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EP0706559B1 - Composition pour lave-vaisselle contenant un agent de blanchiment oxygene, de l'huile de paraffine et un compose benzotriazole pour inhiber le ternissement de l'argent - Google Patents

Composition pour lave-vaisselle contenant un agent de blanchiment oxygene, de l'huile de paraffine et un compose benzotriazole pour inhiber le ternissement de l'argent Download PDF

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Publication number
EP0706559B1
EP0706559B1 EP94921436A EP94921436A EP0706559B1 EP 0706559 B1 EP0706559 B1 EP 0706559B1 EP 94921436 A EP94921436 A EP 94921436A EP 94921436 A EP94921436 A EP 94921436A EP 0706559 B1 EP0706559 B1 EP 0706559B1
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Prior art keywords
composition according
weight
alkyl
composition
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EP94921436A
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German (de)
English (en)
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EP0706559A1 (fr
EP0706559A4 (fr
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Julie Ann Christie
Fiona Susan Macbeath
John Christopher Turner
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Procter and Gamble Co
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Procter and Gamble Co
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Publication of EP0706559A4 publication Critical patent/EP0706559A4/en
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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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent compositions
    • 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
    • C11D3/18—Hydrocarbons
    • 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
    • C11D3/3902—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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/24—Hydrocarbons
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3245—Aminoacids
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3281—Heterocyclic compounds

Definitions

  • the present invention relates to machine dishwashing compositions exhibiting good bleachable stain removal and enhanced anti 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 dishes and glassware, as reflected by numerous patent publications.
  • the present invention is concerned with the silver-tamishing problem encountered when bleaching compositions which contain oxygen-bleaching species are employed in machine dishwashing methods.
  • a problem encountered with the use of such bleaches is the tarnishing of any silverware components of the washload.
  • Oxygen bleaches tend to give rise to the problem of tarnishing more than chlorine bleaches.
  • the level of tarnishing observed 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 a product which maximises bleachable soil cleaning but minimises the occurrence of tarnishing of silverware components of the washload.
  • the rate of release of the oxygen bleach is 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.
  • the rate of release of any organic peroxyacid species to the wash solution is preferably controlled.
  • compositions suitable for use in machine dishwashing methods, having enhanced anti-silver tamishing properties, as well as good cleaning performance, particularly bleachable soil removal performance.
  • compositions are based on oxygen-bleaching species, and preferably are in a compact form and have a pH of 9.6 or greater.
  • EP-A-0,150,387 discloses chlorine-bleach based machine dishwashing compositions containing a paraffin wax as suds suppressor.
  • EP-A-0,180,088 discloses machine dishwashing compositions based on carbonates and silicates, containing paraffin oils as dust binders.
  • a machine dishwashing composition having bleachable stain removal and anti-silver tarnishing properties comprising
  • the rate of release of said available oxygen is such that the available oxygen is completely released from the composition in a time interval of from 3.5 minutes to 10.0 minutes, using the test protocol described in the present description.
  • compositions contain as essential components, an oxygen-releasing bleaching species, a benzotriazole compound and a paraffin oil.
  • the level of available oxygen is controlled.
  • the rate of release of available oxygen and of any organic peroxyacid bleaching species is also controlled.
  • the first essential feature of the compositions of the invention is a bleaching agent selected from oxygen-releasing agents such as inorganic perhydrate salts, peroxyacid bleach precursors, organic peroxyacids and mixtures thereof.
  • inorganic perhydrate salts include perborate, percarbonate, perphosphate, 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 NaBO 2 H 2 O 2 or the tetrahydrate NaBO 2 H 2 O 2 .3H 2 O.
  • Sodium percarbonate which is a preferred perhydrate for inclusion in compositions in accordance with the invention, is an addition compound having a formula corresponding to 2Na 2 CO 3 .3H 2 O 2 , and is available commercially as a crystalline solid.
  • the percarbonate is most preferably incorporated 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.
  • This coating however allows for rapid release of the percarbonate bleach to the wash solution and is therefore not a suitable means for providing controlled release of the percarbonate bleach into a wash solution.
  • Such coatings together with coating processes have previously been described in GB-1,466,799, granted to Interox on 9th March 1977.
  • 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 Na 2 SO 4 .n.Na 2 CO 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 use in the compositions herein. Another perhydrate is monoperoxy phthalic acid.
  • Inorganic perhydrate salts are normally incorporated 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.
  • Suitable peroxyacid bleach precursors typically contain one or more N- or O-acyl groups, which precursors can be selected from a wide range of classes.
  • Suitable classes include, imides and acylated derivatives of imidazoles and oximes, and 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.
  • the acylation products of sorbitol, glucose and all saccharides with benzoylating agents and acetylating agents are also suitable.
  • O-acylated precursor compounds include 2,3,3-tri-methyl hexanoyl oxybenzene sulfonates, benzoyl oxybenzene sulfonates, nonanoyl-6-amino caproyl oxybenzene sulfonates, monobenzoyltetraacetyl glucose, benzoyl peroxide and cationic derivatives of any of the above, including the alkyl ammonium derivatives and pentaacetyl glucose.
  • Phthalic anhydride is a suitable anhydride type precursor.
  • Specific cationic derivatives of the O-acyl precursor compounds include 2-(N,N,N-trimethyl ammonium) ethyl sodium 4-sulphophenyl carbonate chloride, and any of the alkyl ammonium derivatives of the benzoyl oxybenzene sulfonates including the 4-(trimethyl ammonium) methyl derivative.
  • Useful N-acyl compounds are disclosed in GB-A-855735, 907356 and GB-A-1246338.
  • Preferred precursor compounds of the imide type include N-benzoyl succinimide, tetrabenzoyl ethylene diamine, N-benzoyl substituted ureas and the N,N,N 1 N 1 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.
  • N-acylated precursor compounds of the lactam class are disclosed generally in GB-A-955735. Whilst the broadest aspect of the invention contemplates the use of any lactam useful as a peroxyacid precursor, preferred materials comprise the caprolactams and valerolactams.
  • Suitable N-acylated lactam precursors have the formula: wherein n is from 0 to 8, preferably from 0 to 2, and R 6 is H, an alkyl, aryl, alkoxyaryl or alkaryl group containing from 1 to 12 carbons, or a substituted phenyl group containing from 6 to 18 carbon atoms
  • Suitable caprolactam bleach precursors are of the formula: wherein R 1 is H or an alkyl, aryl, alkoxyaryl or alkaryl group containing from 1 to 12 carbon atoms, preferably from 6 to 12 carbon atoms, most preferably R 1 is phenyl.
  • Suitable valerolactams have the formula: wherein R 1 is H or an alkyl, aryl, alkoxyaryl or alkaryl group containing from 1 to 12 carbon atoms, preferably from 6 to 12 carbon atoms.
  • R 1 is selected from phenyl, heptyl, octyl, nonyl, 2,4,4-trimethylpentyl, decenyl and mixtures thereof.
  • the most preferred materials are those which are normally solid at ⁇ 30°C, particularly the phenyl derivatives, ie. benzoyl valerolactam, benzoyl caprolactam and their substituted benzoyl analogues such as chloro, amino alkyl, alkyl, aryl and alkoxy derivatives.
  • Caprolactam and valerolactam precursor materials wherein the R 1 moiety contains at least 6, preferably from 6 to 12 carbon atoms provide peroxyacids on perhydrolysis of a hydrophobic character which afford nucleophilic clean-up.
  • Precursor compounds wherein R 1 comprises from 1 to 6 carbon atoms provide hydrophilic bleaching species which are particularly efficient for bleaching beverage stains.
  • Mixtures of 'hydrophobic' and 'hydrophilic' caprolactams and valerolactams, typically at weight ratios of 1:5 to 5:1, preferably 1:1, can be used herein for mixed stain removal benefits.
  • caprolactam and valerolactam precursors include benzoyl caprolactam, nonanoyl caprolactam, benzoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl caprolactam, 3,5,5-trimethylhexanoyl valerolactam, octanoyl caprolactam, octanoyl valerolactam, decanoyl caprolactam, decanoyl valerolactam, undecenoyl caprolactam, undecenoyl valerolactam, (6-octanamidocaproyl)oxybenzene-sulfonate, (6-nonanamidocaproyl)oxybenzenesulfonate, (6-decanamidocaproyl)-oxybenzenesulfonate, and mixtures thereof.
  • Examples of highly preferred substituted benzoyl lactams include methylbenzoyl caprolactam, methylbenzoyl valerolactam, ethylbenzoyl caprolactam, ethylbenzoyl valerolactam, propylbenzoyl caprolactam, propylbenzoyl valerolactam, isopropylbenzoyl caprolactam, isopropylbenzoyl valerolactam, butylbenzoyl caprolactam, butylbenzoyl valerolactam, tert-butylbenzoyl caprolactam, tert-butylbenzoyl valerolactam, pentylbenzoyl caprolactam, pentylbenzoyl valerolactam, hexylbenzoyl caprolactam, hexylbenzoyl valerolactam, ethoxybenzoyl caprolactam, ethoxybenzo
  • Suitable imidazoles include N-benzoyl imidazole and N-benzoyl benzimidazole and other useful N-acyl group-containing peroxyacid precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.
  • R 1 is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms
  • R 2 is an alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms
  • R 5 is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms and L can be essentially any leaving group.
  • R 1 preferably contains from 6 to 12 carbon atoms.
  • R 2 preferably contains from 4 to 8 carbon atoms.
  • R 1 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 2 . The substitution can include alkyl, aryl, halogen, nitrogen, sulphur and other typical substituent groups or organic compounds.
  • R 5 is preferably H or methyl. R 1 and R 5 should not contain more than 18 carbon atoms in total. Amide substituted bleach activator compounds of this type are described in EP-A-0170386.
  • the L group must be sufficiently reactive for the 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.
  • pKa of the conjugate acid of the leaving group although exceptions to this convention are known. Ordinarily, leaving groups that exhibit such behavior are those in which their conjugate acid has a pKa in the range of from about 4 to about 13, preferably from about 6 to about 11 and most preferably from about 8 to about 11.
  • Preferred bleach precursors are those wherein R 1 , R 2 and R 5 are as defined for the amide substituted compounds and L is selected from the group consisting of: and mixtures thereof, wherein R 1 is an alkyl, aryl, or alkaryl group containing from 1 to about 14 carbon atoms, R 3 is an alkyl chain containing from 1 to 8 carbon atoms, R 4 is H or R 3 , and Y is H or a solubilizing group.
  • the preferred solubilizing groups are -SO 3 - M + , -CO 2 - M + , -SO 4 - M + , -N + (R 3 ) 4 X - and O ⁇ --N(R 3 ) 3 and most preferably -SO 3 - M + and -CO 2 - M + wherein R 3 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.
  • bleach activators with a leaving group that does not contain a solubilizing groups should be well dispersed in the bleaching solution in order to assist in their dissolution.
  • R 1 is H, alkyl, alkaryl, aryl, arylalkyl
  • R 2 , R 3 , R 4 , and R 5 may be the same or different substituents selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxyl, amino, alkyl amino, COOR 6 (wherein R 6 is H or an alkyl group) and carbonyl functions.
  • An especially preferred precursor of the benzoxazin-type is:
  • the peroxyacid bleach precursors are normally incorporated at a level of from 1% to 20% by weight, more preferably from 2% to 10% by weight, most preferably from 3% to 5% by weight of the compositions.
  • compositions may also contain organic peroxyacids, typically at a level of from 1% to 15% 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: wherein R 1 is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms, R 2 is an alkylene, arylene, or alkarylene group containing from 1 to 14 carbon atoms, and R 5 is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms. R 1 preferably contains from 6 to 12 carbon atoms. R 2 preferably contains from 4 to 8 carbon atoms.
  • R 1 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 2 . The substitution can include alkyl, aryl, halogen, nitrogen, sulphur and other typical substituent groups or organic compounds.
  • R 5 is preferably H or methyl. R 1 and R 5 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 diperoxy dodecanedioc acid, diperoxy tetra decanedioc acid, diperoxyhexadecanedioc acid, mono- and diperazelaic acid, mono- and diperbrassylic acid, monoperoxy phthalic acid and its magnesium salt, perbenzoic acid, and their salts as disclosed in, for example, EP-A-0341 947.
  • the level of available oxygen in the present compositions should be carefully controlled; the level of available oxygen should hence be in the range from 0.3% to 2.5%, preferably from 0.5% to 1.7%, more preferably from 0.6% to 1.2%, most preferably from 0.7% to 1.1%, 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.
  • 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 Vol S 2 O 3 (ml) X Molarity X 8 sample mass (g)
  • AvO level is plotted versus time as follows
  • composition contains a source of organic peroxyacid
  • rate of release of the organic peroxyacid species is also preferably controlled.
  • the kinetics of release to a wash solution are preferably such that in the T50 test method herein described the time to achieve a concentration that is 50% of the ultimate concentration of the peroxyacid bleach is from 180 seconds to 480 seconds, more preferably from 200 seconds to 400 seconds, most preferably from 240 seconds to 360 seconds.
  • the controlled release kinetics of the organic peroxyacid herein are defined with respect to a 'T50 test method' which measures the time to achieve 50% of the ultimate concentration/level of the organic peroxyacid when a composition containing the organic peroxyacid is dissolved according to the standard conditions now set out.
  • the standard conditions involve a 1 litre glass beaker filled with 1000 ml of distilled water at 20°C, to which 10g of composition is added. The contents of the beaker are agitated using a magnetic stirrer set at 100 rpm. The ultimate concentration/level is taken to be the concentration/level maximum level of organic peroxyacid attained after addition of the composition to the water-filled beaker.
  • Suitable analytical methods are chosen to enable a reliable determination of the incidental, and ultimate in solution concentrations of the organic peroxyacid, subsequent to the addition of the composition to the water in the beaker.
  • Such analytical methods can include those involving a continuous monitoring of the level of concentration of the component, including for example photometric and conductrimetric methods.
  • methods involving removing titres from the solution at set time intervals, stopping the disssolution process by an appropriate means such as by rapidly reducing the temperature of the titre, and then determining the concentration of the component in the titre by any means such as chemical titrimetric methods, can be employed.
  • Suitable graphical methods including curve fitting methods, can be employed, where appropriate, to enable calculation of the the TA value from raw analytical results.
  • the particular analytical method selected for determining the concentration of the organic peroxyacid component will depend on the nature of that component, and of the nature of the composition containing that component.
  • Controlled rate of release - means
  • a means may be provided for controlling the rate of release of AvO, or of organic peroxyacid to the wash solution.
  • Means for controlling the rate of release of organic peroxyacid may provide for controlled release of the peroxyacid bleach source itself to the wash solution.
  • the means may comprise a means of inhibiting, or preventing the in situ perhydrolysis reaction which releases the peroxyacid into the solution.
  • Such means could, for example, include controlling release of the hydrogen peroxide source to the wash solution, by for example, controlling 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.
  • Preferred coating material is sodium silicate of SiO 2 : Na 2 O ratio from 1.6 : 1 to 3.4 : 1, preferably 2.2:1 to 2.8:1, applied as an aqueous solution to give a level of from 2% to 10%, (normally from 3% to 5%) of silicate solids by weight of the percarbonate.
  • Magnesium silicate can also be included in the coating.
  • Suitable binders include the C 10 -C 20 alcohol ethoxylates containing from 5 - 100 moles of ethylene oxide per mole of alcohol and more preferably the C 15 -C 20 primary alcohol ethoxylates containing from 20 - 100 moles of ethylene oxide per mole of alcohol.
  • binders include certain polymeric materials.
  • 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 10 6 preferably 1000 to 400,000 most preferably 1000 to 10,000 are examples of such polymeric materials.
  • Copolymers of maleic anhydride with ethylene, methylvinyl ether or methacrylic acid, the maleic anhydride constituting at least 20 mole percent of the polymer are further examples of polymeric materials useful as binder agents.
  • polymeric materials may be used as such or in combination with solvents such as water, propylene glycol and the above mentioned C 10 -C 20 alcohol ethoxylates containing from 5 - 100 moles of ethylene oxide per mole.
  • solvents such as water, propylene glycol and the above mentioned C 10 -C 20 alcohol ethoxylates containing from 5 - 100 moles of ethylene oxide per mole.
  • binders include the C 10 -C 20 mono- and diglycerol ethers and also the C 10 -C 20 fatty acids.
  • 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.
  • One method for applying the coating material involves agglomeration.
  • Preferred agglomeration processes include the use of any of the organic binder materials described hereinabove. Any conventional agglomerator/mixer may be used including, but not limited to pan, rotary drum and vertical blender types. Molten coating compositions may also be applied either by being poured onto, or spray atomized onto a moving bed of bleaching agent.
  • 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 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.
  • the paraffin oil is the paraffin oil
  • compositions contain from 0.05% to 2.5%, preferably from 0.1% to 0.6% by weight of the total composition of 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 C 25-45 species with a ratio of cyclic to noncyclic hydrocarbons of from 1:10 to 2:1, preferably from 1:5 to 1:1.
  • compositions of the invention contain as an essential component a benzotriazole compound at a level of from 0.005% to 3%, preferably from 0.02% to 1% and most preferably from 0.05% to 0.5% of benzotriazole compound.
  • benzotriazole compound it is meant a compound of formula, which is benzotriazole, and any derivatives thereof.
  • Derivatives of benzotriazole include those where the available substitution sites of the aromatic ring are wholly or partially substituted.
  • Substituents can include, for example, straight or branched chain alkyl groups containing, for example, from one to twenty carbon atoms in the alkyl chain.
  • Other substituents can include -OH, -SH, phenyl or halogen groups.
  • Other derivatives include bis-benzotriazoles.
  • British Patent, GB-A-1,065,995 describes suitable substituted benzotriazoles of formula where R is a straight or branched chain alkyl group containing from two to twenty atoms, and a process for making such compounds.
  • British Patent, GB-A-1,226,100 describes compositions containing 4, 5, 6, 7-tetrahydrobenzotriazole compounds, which are also suitable for inclusion in the compositions of the invention.
  • British Patent GB-A-1, 180, 437 describes suitable bis-benzotriazoles having the formula and and wherein X represents a straight-chain alkylene group containing from one to six carbon atoms in the chain, being substituted with one or two alkyl groups containing from one to four carbon atoms where the alkylene group contains only one carbon atom, or being substituted with one or more alkyl groups containing from one to four carbon atoms where the alkylene group contains two or more carbon atoms, or being unsubstituted where the alkylene group contains two or more carbon atoms; a 1:1-cycloalkyl residue containing at least five carbon atoms; a carbonyl group; a sulphurlyl group, an oxygen atom; or a sulphur atom:
  • compositions of the invention may additionally contain detergent components such as detergent builder compounds, surfactants, heavy metal ion sequestrants, enzymes, lime soap dispersants, suds controlling agents and mixtures thereof.
  • detergent components such as detergent builder compounds, surfactants, heavy metal ion sequestrants, enzymes, lime soap dispersants, suds controlling agents and mixtures thereof.
  • a highly preferred component of the detergent compositions in accord with the present invention is a detergent builder compound preferably present at a level of from 1% to 80% by weight, more preferably from 10% to 70% by weight, most preferably from 20% to 60% weight of the composition.
  • the level of alkali metal carbonate or bicarbonate in the present compositions should preferably be inferior to 7%, more preferably inferior to 5%, by weight of the total composition. Most preferably the present composition should be free of alkali metal carbonate or bicarbonate species.
  • Suitable detergent builder compounds include, but are not restricted to monomeric polycarboxylates, 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, silicates and mixtures of any of the foregoing.
  • Suitable monomeric or oligomeric carboxylate builders can be selected from a wide range of compounds but such compounds preferably have a first carboxyl logarithmic acidity/constant (pK 1 ) of less than 9, preferably of between 2 and 8.5, more preferably of between 4 and 7.5.
  • pK 1 first carboxyl logarithmic acidity/constant
  • the logarithmic acidity constant is defined by reference to the equilibrium where A is the fully ionized carboxylate anion of the builder salt.
  • acidity constants are defined at 25°C and at zero ionic strength.
  • Literature values are taken where possible (see Stability Constants of Metal-Ion Complexes, Special Publication No. 25, The Chemical Society, London): where doubt arises they are determined by potentiometric titration using a glass electrode.
  • the carboxylate or polycarboxylate builder can be momomeric or oligomeric in type although monomeric polycarboxylates are generally preferred for reasons of cost and performance.
  • Monomeric and oligomeric builders can be selected from acyclic, alicyclic, heterocyclic and aromatic carboxylates having the general formulae
  • Suitable carboxylates containing one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof as disclosed in Belgian Patent Nos. 831,368, 821,369 and 821,370.
  • Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates described in German Offenlegenschrift 2,446,686, and 2,446,687 and U.S. Patent No. 3,935,257 and the sulfinyl carboxylates described in Belgian Patent No. 840,623.
  • Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1,379,241, lactoxysuccinates described in British Patent No. 1,389,732, and aminosuccinates described in Netherlands Application 7205873, and the oxypolycarboxylate materials such as 2-oxa-1,1,3-propane tricarboxylates described in British Patent No. 1,387,447.
  • 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 hydroxycarboxylates 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 components of builder systems of detergent compositions in accordance with the present invention.
  • Suitable water soluble organic salts are the 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.
  • Examples of such salts are polyacrylates of MWt 2000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 20,000 to 70,000, especially about 40,000. These materials are normally used at levels of from 0.5% to 10% by weight more preferably from 0.75% to 8%, most preferably from 1% to 6% by weight of the composition.
  • Water-soluble detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric metaphosphates), phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), and sulfates.
  • the levels of incorporation of carbonates or bicarbonates or mixtures thereof, is however preferably limited to less than 7% by weight of the composition.
  • 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.
  • phosphate builders are the alkali metal tripolyphosphates, sodium, 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.
  • Suitable silicates include the water soluble sodium silicates with an SiO 2 : Na 2 O ratio of from 1.0 to 2.8, with ratios of from 1.6 to 2.4 being preferred, and 2.0 ratio being most preferred.
  • the silicates may be in the form of either the anhydrous salt or a hydrated salt.
  • Sodium silicate with an SiO 2 : Na 2 O ratio of 2.0 is the most preferred silicate.
  • Silicates are preferably present in the machine dishwashing detergent compositions at the invention at a level of from 5% to 50% by weight of the composition, more preferably from 10% to 40% by weight, most preferably from 12% to 25% by weight.
  • Examples of such less water soluble builders include the crystalline layered silicates and the largely water insoluble sodium aluminosilicates.
  • Crystalline layered sodium silicates have the general formula NaMSi x O x+1.y H 2 O wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20. Crystalline layered sodium silicates of this type are disclosed in EP-A-0164514 and methods for their preparation are disclosed in DE-A-3417649 and DE-A-3742043.
  • x in the general formula above has a value of 2, 3 or 4 and is preferably 2. More preferably M is sodium and y is 0 and preferred examples of this formula comprise the ⁇ -, ⁇ -, ⁇ - and ⁇ - forms of Na 2 Si 2 O 5 . These materials are available from Hoechst AG FRG as respectively NaSKS-5, NaSKS-7, NaSKS-11 and NaSKS-6. The most preferred material is ⁇ -Na 2 Si 2 O 5 , NaSKS-6.
  • the crystalline layered sodium silicate material is preferably present in granular detergent compositions as a particulate in intimate admixture with a solid, water-soluble ionisable material.
  • the solid, water-soluble ionisable material is selected from organic acids, organic and inorganic acid salts and mixtures thereof. The primary requirement is that the material should contain at least one functional acidic group of which the pKa should be less than 9, providing a capability for at least partial neutralisation of the hydroxyl ions released by the crystalline layered silicate.
  • incorporation in the particulate of other ingredients additional to the crystalline layered silicate and ionisable water soluble compound can be advantageous particularly in the processing of the particulate and also in enhancing the stability of detergent compositions in which the particulates are included.
  • certain types of agglomerates may require the addition of one or more binder agents in order to assist in binding the silicate and ionisable water soluble material so as to produce particulates with acceptable physical characteristics.
  • the crystalline layered sodium silicate containing particulates can take a variety of physical forms such as extrudates, marumes, agglomerates, flakes or compacted granules.
  • a preferred process for preparing compacted granules comprising crystalline layered silicate and a solid, water-soluble ionisable material has been disclosed in the commonly assigned British Application No. 9108639.7 filed on 23 April 1991.
  • Suitable aluminosilicate zeolites have the unit cell formula Na z [(AlO 2 ) z (SiO 2 )y]. XH 2 O wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264.
  • the aluminosilicate material are in hydrated form and are preferably crystalline, containing from 10% to 28%, more preferably from 18% to 22% water in bound form.
  • the above aluminosilicate ion exchange materials are further characterised by a particle size diameter of from 0.1 to 10 micrometers, preferably from 0.2 to 4 micrometers.
  • particle size diameter herein represents the average particle size diameter of a given ion exchange material as determined by conventional analytical techniques such as, for example, microscopic determination utilizing a scanning electron microscope or by means of a laser granulometer.
  • the aluminosilicate ion exchange materials are further characterised by their calcium ion exchange capacity, which is at least 200 mg equivalent of CaCO 3 water hardness/g of aluminosilicate, calculated on an anhydrous basis, and which generally is in the range of from 300 mg eq./g to 352 mg eq./g.
  • the aluminosilicate ion exchange materials herein are still further characterised by their calcium ion exchange rate which is at least 130 mg equivalent of CaCO 3 / litre / minute / (g/litre) [2 grains Ca + + / gallon/ minute/ gram/ gallon)] of aluminosilicate (anhydrous basis), and which generally lies within the range of from 130 mg equivalent of CaCO 3 / litre/ minute/ (gram/litre) [2 grains/ gallon/ minute/ (gram/ gallon)] to 390 mg equivalent of CaCO 3 / litre/ minute/ (gram/litre) [4 grains/ gallon/ minute/ (gram/ gallon)], based on calcium ion hardness.
  • Optimum aluminosilicates for builder purposes exhibit a calcium ion exchange rate of at least 260 mg equivalent of CaCO 3 /litre/ minute/ (gram/litre) [4 grains/gallon/minute/ (gram/ gallon)].
  • the aluminosilicate ion exchange materials can be naturally occurring materials, but are preferably synthetically derived. A method for producing aluminosilicate ion exchange materials is discussed in US Patent No. 3,985,669. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof.
  • Zeolite A has the formula Na 12 [(AlO 2 ) 12 (SiO 2 ) 12 ].
  • xH 2 O wherein x is from 20 to 30, especially 27.
  • Zeolite X has the formula Na 86 [(AlO 2 ) 86 (SiO 2 ) 106 ].
  • 276 H 2 O has the formula Na 6 [(AlO 2 ) 6 (SiO 2 ) 6 ] 7.5 H 2 O).
  • the heavy metal ion sequestrant The heavy metal ion sequestrant
  • the detergent compositions further contain narrowly defined levels of a heavy metal ion sequestrant, such levels being in the range 0.005% to 3%, preferably 0.01 to 1%, most preferably 0.05% to 0.8%, by weight of the total composition.
  • Suitable heavy-metal sequestrant for use herein include organic phosphonates, such as amino alkylene poly (alkylene phosphonate), alkali metal ethane-1-hydroxy disphosphonates, nitrilo trimethylene phosphonates.
  • Preferred among above species are diethylene triamine penta (methylene phosphonate), hexamethylene diamine tetra (methylene phosphonate) and hydroxy-ethylene-1,1-diphosphonate.
  • the phosphonate compounds may be present either in their acid form or as a complex of either an alkali or alkaline metal ion, the molar ratio of said metal ion to said phosphonate compound being at least 1:1.
  • Such complexes are described in US-A-4,259,200.
  • the organic phosphonate compounds are in the form of their magnesium salt.
  • Suitable sequestrant for inclusion in the compositions in accordance with the invention include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetracetic acid, ethylenetriamine pentacetic acid, ethylenediamine disuccinic acid or the water soluble alkali metal salts thereof.
  • Preferred EDDS compounds are the free acid form and the sodium or magnesium salt or complex thereof. Examples of such preferred sodium salts of EDDS include Na 2 EDDS and Na 3 EDDS. Examples of such preferred magnesium complexes of EDDS include MgEDDS and Mg 2 EDDS. The magnesium complexes are the most preferred for inclusion in compositions in accordance with the invention.
  • sequestrants for use herein are iminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic acid, described in EPA 317 542 and EPA 399 133.
  • the heavy metal ion sequestrant herein can consist of a mixture of the above described species.
  • Chlorine bleaches include the alkali metal hypochlorites and chlorinated cyanuric acid salts.
  • the use of chlorine bleaches in the composition of the invention is optional and preferably minimized, and more preferably the present compositions contain no chlorine bleach.
  • a highly preferred component of the compositions of the invention is a surfactant system comprising surfactant selected from anionic, cationic, nonionic, ampholytic and zwitterionic surfactants and mixtures thereof.
  • the surfactant system is preferably present at a level of from 0.5% to 30% by weight, more preferably from 1% to 25% by weight, most preferably from 2% to 20% by weight of the compositions.
  • Sulphonate and sulphate surfactants are useful herein.
  • Sulphonates include alkyl benzene sulphonates having from 5 to 15 carbon atoms in the alkyl radical, and alpha-sulphonated methyl fatty acid esters in which the fatty acid is derived from a C 6 -C 18 fatty source.
  • Preferred sulphate surfactants are alkyl sulphates having from 6 to 16, preferably 6 to 10 carbon atoms in the alkyl radical.
  • Useful surfactant system comprises a mixture of two alkyl sulphate materials whose respective mean chain lengths differ from each other.
  • the cation in each instance is again an alkali metal, preferably sodium.
  • the alkyl sulfate salts may be derived from natural or synthetic hydrocarbon sources.
  • the C 6 -C 16 alkyl ethoxysulfate salt comprises a primary alkyl ethoxysulfate which is derived from the condensation product of a C 6 -C 16 alcohol condensed with an average of from one to seven ethylene oxide groups, per mole.
  • alkali metal sarcosinates of formula R-CON (R 1 ) CH 2 COOM wherein R is a C 5 -C 17 linear or branched alkyl or alkenyl group, R 1 is a C 1 -C 4 alkyl group and M is an alkali metal ion.
  • R is a C 5 -C 17 linear or branched alkyl or alkenyl group
  • R 1 is a C 1 -C 4 alkyl group
  • M is an alkali metal ion.
  • Preferred examples are the lauroyl, Cocoyl (C 12 -C 14 ), myristyl and oleyl methyl sarcosinates in the form of their sodium salts.
  • alkyl ester sulfonate surfactants which include linear esters of C 8 -C 20 carboxylic acids (i.e., fatty acids) which are sulfonated with gaseous SO 3 according to 'The Journal of the American Oil Chemists Society," 52 (1975), pp. 323-329.
  • Suitable starting materials would include natural fatty substances as derived from tallow, palm oil.
  • the preferred alkyl ester sulfonate surfactants have the structural formula: wherein R 3 is a C 8 -C 20 hydrocarbyl, preferably an alkyl, or combination thereof, R 4 is a C 1 -C 6 hydrocarbyl, preferably an alkyl, or combination thereof, and M is a cation which forms a water soluble salt with the alkyl ester sulfonate.
  • Suitable salt-forming cations include metals such as sodium, potassium, and lithium, and substituted or unsubstituted ammonium cations, such as monoethanolamine, diethanolamine, and triethanolamine.
  • R 3 is C 10 -C 16 alkyl
  • R 4 is methyl, ethyl or isopropyl.
  • methyl ester sulfonates wherein R 3 is C 10 -C 16 alkyl.
  • One preferred class of nonionic surfactants useful in the present invention comprises the water soluble ethoxylated C 6 -C 16 fatty alcohols and C 6 -C 16 mixed ethoxylatedlpropoxylated fatty alcohols and mixtures thereof.
  • the ethoxylated fatty alcohols are the C 10 -C 16 ethoxylated fatty alcohols with a degree of ethoxylation of from 3 to 50, most preferably these are the C 12 -C 16 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 16 carbon atoms, a degree of ethoxylation of from 3 to 30 and a degree of propoxylation of from 1 to 10.
  • C6-C16 alcohol itself can be obtained from natural or synthetic sources.
  • C6-C16 alcohols derived from natural fats, or Ziegler olefin build-up, or OXO synthesis can form suitable sources for the alkyl group.
  • Examples of synthetically derived materials include Dobanol 25 (RTM) sold by Shell Chemicals (UK) Ltd which is a blend of C 12 -C 15 alcohols, Ethyl 24 sold by the Ethyl Corporation which is a blend of C 12 -C 15 alcohols, and a blend of C 13 -C 15 alcohols in the ratio 67% C 13 , 33% C 15 sold under the trade name Lutensol by BASF GmbH and Synperonic (RTM) by ICI Ltd., and Lial 125 sold by Liquichimica Italiana.
  • Examples of naturally occuring materials from which the alcohols can be derived are coconut oil and palm kernel oil and the corresponding fatty acids.
  • Nonionic surfactants comprises alkyl polyglucoside compounds of general formula RO (C n H 2n O) t Z x wherein Z is a moiety derived from glucose; R is a saturated hydrophobic alkyl group that contains from 6 to 16 carbon atoms preferably from 6 to 14 carbon atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.1 to 4, the compounds including less than 10% unreacted fatty alcohol and less than 50% short chain alkyl polyglucosides.
  • RO C n H 2n O
  • t Z x alkyl polyglucoside compounds of general formula RO (C n H 2n O) t Z x wherein Z is a moiety derived from glucose; R is a saturated hydrophobic alkyl group that contains from 6 to 16 carbon atoms preferably from 6 to 14 carbon atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.1 to 4, the compounds including less than 10% unreacted fatty
  • Another preferred nonionic surfactant is a polyhydroxy fatty acid amide surfactant compound having the structural formula: wherein R 1 is H, C 1 -C 4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof, preferably C 1 -C 4 alkyl, more preferably C 1 or C 2 alkyl, most preferably C 1 alkyl (ie., methyl); and R 2 is a C 5 -C 15 hydrocarbyl, preferably straight chain C 5 -C 13 alkyl or alkenyl, more preferably straight chain C 5 -C 11 alkyl or alkenyl, most preferably straight chain C 5 -C 9 alkyl or alkenyl, or mixture thereof: and Z is a polyhydroxyhydrocarbyl having linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxlylated derivative (preferably ethoxylated or propoxylated) thereof.
  • Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl.
  • Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose.
  • high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be utilized as well as the individual sugars listed above. These corn syrups may yield a mix of sugar components for Z. It should be understood that it is by no means intended to exclude other suitable raw materials.
  • Z preferably will be selected from the group consisting of -CH 2 -(CHOH) n -CH 2 OH, -CH(CH 2 OH)-(CHOH) n-1 -CH 2 OH, -CH 2 -(CHOH) 2 (CHOR')(CHOH)-CH 2 OH, where n is an integer from 3 to 5, inclusive, and R' is H or a cyclic or aliphatic monosaccharide, and alkoxylated derivatives thereof. Most preferred are glycityls wherein n is 4, particularly - CH 2 -(CHOH) 4 -CH 2 OH.
  • R 1 can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-2-hydroxy ethyl, or N-2-hydroxy propyl.
  • R 2 -CO-N ⁇ can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, or tallowamide.
  • Z can be 1-deoxyglucityl, 2-deoxyfrucittyl, 1-deoxymaltityl, 1-deoxylactityl, 1-deoxygalactityl or 1-deoxymannityl, or 1-deoxymalto-triotityl.
  • Preferred compounds are N-methyl N-1deoxyglucityl C 14 -C 18 fatty acid amides.
  • a further class of surfactants are the semi-polar surfactants such as amine oxides.
  • Suitable amine oxides are selected from mono C 6 -C 20 , preferably C 6 -C 10 N-alkyl or alkenyl amine oxides and propylene-1,3-diamine dioxides wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxpropyl groups.
  • Cationic surfactants can also be used in the detergent compositions herein and suitable quaternary ammonium surfactants are selected from mono C 6 -C 16 , preferably C 6 -C 10 N-alkyl or alkenyl ammonium surfactants wherein remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.
  • Another optional ingredient useful in detergent compositions is one or more enzymes.
  • Preferred enzymatic materials include amylases, neutral and alkaline proteases, lipases, and esterases conventionally incorporated 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 and Savinase by Novo Industries A/S (Denmark) and Maxatase by International Bio-Synthetics, Inc. (The Netherlands).
  • Protease enzyme may be incorporated into the compositions in accordance with the invention at a level of from 0.005% to 2% active enzyme by weight of the composition.
  • Preferred amylases include, for example, ⁇ -amylases obtained from a special strain of B licheniforms, described in more detail in GB 1,269,839 (Novo).
  • Preferred commercially available amylases include for example, Rapidase, sold by International Bio-Synthetics Inc, and Termamyl, sold by Novo Industries A/S. The invention at a level of from 0.001% to 2% active enzyme by weight of the composition.
  • a preferred lipase is derived from Pseudomonas pseudoalcaligenes, which is described in Granted European Patent, EP-B-0218272.
  • Another preferred lipase herein is obtained by cloning the gene from Humicola lanuginosa and expressing the gene is Aspergillus oryza, as host, as described in European Patent Application, EP-A-0258068, which is commercially available from Novo Industri A/S, Bagsvaerd, Denmark, under the trade name Lipolase. This lipase is also described in U.S. Patent 4,810,414, Huge-Jensen et al, issued March 7, 1989.
  • Another optional ingredient is a lime soap dispersant compound, present at a level of from 0.05% to 40% by weight, more preferably from 0.1% to 20% by weight, most preferably from 0.25% 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 dispersants include C13-15 ethoxylated alcohol sulphates with an average degree of ethoxylation of 3.
  • Another optional component of the detergent compositions of the invention is a silicone suds controlling agent present at levels of from 0.01% to 5% by weight, more preferably from 0.05% to 3% by weight, most preferably from 0.05% to 1% by weight of the composition.
  • silicone suds controlling agent any suds controlling agent which comprises a silicone antifoam compound.
  • silicone suds controlling agents include agents containing silicone-silica mixtures and particulates in which the silicone, or silicone-silica mixture, is incorporated in a water-soluble or water-dispersible carrier material.
  • the silicone suds controlling agents may comprise silicone, or silicone-silica mixtures dissolved or dispersed in a liquid carrier and applied by spraying on to one or more of the other components of the detergent composition.
  • silicone silicone has become a generic term which encompasses a variety of relatively high molecular weight polymers containing siloxane units and hydrocarbyl group of various types.
  • the silicone antifoam compounds can be described as siloxanes having the general structure: where each R independently can be an alkyl or an aryl radical. Examples of such substituents are methyl, ethyl, propyl, isobutyl, and phenyl.
  • Preferred polydiorganosiloxanes are polydimethylsiloxanes having trimethylsilyl endblocking units and having a viscosity at 25°C of from 5 x 10 -5 m 2 s -1 to 0.1 m 2 s -1 i.e. a value of n in the range 40 to 1500. These are preferred because of their ready availability and their relatively low cost
  • a preferred type of silicone suds controlling agent useful in the compositions herein comprises a mixture of an alkylated siloxane of the type hereinabove disclosed and solid silica.
  • the solid silica can be a fumed silica, a precipitated silica or a silica made by the gelformation technique.
  • the silica particles suitable have an average particle size of from 0.1 to 50 micrometers, preferably from 1 to 20 micrometers and a surface area of at least 50 m 2 /g. These silica particles can be rendered hydrophobic by treating them with dialkylsilyl groups and/or trialkylsilyl groups either bonded directly onto the silica or by means of a silicone resin. It is preferred to employ a silica the particles of which have been rendered hydrophobic with dimethyl and/or trimethyl silyl groups.
  • the suds controlling agents for inclusion in the detergent compositions in accordance with the invention suitably contain an amount of silica such that the weight ratio of silica to silicone lies in the range from 1:100 to 3:10, preferably from 1:50 to 1:7.
  • a preferred silicone suds controlling agent is represented by a hydrophobic silanated (most preferably trimethyl-silanated)silica having a particle size in the range from 10 nanometers to 20 nanometers and a specific surface area above 50 m 2 /g, intimately admixed with dimethyl silicone fluid having a molecular weight in the range from 500 to 200,000 at a weight ratio of silicone to silanated silica of from 1:1 to 1:2.
  • a hydrophobic silanated (most preferably trimethyl-silanated)silica having a particle size in the range from 10 nanometers to 20 nanometers and a specific surface area above 50 m 2 /g, intimately admixed with dimethyl silicone fluid having a molecular weight in the range from 500 to 200,000 at a weight ratio of silicone to silanated silica of from 1:1 to 1:2.
  • Another preferred silicone suds controlling agent is disclosed in Bartollota et Al. US Patent 3,933,672.
  • Other particularly useful suds suppressors are the self-emulsifying silicone suds suppressors, described in German Patent Application DTOS 2,646,126 published April 28, 1977.
  • An example of such a compound is DC0544, commercially available from Dow Coming, which is a siloxane/glycol copolymer.
  • a highly preferred silicone suds controlling agent is a particulate of the type disclosed in EP-A-0210731 comprising a silicone antifoam and an organic material having a melting point in the range 50° to 85°C, wherein the organic material comprises a monoester of glycerol and a fatty acid having a carbon chain containing from 12 to 20 carbon atoms.
  • EP-A-0210721 discloses similar particulate suds controlling agents wherein the organic material however, is a fatty acid or alcohol having a carbon chain containing from 12 to 20 carbon atoms, or a mixture thereof, with a melting point of from 45°C to 80°C.
  • the preferred methods of incorporation of the silicone suds controlling agents comprise either application of the silicone suds controlling agent in liquid form by spray-on to one or more of the major components of the composition or alternatively the formation of the silicone suds controlling agents into separate particulates that can then be mixed with the other solid components of the composition.
  • the incorporation of the suds controlling agents as separate particulates also permits the inclusion therein of other suds controlling materials such as C 20 -C 24 fatty acids, microcrystalline waxes and high MWt copolymers of ethylene oxide and propylene oxide which would otherwise adversely affect the dispersibility of the matrix. Techniques for forming such suds controlling particulates are disclosed in the previously mentioned Bartolotta et al US Patent No. 3,933,672.
  • compositions of the invention include antiredeposition, and soil-suspension agents, corrosion inhibitors, perfumes, colours and filler salts, with sodium sulfate being a preferred filler salt.
  • compositions of the invention can be formulated in any desirable form such as powders, granulates, pastes, liquids, gels and tablets, granular forms being preferred.
  • the bulk density of granular 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.
  • Bulk density is measured by means of a simple funnel and cup device consisting of a conical funnel moulded rigidly on a base and provided with a flap valve at its lower extremity to allow the contents of the funnel to be emptied into an axially aligned cylindrial cup disposed below the funnel.
  • the funnel is 130 mm and 40 mm at its respective upper and lower extremities. It is mounted so that the lower extremity is 140 mm above the upper surface of the base.
  • the cup has an overall height of 90 mm, an internal height of 87 mm and an internal diameter of 84 mm. Its nominal volume is 500 ml.
  • the funnel is filled with powder by hand pouring, the flap valve is opened and powder allowed to overfill the cup.
  • the filled cup is removed from the frame and excess powder removed from the cup by passing a straight edged implement e.g. a knife, across its upper edge.
  • the filled cup is then weighed and the value obtained for the weight of powder doubled to provide the bulk density in g/litre. Replicate measurements are made as required.
  • 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 viscosity control agent or a thixotropic agent to provide a suitable liquid product form.
  • Suitable thixotropic or viscosity control agents include methyl cellulose, carboxymethylcellulose, starch, polyvinyl, pyrrolidone, gelatin, colloidal silica, and natural or synthetic clay minerals.
  • Pasty compositions in accordance with the invention generally have viscosities of about 5,000 centipoise and up to several hundred million centipoise.
  • a small amount of a solvent or solubilizing agent or of a gel-forming agent can be included. Most commonly, water is used in this context and forms the continuous phase of a concentrated dispersion. Certain nonionic surfactants at high levels form a gel in the presence of small amount of water and other solvents. Such gelled compositions are also envisaged in the present invention.
  • the pH of a 1% solution of the present compositions is preferably from 9.6 to 12, preferably from 9.8 to 11.5, most preferably from 10.0 to 11.0.
  • a preferred making process for the compositions herein comprises pre-mixing of the paraffin oil with a dispersing agent and the resultive intimate pre-mix being sprayed onto the remainder of the composition.
  • the dispersing agent can advantageously consist of a nonionic surfactant such as described hereinabove, which therefore serves two functions in the present composition.
  • a preferred dispersing agent is Plurafac LF404 sold by BASF.
  • An alternate route consists in spraying the intimate mixture of paraffin oil and dispersing agent onto the particles of bleaching agent, resulting in a reduction in the rate of dissolution in water of said bleaching agent and therefore providing a control over the rate of release of available oxygen.
  • the coated particles of bleaching agent are then dry-mixed with the remainder of the composition.
  • the particle of bleaching agents are compacted before being dry-mixed with the remainder of the composition .
  • This technique slows down the dissolution rate in water, and is therefore advantageously applied to otherwise fast dissolving species like perborate monohydrate.
  • the paraffin oil is typically compacted along with the bleaching species, and optionally other ingredients like sodium sulphate and/or binders.
  • the resulting particles are then dry-mixed with the remainder of the ingredients.
  • the following machine dishwashing detergents according to the invention are prepared (parts by weight): Ingredients Parts by weight I II III IV citrate 38.0 35.0 40.0 35.0 MA/AA 4.0 6.0 2.0 4.0 2 ratio silicate (2.0 ratio) 26.0 30.0 20.0 30.0 AvO level 0.8 0.8 1.0 1.0 Perborate monohydrate - 5.05 - - Perborate tetrahydrate 8.0 - 9.0 9.0 TAED 2.5 2.2 3.0 2.2 Paraffin oil 0.5 0.5 0.3 0.3 Protease 2.0 2.5 2.2 2.0 Amylase 1.5 0.5 1.0 1.0 Lipase - - 2.0 - Nonionic 1.54 1.0 1.5 1.5 Anionic - 3.0 - - DTPMP 0.1 0.2 - - Benzotriazole 0.1 0.1 0.1 0.2 0.2 EDDS 0.1 - 0.15 - Limesoap dispersant - - 2.5 - Suds suppressor - 1.0 - - Sulphate balance to 100 pH 10.7 10.7 10.
  • composition A in accord with the invention was compared for anti-silver tarnishing performance, to Compositions B and C.
  • Composition B contains no paraffin oil or benzotriazole.
  • Composition C contains paraffin but no benzotriazole.
  • Composition A Composition B
  • Composition C citrate 38.0 38.0 38.0 MA/AA 4.0 4.0 4.0 2 ratio silicate (2.0 ratio) 26.0 26.0 26.0
  • AvO level 0.8 1.5
  • Paraffin oil 0.5 - 0.5 Benzotriazole 0.15 - - Protease 2.0
  • test protocol employed comprised machine testing, using a Bosch Siemens dishwasher, 20g product dosage, 65°C economy cycles, and 20 cycles.
  • Results were as follows : (average of the 4 gradings from the panellists) Comp. A Comp. B Comp. C 0.0 4.0 1.5 Composition A shows superior anti-silver tarnishing performance over Compositions B and C, in accord with the invention.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
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Claims (11)

  1. Composition pour lave-vaisselle ayant des propriétés d'élimination des taches lessivables et d'inhibition du ternissement de l'argent, comprenant
    un agent de blanchiment dégageant de l'oxygène, dans lequel la teneur en agent de blanchiment dégageant de l'oxygène étant telle que le niveau d'oxygène disponible mesuré selon le présent procédé est compris entre 0,3 % et 2,5 % ;
    de 0,05 % à 2,5 % en poids d'une huile de paraffine ; et
    de 0,005 % à 3 % en poids d'un composé de benzotriazole.
  2. Composition selon la revendication 1 dans laquelle la vitesse de libération de l'oxygène disponible est telle que l'oxygène disponible est complètement libéré de la composition en un intervalle de temps compris entre 3,5 et 10 minutes en utilisant le protocole exposé dans la présente description.
  3. Composition selon les revendications 1 à 2 contenant une source de peroxyacide organique, où selon le procédé expérimental T50 ici décrit, la durée nécessaire pour obtenir une concentration qui est de 50 % de la concentration finale du peroxyacide est de 180 secondes à 480 secondes.
  4. Composition selon les revendications 1 à 3 dans laquelle l'huile de paraffine est présente à un niveau compris entre 0,1 % et 0,6 %.
  5. Composition selon les revendications 1 à 4 dans laquelle l'huile de paraffine est choisie parmi les hydrocarbures aliphatiques principalement ramifiés ayant de 20 à 50, de préférence de 25 à 45 atomes de carbone, avec un rapport des hydrocarbures cycliques aux hydrocarbures non cycliques compris entre 1:5 et 1:1.
  6. Composition selon les revendications 1 à 5 dans laquelle le composé de benzotriazole est présent à des niveaux allant de 0,02 % à 1 %.
  7. Composition selon les revendications 1 à 6 dans laquelle le composé de benzotriazole est présent à des niveaux allant de 0,05 % à 0,5 %.
  8. Composition selon les revendications 1 à 7 dans laquelle le composé de benzotriazole est le benzotriazole.
  9. Composition selon les revendications 1 à 8 dans laquelle l'agent de blanchiment libérant de l'oxygène comprend en combinaison un sel perhydrate inorganique et un précurseur de blanchiment peroxyacide.
  10. Composition selon les revendications 1 à 9 contenant un séquestrant d'ion métallique lourd à un niveau allant de 0,005 % à 3 % en poids.
  11. Composition selon l'une quelconque des revendications 1 à 10 contenant en outre un composant détergent choisi parmi un composé adjuvant de détergent et un agent tensioactif.
EP94921436A 1993-07-01 1994-06-30 Composition pour lave-vaisselle contenant un agent de blanchiment oxygene, de l'huile de paraffine et un compose benzotriazole pour inhiber le ternissement de l'argent Expired - Lifetime EP0706559B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP94921436A EP0706559B1 (fr) 1993-07-01 1994-06-30 Composition pour lave-vaisselle contenant un agent de blanchiment oxygene, de l'huile de paraffine et un compose benzotriazole pour inhiber le ternissement de l'argent

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP93201918 1993-07-01
EP93201918 1993-07-01
PCT/US1994/007405 WO1995001416A1 (fr) 1993-07-01 1994-06-30 Composition pour lave-vaisselle contenant un agent de blanchiment oxygene, de l'huile de paraffine et un compose benzotriazole pour inhiber le ternissement de l'argent
EP94921436A EP0706559B1 (fr) 1993-07-01 1994-06-30 Composition pour lave-vaisselle contenant un agent de blanchiment oxygene, de l'huile de paraffine et un compose benzotriazole pour inhiber le ternissement de l'argent

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EP0706559A1 EP0706559A1 (fr) 1996-04-17
EP0706559A4 EP0706559A4 (fr) 1996-04-24
EP0706559B1 true EP0706559B1 (fr) 2001-08-08

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AT (1) ATE204016T1 (fr)
AU (1) AU7216594A (fr)
DE (1) DE69427912T2 (fr)
ES (1) ES2158899T3 (fr)
WO (1) WO1995001416A1 (fr)

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WO1995001416A1 (fr) 1995-01-12
EP0706559A1 (fr) 1996-04-17
ES2158899T3 (es) 2001-09-16
ATE204016T1 (de) 2001-08-15
EP0706559A4 (fr) 1996-04-24
DE69427912D1 (de) 2001-09-13
AU7216594A (en) 1995-01-24
DE69427912T2 (de) 2002-04-04

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