of compounds of this type include certain of the commercially-available Pluronic ⁇ M surfactants, marketed by BASF.
  • condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine are suitable for use herein.
  • the hydrophobic moiety of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of from about 2500 to about 3000.
  • this type of nonionic surfactant include certain of the commercially available TetronicTM compounds, marketed by BASF.
  • the detergent compositions of the invention preferably contain as an optional component a heavy metal ion sequestrant.
  • heavy metal ion sequestrant it is meant herein components which act to sequester (chelate) heavy metal ions. These components may also have calcium and magnesium chelation capacity, but preferentially they show selectivity to binding heavy metal ions such as iron, manganese and copper.
  • Heavy metal ion sequestrants are generally present at a level of from 0.005% to 20% , preferably from 0.1 % to 10% , more preferably from 0.25% to 7.5% and most preferably from 0.5 % to 5 % by weight of the compositions.
  • Heavy metal ion sequestrants which are acidic in nature, having for example phosphonic acid or carboxylic acid functionalities, may be present either in their acid form or as a complex/salt with a suitable counter cation such as an alkali or alkaline metal ion, ammonium, or substituted ammonium ion, or any mixtures thereof.
  • a suitable counter cation such as an alkali or alkaline metal ion, ammonium, or substituted ammonium ion, or any mixtures thereof.
  • any salts/complexes are water soluble.
  • the molar ratio of said counter cation to the heavy metal ion sequestrant is preferably at least 1 : 1.
  • Suitable heavy metal ion sequestrants for use herein include organic phosphonates, such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1 -hydroxy disphosphonates and nitrilo trimethylene phosphonates.
  • organic phosphonates such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1 -hydroxy disphosphonates and nitrilo trimethylene phosphonates.
  • Preferred among the above species are diethylene triamine penta (methylene phosphonate), ethylene diamine tri (methylene phosphonate) hexamethylene diamine tetra (methylene phosphonate) and hydroxy-ethylene 1 ,1 diphosphonate.
  • Suitable heavy metal ion sequestrant for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetracetic acid, ethylenetriamine pentacetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2- hydroxypropylenediamine disuccinic acid or any salts thereof.
  • EDDS ethylenediamine-N,N'-disuccinic acid
  • alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof Especially preferred is ethylenediamine-N,N'-disuccinic acid (EDDS) or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof.
  • Preferred EDDS compounds are the free acid form and the sodium or magnesium salt or complex thereof.
  • the detergent compositions in addition to the bismuth diphosphonate compound, preferably contain a crystal growth inhibitor component, preferably an additional organodiphosphonate component, inco ⁇ orated preferably at a level of from 0.01 % to 5% , more preferably from 0.1 % to 2% by weight of the compositions.
  • organo diphosphonate it is meant herein an organo diphosphonate salt or organo diphosphonic acid which does not contain nitrogen as part of its chemical structure. This definition therefore excludes the organo aminophosphonates, which however may be included in compositions of the invention as heavy metal ion sequestrant components.
  • the organo diphosphonate is preferably a C1-C4 diphosphonate, more preferably a C2 diphosphonate, such as ethylene diphosphonate, or most preferably ethane 1 -hydroxy- 1 , 1 -diphosphonate (HEDP) and may be present in partially or fully ionized form, particularly as a salt or complex.
  • HEDP ethane 1 -hydroxy- 1 , 1 -diphosphonate
  • Another optional ingredient useful in the detergent compositions is one or more enzymes.
  • Preferred enzymatic materials include the commercially available lipases, amylases, neutral and alkaline proteases, esterases, cellulases, pectinases, lactases and peroxidases conventionally inco ⁇ orated into detergent compositions. Suitable enzymes are discussed in US Patents 3,519,570 and 3,533, 139.
  • protease enzymes include those sold under the tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo Industries A/S (Denmark), those sold under the tradename Maxatase, Maxacal and Maxapem by Gist-Brocades, those sold by Genencor International, and those sold under the tradename Opticlean and Optimase by Solvay Enzymes.
  • Protease enzyme may be inco ⁇ orated into the compositions in accordance with the invention at a level of from 0.0001 % to 4% active enzyme by weight of the composition.
  • Preferred amylases include, for example, ⁇ -amylases obtained from a special strain of B licheniformis, described in more detail in GB-1 ,269,839 (Novo).
  • Preferred commercially available amylases include for example, those sold under the tradename Rapidase by Gist-Brocades, and those sold under the tradename Termamyl and BAN by Novo Industries A/S.
  • Amylase enzyme may be inco ⁇ orated into the composition in accordance with the invention at a level of from 0.0001 % to 2% active enzyme by weight of the composition.
  • Lipolytic enzyme may be present at levels of active lipolytic enzyme of from 0.0001 % to 2% by weight, preferably 0.001 % to 1 % by weight, most preferably from 0.001 % to 0.5% by weight of the compositions.
  • the lipase may be fungal or bacterial in origin. Lipase from chemically or genetically modified mutants of these strains are also useful herein.
  • a preferred lipase is described in Granted European Patent, EP-B- 0218272.
  • An especially preferred lipase herein is obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Aspergillus oryza.
  • Preferred enzyme-containing compositions herein may comprise from about 0.001 % to about 10% , preferably from about 0.005% to about 8% , most preferably from about 0.01 % to about 6% , by weight of an enzyme stabilizing system.
  • the enzyme stabilizing system can be any stabilizing system which is compatible with the detersive enzyme.
  • Such stabilizing systems can comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acid, boronic acid, chlorine bleach scavengers and mixtures thereof.
  • Such stabilizing systems can also comprise reversible enzyme inhibitors, such as reversible protease inhibitors.
  • Organic polymeric compounds may be added as preferred components of the detergent compositions in accord with the invention.
  • organic polymeric compound it is meant essentially any polymeric organic compound commonly used as dispersants, and anti-redeposition and soil suspension agents in detergent compositions.
  • Organic polymeric compound is typically inco ⁇ orated in the detergent compositions of the invention at a level of from 0.1 % to 30% , preferably from 0.5% to 15 %, most preferably from 1 % to 10% by weight of the compositions.
  • organic polymeric compounds include the water soluble organic homo- or co-polymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms.
  • Polymers of the latter type are disclosed in GB-A-1 ,596,756.
  • salts are polyacrylates of molecular weight 2000-10000 and their copolymers with any suitable other monomer units including modified acrylic, fumaric, maleic, itaconic, aconitic, mesaconic, citraconic and methylenemalonic acid or their salts, maleic anhydride, acrylamide, alkylene, vinylmethyl ether, styrene and any mixtures thereof.
  • Preferred are the copolymers of acrylic acid and maleic anhydride having a molecular weight of from 20,000 to 100,000.
  • Preferred commercially available acrylic acid containing polymers having a molecular weight below 15,000 include those sold under the tradename Sokalan PA30, PA20, PA15, PA10 and Sokalan CP10 by BASF GmbH, and those sold under the tradename Acusol 45N by Rohm and Haas.
  • Preferred acrylic acid containing copolymers include those which contain as monomer units: a) from 90% to 10% , preferably from 80% to 20% by weight acrylic acid or its salts and b) from 10% to 90%, preferably from 20% to 80% by weight of a substituted acrylic monomer or its salts having the general formula -[CR2-CR ⁇ (CO-0-R3)]- wherein at least one of the substituents R ⁇ , R2 or R3, preferably R ⁇ or R2 is a 1 to 4 carbon alkyl or hydroxyalkyl group, R ⁇ or R2 can be a hydrogen and R3 can be a hydrogen or alkali metal salt.
  • R ⁇ is methyl
  • R2 is hydrogen (i.e. a methacrylic acid monomer).
  • the most preferred copolymer of this type has a molecular weight of 3500 and contains 60% to 80% by weight of acrylic acid and 40% to 20% by weight of methacrylic acid.
  • polyamino compounds are useful herein including those derived from aspartic acid such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.
  • the detergent compositions of the invention may contain a lime soap dispersant compound, preferably present at a level of from 0.1 % to 40% by weight, more preferably 1 % to 20% by weight, most preferably from 2% to 10% by weight of the compositions.
  • a lime soap dispersant is a material that prevents the precipitation of alkali metal, ammonium or amine salts of fatty acids by calcium or magnesium ions.
  • Preferred lime soap disperant compounds are disclosed in PCT Application No. WO93/08877 (attorney's docket no. CM466M).
  • the detergent compositions of the invention when formulated for use in machine washing compositions, preferably comprise a suds suppressing system present at a level of from 0.01 % to 15% , preferably from 0.05% to 10% , most preferably from 0.1 % to 5% by weight of the composition.
  • Suitable suds suppressing systems for use herein may comprise essentially any known antifoam compound, including, for example silicone antifoam compounds, 2-alkyl and alcanol antifoam compounds.
  • Preferred suds suppressing systems and antifoam compounds are disclosed in PCT Application No. WO93/08876 (attorney's docket no. CM465M) and copending European Application No. 93870132.3 (attorney's docket no. CM562F).
  • the detergent compositions herein may also comprise from 0.01 % to 10 % , preferably from 0.05% to 0.5% by weight of polymeric dye transfer inhibiting agents.
  • the polymeric dye transfer inhibiting agents are preferably selected from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N- vinylimidazole, polyvinylpyrrolidonepolymers or combinations thereof.
  • the present detergent compositions are preferably not formulated to have an unduly high pH, in preference having a pH measured as a 1 % solution in distilled water of from 8.0 to 12.0, more preferably from 9.0 to 11.8, most preferably from 9.5 to 11.5.
  • the detergent compositions of the invention can be formulated in any desirable form such as powders, granulates, pastes, liquids, gels and tablets, solid, particularly granular forms being preferred.
  • the bulk density of the granular detergent compositions in accordance with the present invention is typically of at least 650 g/litre, more usually at least 700 g/litre and more preferably from 800 g/litre to 1200 g/litre.
  • the particle size of the components of granular compositions in accordance with the invention should preferably be such that no more that 5 % of particles are greater than 1.4mm in diameter and not more than 5 % of particles are less than 0.15mm in diameter.
  • the liquid should be thixotropic (ie; exhibit high viscosity when subjected to low stress and lower viscosity when subjected to high stress), or at least have very high viscosity, for example, of from 1 ,000 to 10,000,000 centipoise.
  • a preferred machine dishwashing method comprises treating soiled articles selected from crockery, glassware, hollowware, silverware and cutlery and mixtures thereof, with an aqueous liquid having dissolved or dispensed therein an effective amount of a machine dishwashing composition in accord with the invention.
  • an effective amount of the machine dishwashing composition it is meant from 8g to 60g of product dissolved or dispersed in a wash solution of volume from 3 to 10 litres, as are typical product dosages and wash solution volumes commonly employed in conventional machine dishwashing methods.
  • Nonionic C13-C15 mixed ethoxylated/propoxylated fatty alcohol with an average degree of ethoxylation of 3.8 and an average degree of propoxylation of 4.5 sold under the tradename Plurafac LF404 by BASF Gmbh (low foaming)
  • Cationic precursor Cationic peroxyacid bleach precursor salt of trialkyl ammonium methylene C5-alkyl caprolactam with tosylate
  • DETPMP Diethylene triamine penta (methylene phosphonic acid), marketed by Monsanto under the tradename Dequest 2060
  • Paraffin Paraffin oil sold under the tradename Winog 70 by Wintershall.
  • Protease Proteolytic enzyme sold under the tradename Savinase by Novo Industries A/S (approx 2% enzyme activity).
  • Amylase Amylolytic enzyme sold under the tradename Termamyl 60T by Novo Industries A/S (approx 0.9% enzyme activity)
  • pH Measured as a 1 % solution in distilled water at
  • Agglomerate particles containing bismuth diphosphonate compounds were prepared as follows:
  • Bismuth HEDP particles were made by co-agglomeration of a solution formed by mixing the 1 :2.1 , 1 :3.5 and 1 :5.0 alkaline bismuth HEDP solutions with an alkaline solution (pH 12.0) of 480N binder, (formed by adding 333g of 480N binder with lOg of 50% NaOH) with sodium sulfate powder.
  • alkaline bismuth HEDP added to the alkaline 480N binder solution were:
  • the agglomeration was carried out 20 minutes after preparation of the alkaline bismuth HEDP/binder solution as follows: 500g of anyhydrous sodium sulfate powder was placed in a Kenwood Chef (tradename) mixing bowl. The K-beater (tradename) attachment was secured to the mixer and the sulfate mixed. During this mixing the alkaline bismuth HEDP/binder solution was trickled slowly onto the sulfate until this became slightly moist. The mixing was then stopped and the contents of the mixing bowl transferred to a fluid bed drier glass vessel. The sulphate was therein dried whilst fluidising at 80-90°C.
  • compositions A is a comparative composition
  • compositions B to H are in accord with the invention.
  • the Bismuth HEDP particles were made in accord with the process set out in Example 1.
  • compositions B to D were compared to that of comparative Composition A using the following twenty cycle test procedure.
  • a set of three silver spoons were placed in the cutlery basket of each of four Bosch (tradename) machine dishwashers.
  • a spike comprising 10 cm ⁇ of 0.262% by weight CaCl2.
  • 6H2O solution was added by pipette to the bottom of each dishwasher.
  • the 65 °C wash setting was selected, the wash process comprising main wash and rinse cycles. 20 grams of each composition was employed for each complete wash process.
  • the feed water hardness was 8° Clark Hardness (114.3 ppm CaC03 equivalent). Each set of three spoons was washed five times in each of the four machines (ie: 20 complete wash 4- rinse cycles).
  • the spoons were removed and then graded for silver tarnishing.
  • the grading was performed by 4 expert graders and the results averaged for each of the four sets of three spoons. Grading was through visual inspection according to the following scale :
  • Results were as follows : (average of the 4 gradings from the panellists)
  • Composition C as defined above, was stored in a plastic bottle for two weeks at 40°C and ambient humidity. The performance testing protocol as described above was then repeated with the Composition after storage. A tarnish grade of 0.5 was obtained, indicating that the bismuth/HEDP compound does not lose performance capability upon storage under these conditions.

Landscapes

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

Abstract

L'invention concerne un composé de diphosphonate de bismuth, dans lequel le rapport molaire bismuth/diphosphonate est compris entre 1:0,7 et 1:7. L'invention concerne également des compositions de blanchiment et des compositions détergentes conçues pour être utilisées dans le lavage de vaisselle en machine et présentant un effet ternissant de l'argent réduit ainsi que de bonnes propriétés lavantes. Ces compositions contiennent un agent de blanchiment à l'oxygène et le composé de diphosphonate de bismuth. On décrit également des procédés préférés pour produire lesdites compositions.
EP97905571A 1996-01-11 1997-01-09 Compositions pour lavage de vaisselle en machine Withdrawn EP0948593A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB9600553 1996-01-11
GB9600553A GB2309032A (en) 1996-01-11 1996-01-11 Bismuth salts and complexes with nitrogen-free organic diphosphonic acids
PCT/US1997/000471 WO1997025405A1 (fr) 1996-01-11 1997-01-09 Compositions pour lavage de vaisselle en machine

Publications (2)

Publication Number Publication Date
EP0948593A1 true EP0948593A1 (fr) 1999-10-13
EP0948593A4 EP0948593A4 (fr) 1999-10-13

Family

ID=10786899

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97905571A Withdrawn EP0948593A1 (fr) 1996-01-11 1997-01-09 Compositions pour lavage de vaisselle en machine

Country Status (5)

Country Link
EP (1) EP0948593A1 (fr)
BR (1) BR9706928A (fr)
CA (1) CA2242418A1 (fr)
GB (1) GB2309032A (fr)
WO (1) WO1997025405A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005037975A1 (fr) * 2003-10-17 2005-04-28 Reckitt Benckiser N.V. Composition permettant de proteger les articles de verre dans un lave-vaisselle
GB0625586D0 (en) * 2006-12-21 2007-01-31 Reckitt Benckiser Nv Composition
US9144538B2 (en) 2013-02-08 2015-09-29 The Procter & Gamble Company Cosmetic compositions containing substituted azole and methods for alleviating the signs of photoaged skin
US9138393B2 (en) 2013-02-08 2015-09-22 The Procter & Gamble Company Cosmetic compositions containing substituted azole and methods for improving the appearance of aging skin
MX2019009688A (es) 2017-02-17 2019-12-18 Virox Tech Inc Soluciones desinfectantes basadas en peroxido que contienen sales inorganicas.

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1586067A (en) * 1976-10-28 1981-03-18 Procter & Gamble Detergent composition
EP0070587A1 (fr) * 1981-07-17 1983-01-26 THE PROCTER & GAMBLE COMPANY Composition du moyen d'aide de lavage
US4517060A (en) * 1983-05-27 1985-05-14 Schering Aktiengesellschaft Method and bath for electrodepositing a violet-colored gold-copper-bismuth alloy
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
WO1996022348A1 (fr) * 1995-01-20 1996-07-25 The Procter & Gamble Company Compositions pour lave-vaisselle contenant un agent de blanchiment oxygene et un sel de bismuth permettant de reduire le ternissement de l'argent

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4856593A (en) * 1987-09-21 1989-08-15 Conoco Inc. Inhibition of hydrate formation
GB8813889D0 (en) * 1988-06-11 1988-07-13 Micro Image Technology Ltd Solutions of permonosulphuric acid
GB8813891D0 (en) * 1988-06-11 1988-07-13 Micro Image Technology Ltd Solutions of perhalogenated compounds
US5534180A (en) * 1995-02-03 1996-07-09 Miracle; Gregory S. Automatic dishwashing compositions comprising multiperacid-forming bleach activators

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1586067A (en) * 1976-10-28 1981-03-18 Procter & Gamble Detergent composition
EP0070587A1 (fr) * 1981-07-17 1983-01-26 THE PROCTER & GAMBLE COMPANY Composition du moyen d'aide de lavage
US4517060A (en) * 1983-05-27 1985-05-14 Schering Aktiengesellschaft Method and bath for electrodepositing a violet-colored gold-copper-bismuth alloy
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
WO1996022348A1 (fr) * 1995-01-20 1996-07-25 The Procter & Gamble Company Compositions pour lave-vaisselle contenant un agent de blanchiment oxygene et un sel de bismuth permettant de reduire le ternissement de l'argent

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO9725405A1 *

Also Published As

Publication number Publication date
CA2242418A1 (fr) 1997-07-17
GB2309032A (en) 1997-07-16
WO1997025405A1 (fr) 1997-07-17
EP0948593A4 (fr) 1999-10-13
GB9600553D0 (en) 1996-03-13
BR9706928A (pt) 1999-07-20

Similar Documents

Publication Publication Date Title
US6162259A (en) Machine dishwashing and laundry compositions
US5827808A (en) Dishwashing method
US6165970A (en) Detergent composition comprising acrylic acid-based polymer and amino tricarboxylic acid-based compound
US6221430B1 (en) Process for making a detergent particle
GB2311536A (en) Dishwashing and laundry detergents
GB2311535A (en) Detergent compositions
GB2320255A (en) Process for making tabletted detergent compositions
GB2283494A (en) Machine dishwashing
EP0948593A1 (fr) Compositions pour lavage de vaisselle en machine
US5843877A (en) Machine dishwashing compositions containing an oxygen bleach and a bismuth salt to reduce silver tarnishing
WO1996022348A1 (fr) Compositions pour lave-vaisselle contenant un agent de blanchiment oxygene et un sel de bismuth permettant de reduire le ternissement de l'argent
WO1998051769A1 (fr) Procede anti-ternissant pour l'argenterie ternie
EP0889947A1 (fr) Composition detergente pour lave-vaisselle
EP0726933A1 (fr) Compositions detergentes
GB2309974A (en) Use of cellulose ethers for soil removal
GB2309975A (en) Use of cellulose ethers in dishwashing
WO1996017051A1 (fr) Compositions detergentes pour lave-vaisselle contenant des melanges de silicates
EP0794999A1 (fr) Poudre non ternissante pour lave-vaisselle contenant un agent de blanchiment a l'oxygene, un metasilicate et un silicate a haute teneur en silice
EP0944711A1 (fr) Procede de fabrication de compositions detergentes se presentant sous forme de pastilles
GB2307696A (en) Machine dishwashing compositions

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19980731

A4 Supplementary search report drawn up and despatched

Effective date: 19990804

AK Designated contracting states

Kind code of ref document: A4

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LI LU NL PT SE

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LI LU NL PT SE

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20010801