EP0692947A1 - Procede de lavage en lave-vaisselle utilisant un catalyseur organometallique et une enzyme pour produire du peroxyde d'hydrogene - Google Patents

Procede de lavage en lave-vaisselle utilisant un catalyseur organometallique et une enzyme pour produire du peroxyde d'hydrogene

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Publication number
EP0692947A1
EP0692947A1 EP94913945A EP94913945A EP0692947A1 EP 0692947 A1 EP0692947 A1 EP 0692947A1 EP 94913945 A EP94913945 A EP 94913945A EP 94913945 A EP94913945 A EP 94913945A EP 0692947 A1 EP0692947 A1 EP 0692947A1
Authority
EP
European Patent Office
Prior art keywords
dishwashing method
metallo
water
derivatives
detergent composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP94913945A
Other languages
German (de)
English (en)
Other versions
EP0692947A4 (fr
Inventor
Marnix Karel Christiane Moens
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
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Procter and Gamble Co
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Filing date
Publication date
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to EP94913945A priority Critical patent/EP0692947A4/fr
Publication of EP0692947A1 publication Critical patent/EP0692947A1/fr
Publication of EP0692947A4 publication Critical patent/EP0692947A4/fr
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—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
    • C11D3/16—Organic compounds
    • C11D3/168—Organometallic compounds or orgometallic complexes
    • 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
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38654—Preparations containing enzymes, e.g. protease or amylase containing oxidase or reductase

Definitions

  • the present invention relates to a dishwashing composition and method for inhibiting the redeposition of coloured food soils from the wash solution onto articles in the wash.
  • Coloured food soils comprising natural dyestuffs, may be removed from the articles being washed and then redeposit from the wash solution onto other articles in the wash or onto the interior of the vessel holding the wash solution such as a dishwashing machine.
  • the problem is particularly noticeable when the washload includes articles soiled by foods naturally containing significant levels of coloured dyestuff molecules, including for example tomato sauce, fruit juices such as blackcurrant juice,and curry.
  • plastic articles in the wash, and areas of the interior of a dishwashing machine, which are made of plastic, are particularly susceptible to the deposition of coloured food dyes from the wash liquor.
  • a solution to the problem of dye transfer in laundering operations is to bleach the fugitive dyes washed out of dyed fabrics before they have the opportunity to become attached to other articles in the wash.
  • GB 2 101 167 describes a stable liquid bleaching composition containing a hydrogen peroxide precursor which is activated to yield hydrogen peroxide on dilution.
  • U.S. Patent 4,077,768 describes a process for inhibiting dye transfer by the use of an oxidizing bleaching agent together with a catalytic compound such as iron porphins.
  • a catalytic compound such as iron porphins.
  • the effectiveness of this process tends to be limited, praticularly in the way that the oxidsing bleaching agent has to be added dropwise in order to obtain the most effective dye transfer inhibition.
  • Copending EP Patent Application 91202655.6 filed October 9, 1991 provides an efficient dye transfer inhibiting composition which overcomes this limitation of the process of U. S. Patent 4,077,768 and provides a practical way of controlling a low steady state level of hydrogen peroxide.
  • the aforementioned copending EP Patent Application relates to dye transfer inhibiting compositions comprising an enzymatic system capable of generating hydrogen peroxide and metallo catalysts, especially for use in laundering operations.
  • the hydrogen peroxide is enzy atically generated in situ by using a hydrogen peroxide precursor plus an oxidase enzyme eg: glucose or alcohol as hydrogen peroxide precursors and respectively glucose oxidase or alcohol oxidase as the enzyme system.
  • a hydrogen peroxide precursor plus an oxidase enzyme eg: glucose or alcohol as hydrogen peroxide precursors and respectively glucose oxidase or alcohol oxidase as the enzyme system.
  • the present invention therefore provides a method for dishwashing operations,especially machine dishwashing operations,which mitigates the problem of coloured food dyestuff deposition.
  • the present invention relates to a dishwashing method wherein the articles to be washed are treated with an effective amount of a detergent composition
  • a detergent composition comprising: A. a metallo catalyst selected from
  • metallo porphin and water-soluble or water dispersable derivatives thereof; b) metallo porphyrin and water-soluble or water- dispersable derivatives thereof c) metallo phthalocyanine and water-soluble or water-dispersable derivatives thereof; and
  • said detergent composition further comprises certain specific polymers which when added to the detergent composition enhance the overall performance of the dishwashing method.
  • the addition of said polymers eliminates or reduces the deposition of the catalyst onto the articles in the wash.
  • the polymer is selected from
  • the detergent composition further comprises certain amine base catalyst stabilizers which are capable of binding to the 5th ligand of the metallo catalyst, and which enhance the performance of the dishwashing method
  • certain amine base catalyst stabilizers which are capable of binding to the 5th ligand of the metallo catalyst, and which enhance the performance of the dishwashing method
  • the addition of said catalyst stabilizers reduces the rate of self-destruction of the catalyst resulting in improved through-the-wash stability of the catalyst. Benefits are also obtained in the presence of catalyst stabilizers, due to a substantial reduction in the amount of catalyst deposited onto the articles in the wash.
  • said catalyst stabilizers accelerate the oxidation activity of the catalyst thereby increasing the rate of dye bleaching.
  • the detergent compositions for use in accord with the method of the invention are largely free of conventional bleaching agents such as inorganic perhydrate salts, bleach activators and preformed peracids. Whilst this means that careful formulation is required to ensure that bleachable stain removal is not impaired in the absence of these conventional bleaching agents, their absence may provide benefits in the form of reduced bleach related silver tarnishing.
  • conventional bleaching agents such as inorganic perhydrate salts, bleach activators and preformed peracids. Whilst this means that careful formulation is required to ensure that bleachable stain removal is not impaired in the absence of these conventional bleaching agents, their absence may provide benefits in the form of reduced bleach related silver tarnishing.
  • metallo porphin and water-soluble or water dispersable derivatives thereof; b) metallo porphyrin and water-soluble water- dispersable derivatives thereof c) metallo phtalocyanine and water-soluble or water-dispersable derivatives thereof; and B. an enzymatic system capable of generating hydrogen peroxide
  • compositions may be used in essentially any method for washing dishes, including methods with rinsing steps for which a separate rinse aid composition may be added.
  • the metallo catalyst and enzymatic hydrogen peroxide source may also be added as components of any rinse aid. Preferred machine and manual machine dishwashing methods are hereinafter described.
  • a preferred machine dishwashing method comprises treating soiled articles selected from crockery, glassware, hollowware and cutlery and mixtures thereof, with an aqueous liquid having dissolved or dispensed therein an effective amount of the detergent compositions as described herein.
  • an effective amount of the 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.
  • soiled dishes are contacted with an effective amount, typically from about 0.5g to about 20g (per 25 dishes being treated) , preferably from about 3g to about log, of the detergent compositions described herein.
  • an effective amount typically from about 0.5g to about 20g (per 25 dishes being treated) , preferably from about 3g to about log, of the detergent compositions described herein.
  • the actual amount of detergent composition used will be based on the judgement of user, and will depend upon factors such as the particular product formulation of the composition, the concentration of the composition, the number of soiled dishes to be cleaned and the degree of soiling of the dishes.
  • a concentrated solution of the detergent composition is applied to the surface of the dishes to be washed.
  • concentrated solution of the composition it is meant no less than a 20% by weight, preferably no less than 50% by weight product dilution, and most preferably the composition is applied in undiluted form.
  • the preferred usage range of the catalyst in the wash is 10 ⁇ 8 molar to 10 ⁇ 3 molar, more preferred 10" 6 - 10 ⁇ 4 molar.
  • the essential metallo porphin structure may be visualized as indicated in Formula I in the accompanying drawings.
  • Formula I the atom positions of the porphin structure are numbered conventionally and the double bonds are put in conventionally. In other formula, the double bonds have been omitted in the drawings, but are actually present as in I.
  • Preferred metallo porphin structures are those substituted at one or more of the 5, 10, 15 and 20 carbon positions of Formula I (Meso positions) , with a phenyl or pyridyl substituent selected from the group consisting of
  • n and m may be 0 or 1; A may be sulfate, sulfonate, phosphate or carboxylate groups; and B is C- ⁇ - C 10 alkyl, polyethoxy alkyl or hydroxy alkyl.
  • Preferred molecules are those in which the substituents on the phenyl or pyridyl groups are selected from the group consisting of
  • a particularly preferred metallo phorphin is one in which the molecule is substituted at the 5, 10, 15, and 20 carbon positions with the substituent
  • This preferred compound is known as metallo tetrasulfonated tetraphenylporphin.
  • X 2 of Formula I represents an anion, preferably OH" or Cl ⁇ .
  • the compound of Formula I may be substituted at one or more of the remaining carbon positions with C-L-C-LQ alkyl, hydroxyalkyl or oxyalkyl groups.
  • Porphin derivatives also include chlorophyls, chlorines, i.e. isobacterio chlorines and bacteriochlorines.
  • Metallo porphyrin and water-soluble or water-dispersable derivatives thereof have a structure given in formula II.
  • X can be alkyl, alkyl carboxy, alkyl hydroxyl, vinyl, alkenyl, alkyl sulfate, alkylsulfonate, sulfate, sulfonate.
  • X 2 of Formula II represents an anion, preferably OH ⁇ or CL ⁇ .
  • the symbol X* can be alkyl, alkylcarboxy, alkylhydroxyl, vinyl, alkenyl, alkylsulfate, alkylsulfonate, sulfate, sulfonate, aryl.
  • Metallo phthalocyanine and derivatives have the structure indicated in Formula III, wherein the atom positions of the phthalocyanine structure are numbered conventionally.
  • the anionic groups in the above structures contain cations selected from the group consisting of sodium and potassium cations or other non- interfering cations which leave the structures water- soluble.
  • Preferred phthalocyanine derivatives are metallo phthalocyanine trisulfonate and metallo phthalocyanine tetrasulfonate.
  • substitution of the central metal is substitution of the central metal by Fe, Mn, Co, Rh, Cr, Ru, Mo or other transition metals.
  • the choice of the substituent groups can be used to control the solubility of the catalyst in water or in detergent solutions. Yet again, especially where it is desired to avoid attacking dyes attached to solid surfaces, the substituents can control the affinity of the catalyst compound for the surface.
  • strongly negatively charged substituted compounds for instance the tetrasulfonated porphin, may be repelled by negatively charged stains or stained surfaces and are therefore most likely not to cause attack on fixed dyes, whereas the cationic or zwitterionic compounds may be attracted to, or at least not repelled by such stained surfaces.
  • the oxidizing agent, hydrogen peroxide is generated in situ by using an enzymatic hydrogen peroxide generation system.
  • the enzyme used in the present invention is an oxidase.
  • the oxidase is present by 0.1 - 20000 units, preferably 0.5 to 5000 units per gram of the composition. One unit is the amount of enzyme needed to convert 1 mole of glucose substrate per minute.
  • Suitable oxidases are urate oxidase, galactose oxidase, alcohol oxidases, amine oxidases, amino acid oxidases, cholesterol oxidase and glucose oxidase, malate oxidase, glycollate oxidase, hexose oxidase, aryl alcohol oxidase, L-gulonolactose oxidase, pyranose oxidase, L-sorbose oxidase, pyridoxine 4-oxidase, 2-2-hydroxyacid oxidase, choline oxidase, ecdysone oxidase.
  • the preferred enzymatic systems are alcohol and aldehyde oxidases, glucose oxidase.
  • the more preferred systems for granular detergent application would have solid alcohols, e.g. glucose whose oxidation is catalysed by glucose oxidase to glucoronic acid with the formation of hydrogen peroxide.
  • solid alcohols e.g. glucose whose oxidation is catalysed by glucose oxidase to glucoronic acid with the formation of hydrogen peroxide.
  • liquid alcohols which could for example, also act as solvents.
  • An example is ethanol/ethanol oxidase.
  • the quantity of oxidase to be employed in compositions according to the invention should be at least sufficient to provide in the wash a constant generation of 0.005 to 10 ppm AvO per minute in the wash process.
  • glucose oxidase this can be achieved at room temperature and at pH 6 to 11, preferentially 7.5 to 10.5 with 1-20000 U/l glucose oxidase, 0.005 to 2% glucose under constant aeration in the washing process.
  • the dye transfer inhibiting benefits can be optimized by adding small amounts of polymers to the detergent composition.
  • These polymers of the present invention reduce the deposition of the porphin catalyst onto the articles in the wash.
  • the compounds suitable for the present invention having reduced deposition effect of the porphin catalyst are polymers having alkoxy moieties. These polymers include copolymeric blocks of ethylene terephthalate and polyethylene oxide or polypropylene oxide terephthalate and the like. These polymers are often used as soil release agents.
  • More preferred alkoxy containing polymers include polyethylene glycol or polypropylene glycol and derivatives thereof.
  • copolymers of said polymers e.g Pluriol (R ) .
  • Another preferred soil release agent is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephtalate. More specifically, these polymers are comprised of repeating units of ethylene terephthalate and PEO terephthalate in a mole ratio of ethylene terephtalate units to PEO terephthalate units of from 25:75 to 35:65, said PEO terephthalate units containing polyethylene oxide having molecular weights of from 300 to 2000. The molecular weight of this polymer is in the range of from 3,000 to 55,000.
  • PEO polyethylene oxide
  • Another preferred polymeric soil release agent is a polyester with repeating units of ethylene terephthalate containing 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, and the mole ratio of ethylene terephthalate units to polyoxyethylene terephthalate units in the polymeric compound is between 2:1 and 6:1.
  • Highly preferred polymers are compounds of formula :
  • the R 4 moieties are R 1 or R 3 moieties, or mixtures thereof; each X is ethyl or preferably methyl; each n is from 12 to 43; when w is 0, u + v is from 3 to 10; when w is at least 1, u + v + w is from 3 to 10.
  • Particularly preferred block polyesters are those where v is 0, i.e. the linear block polyesters.
  • u typically ranges from 3 to 8, especially for those made from dimethyl terephthalate, ethylene glycol (or 1,2-propylene glycol) and methyl capped polyethylene glycol.
  • the most water soluble of these linear block polyesters are those where u is from 3 to 5.
  • alkoxylated polyamines are alkoxylated polyamines. Such materials can conveniently be represented as molecules of the empirical structures with repeating units :
  • R is a hydrocarbyl group, usually of 2-6 carbon atoms;
  • R 1 may be a C 1 -C 20 hydrocarbon; the alkoxy groups are ethoxy, propoxy, and the like, and y is 2-30, most preferably from 10-20;
  • n is an integer of at least 2, preferably from 2-20, most preferably 3-5; and
  • X ⁇ is an anion such as halide or methylsulfate, resulting from the quaternization reaction.
  • polyethylene i ines i.e., the polymerized reaction product of ethylene oxide with ethylene-i ine, having the general formula :
  • polymers suitable for use in the present invention are alkoxylated nonionic surfactants.
  • the alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms.
  • Preferred nonionic surfactants for use in the present invention are nonionic surfactants having at least 3, preferably at least 5 ethoxy groups and a C ⁇ o-C 2 o alkyl chain.
  • Suitable nonionic surfactants include polyethyleneoxide condensates of alkyl phenols, condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol or ethylenediamine.
  • Semi-polar nonionic detergent surfactants which include water-soluble amine oxides, water-soluble phosphine oxides and water-soluble sulfoxides are suitable.
  • Hydroxy containing polymers e.g. polyvinyl alcohol and polyaminoacids containing hydroxyl groups such as polyserine, polythreonine and polytyrosine as well as thiol containing polymers such as polycysteine are suitable.
  • Amide containing polymers are also suitable. These include compounds of formula :
  • R- ⁇ is amino acid side chain, or alkyl ( c l ⁇ c 12) or ar yl groups
  • amide containing polymer is polyvinyl pyrolidone or alkoxylated derivatives thereof.
  • polymers suitable for the present invention are polyurethanes, polyacrylonitrile and polyamines including polyaminoacids containing basic amino acids such as dia ino monocarboxylic aminoacids e.g. lysine, arginine, histidine ...) , polyethylenimine and ethoxylated amine containing polymers (e.g. tetraethylene pentamine etc.).
  • heterocyclic amines such as polyvinyl pyridine and derivatives thereof are suitable.
  • Particulary preferred heterocyclic amine is polyvinylimidazoline.
  • the polymers suitable for the present invention have an average molecular weight within the range of about 1000 to 50,000, preferably from 2000 to 25,000 and most preferred from 2000 to 15,000.
  • the level of polymer in the detergent composition is from 0.01 to 5% by weight, preferably from 0.1 to 2% and most preferred from 0.2 to 1%
  • the dye transfer inhibiting benefits can be optimized by adding small amounts of catalyst stabilizers.
  • catalyst e.g. metallo porphins are susceptible to self-destruction.
  • the level of catalyst should be such that sufficient active catalyst is present to bleach the dyes throughout the total wash cycle.
  • amine base catalyst stabilizers capable of binding the 5th ligand of the central atom in the metallo porphin structure.
  • Preferred heterocyclic compounds suitable for the present invention are imidazole compounds of the formula :
  • Y is hydrogen or oxygen or a C 1 -C 12 alkyl
  • R j L R- and R 2 are selected independently hydrogen or C ⁇ C 30 alkyl or alkenyl groups
  • X is selected from the group of : N
  • R 3 is a C ⁇ -C 5 alkanediyl group, or is
  • n being an integer from 0 to 10
  • m is an integer from 0 to 2
  • n+m>l R being a C 1 _ 4 alkyl group or hydrogen.
  • imidazole derivatives including histidine, purines, hipoxanthine, imidazolidicarboxylic acid, histamine, polyhistidine, alkylated imidazole.
  • heterocyclic compounds suitable for the present invention are pyridine and alkylated pyridines and d erivatives thereof, pyrole and derivatives thereof.
  • Non heterocyclic compounds capable of binding the 5th ligand of the central atom in the porphin structure are suitable. These non heterocyclic compounds include non heterocyclic amines, having the formula (C 2 H 5 ) 3 N, C 3 H 7 NH 2 , (C 6 H 11 ) 2 NH, 1,5 - diazabicyclo[4.3.0]non-5-ene.
  • the catalyst stabilizers of the present invention reduce the deposition of the porphin catalyst onto the articles in the wash.
  • the amine base catalyst stabilizer is present in a molar ratio of iron porphin to amine base catalyst from 1:1 to 1:5000, preferably from 1:1 to 1:2500.
  • the detergent compositions for use in accord with the dishwashing method of the invention may comprise additional ingredients, which are often quite desirable ones.
  • a highly preferred component of a machine dishwashing detergent composition for use in a machine dishwashing method in accord with the present invention is detergent builder compound present at a level of from 1% to 80% by weight, preferably from 10% to 70% by weight, most preferably from 20% to 60% weight of the composition.
  • Suitable water-soluble detergent builder compounds include, but are not restricted to monomeric poly arboxylates, of 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 water-soluble 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 ) of less than 9, preferably of between 2 and 8.5, more preferably of between 4 and 7.5.
  • pK carboxyl logarithmic acidity/constant
  • the logarithmic acidity constant is defined by reference to the equilibrium
  • 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 omomeric 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
  • R ⁇ represents H,C 1 __ 30 alkyl or alkenyl optionally substituted by hydroxy, carboxy, sulfo or phosphono groups or attached to a polyethylenoxy moiety containing up to 20 ethyleneoxy groups
  • R 2 represents H, C*L_ 4 alkyl, alkenyl or hydroxy alkyl, or alkaryl, sulfo, or phosphono groups
  • X represents a single bond; O; S; SO; S0 2 ; or NR ⁇ ;
  • Y represents H; carboxy;hydroxy; carboxymethyloxy; or c l-30 alkyl or alkenyl optionally substituted by hydroxy or carboxy groups;
  • Z represents H; or carboxy; m is an integer from 1 to 10; n is an integer from 3 to 6; p, q are integers from 0 to 6, p + q being from 1 to 6; and wherein, X, Y, and Z each have the same or different representations when repeated in a given molecular formula, and wherein at least one Y or Z in a molecule contain a carboxy1 group.
  • 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-l,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, l,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 meta-phosphates) , phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates) , and sulfates.
  • 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 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 Si0 2 : Na 2 0 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 Si0 2 : Na 2 0 ratio of 2.0 is the most preferred silicate.
  • Silicates are preferably present in machine dishwashing detergent compositions at a level of from 5% to 50% by weight of the composition, more preferably from 10% to 40% by weight.
  • compositions may also include less water soluble builders although preferably their levels of incorporation are minimized.
  • less water soluble builders include the crystalline layered silicates and the largely water insoluble, sodium aluminosilicates.
  • Crystalline layered sodium silicates have the general formula
  • M is sodium or hydrogen
  • x is a number from 1.9 to 4
  • 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 o f 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 c ⁇ - , ⁇ -, y - and S - forms of Na 2 Si 2 0 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 ⁇ 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 on 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 [ (A10 2 ) 2 (Si0 2 )y] . XH 2 0 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.
  • 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 CaC0 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 CaC0 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 CaC0 3 / litre/ minute/ (gram/litre) [2 grains/ gallon/ minute/ (gram/ gallon) ] to 390 mg equivalent of CaC0 3 / litre/ minute/ (gram/litre) [4 grains/ gallon/ minute/ (gram/ gallon)], based on calcium ion hardness.
  • Optimum alu inosilicates for builder purpose exhibit a calcium ion exchange rate of at least 260 mg equivalent o f CaC0 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
  • Zeolite X has the formula Nagg [ (A10 2 ) 35 (Si0 2 ) 106 ] • 276 H 2 ° has the formula Na 6 [ (A10 2 ) 6 (Si0 2 ) 6 ] 7.5 H 2 0) .
  • a highly preferred component of the compositions for use in accord with the invention is a surfactant system comprising surfactant selected from anionic, cationic, nonionic ampholytic and zwitterionic surfactants and mixtures thereof.
  • the surfactant system is present at a level of from 0.5% to 50% by weight, more preferably 1% to 40% by weight, most preferably from 2% to 30% 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 testers in which the fatty acid is derived from a C 6 -C18 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 Cg-Ci ⁇ alkyl ethoxysulfate salt comprises a primary alkyl ethoxysulfate which is derived from the condensation product of a Cg-C ⁇ g alcohol condensed with an average of from one to seven ethylene oxide groups, per mole.
  • anionic surfactants suitable for the purposes of the invention are the alkali metal sarcosinates of formula
  • R-CON (R 1 ) CH 2 COOM wherein R is a C 5 -C 1 7 linear or branched alkyl or alkenyl group, R 1 is a C*L-C 4 alkyl group and M is an alkali metal ion.
  • R is a C 5 -C 1 7 linear or branched alkyl or alkenyl group
  • R 1 is a C*L-C 4 alkyl group
  • M is an alkali metal ion.
  • Preferred examples are the lauroyl, Cocoyl (C 12 ⁇ c 1 4) ' 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 S0 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, etc.
  • the preferred alkyl ester sulfonate surfactants have the structural formula:
  • R 3 is a C 8 -C 20 hydrocarbyl, preferably an alkyl, or combination thereof
  • R 4 is a C ⁇ Cg hydrocarbyl, preferably an alkyl, or combination thereof
  • 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 1 6 alkyl
  • R is methyl, ethyl or isopropyl.
  • the methyl ester sulfonates wherein R 3 is C ⁇ Q -C ⁇ g alkyl.
  • One class of nonionic surfactants useful in the present invention comprises the water soluble ethoxylated Cg-C- ⁇ g fatty alcohols and Cg-C- ⁇ g mixed ethoxylated/propoxylated fatty alcohols and mixtures thereof.
  • the ethoxylated fatty alcohols are the C ⁇ o -c 1 6 ethoxylated fatty alcohols with a degree of ethoxylation of from 3 to 50, most preferably these are the C 12 -C ⁇ 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, a blend of C 12 -C 15 alcohols, Ethyl 24 sold by the Ethyl Corporation, 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.
  • Another class of nonionic surfactants comprises alkyl polyglucoside compounds of general formula
  • 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.
  • Compounds of this type and their use in detergent compositions are disclosed in EP-B 0070074, 0070077, 0075996 and 0094118.
  • Another preferred nonionic surfactant is a polyhydroxy fatty acid amide surfactant compound having the structural formula: O R-L
  • R 1 is H, C ⁇ ⁇ hydrocarbyl, 2-hydroxy ethyl, 2- hydroxy propyl, or a mixture thereof, preferably C 1 -C alkyl, more preferably C ⁇ or C 2 alkyl, most preferably C 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 ⁇ -Cn alkyl or alkenyl, most preferably straight chain C5-C9 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, coca ide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, or tallowa ide.
  • 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-ldeoxyglucityl C ⁇ -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 Cg-C 0 , preferably C 6 -C 10 N-alkyl or alkenyl amine oxides and propylene-l,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 -C ⁇ g, preferably Cg- 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 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.
  • Amylase enzymes may be incorporated 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 orvza. 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.
  • the detergent compositions may 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 about 32:68; a paraffin oil meeting these characteristics is sold by Wintershall, Salzbergen, Germany, under the trade name WINOG 70.
  • Another optional ingredient is a lime soap dispersant compound, present at a level of from 0.05% to 40% by weight, more preferably 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.
  • compositions may fully contain from 0.05% to 2% by weight of the composition, preferably from 0.05% to 1% by weight, most preferably from 0.1% to 0.5% by weight of a chelant (heavy metal sequestrant) .
  • a chelant heavy metal sequestrant
  • a suitable chelant for inclusion in the detergent compositions in accordance with the invention is ethylenediamine-N,N'-disuccinic acid (EDDS) or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof.
  • EDDS compounds are the free acid form and the sodium or magnesium salt thereof. Examples of such preferred sodium salts of EDDS include Na 2 EDDS and Na 4 EDDS. Examples of such preferred magnesium salts of EDDS include MgEDDS and Mg 2 EDDS. The magnesium salts are the most preferred for inclusion in compositions in accordance with the invention.
  • chelants include the organic phosphonates, including amino alkylene poly (alkylene phosphonate) , alkali metal ethane 1-hydroxy diphosphonates, nitrilo trimethylene phosphonates, ethylene diamine tetra methylene phosphonates and diethylene triamine penta methylene phosphonates.
  • 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 where present are in the form of their magnesium salt.
  • the level of phosphorus containing chelants in the compositions of the invention is preferably minimised, with their complete exclusion from the compositions being most preferred.
  • 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 mixutes 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 :
  • each R independently can be an alkyl or an aryl radical.
  • 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 to 0.1m 2 /s 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 50m 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 about 500 to about 200,000 at a weight ratio of silicone to silanated silica of from about 1:1 to about 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 Corning, 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.
  • silicone suds controlling agents are described in copending European Application 91870007.1 in the name of the Procter and Gamble Company which discloses granular suds controlling agents comprising a silicone antifoam compound, a carrier material an organic coating material and glycerol at a weight ratio of glycerol: silicone antifoam compound of 1:2 to 3:1.
  • Copending European Application 91201342.0 also discloses highly preferred granular suds controlling agents comprising a silicone antifoam compound, a carrier material, an organic coating material and crystalline or amorphous aluminosilicate at a weight ratio of aluminosilicate: silicone antifoam compound of 1:3 to 3:1.
  • Ther preferred carrier material in both of the above described highly preferred granular suds controlling agents is starch.
  • 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 20 - 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 suitable for inclusion in the compositions include antiredeposition, and soil-suspension agents, corrosion inhibition, perfumes, colours and filler salts, with sodium sulfate being a preferred filler salt.
  • compositions can be formulated in any desirable form such as powders, granulates, pastes, liquids, gels and tablets.
  • the bulk density of granular compositions 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 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, carboxy ethylcellulose, 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 also envisaged in the present invention.
  • the pH of a 1% solution of the present compositions is preferably from 6 to 12.
  • Granular compositions for use in accordance with the present invention can be made via a variety of methods including dry mixing, spray drying, agglomeration and granulation.
  • a preferred method of making the granular compositions involves a combination of dry mixing and agglomeration techniques.
  • the following technique can be used to characterize polymers spectrophotometrically to check if they have the potential to reduce porphin deposition.
  • a 0.1M phosphate buffer solution whose pH has been adjusted to desired pH, is prepared in which the metal porphin concentration is about 10 ⁇ 5 molar.
  • add increasing amounts of the polymer starting with 10 ppm and up to 1000 ppm. Gently shake the sample after each addition of polymer and wait for a few minutes before measuring the spectrum again. Compare the spectrum to the original spectrum of the porphin solution. Look for the following differences :
  • Fe(III)TPPS was scanned between 350 and 500 nm.
  • the absorbance peak occurs at about 414 nm.
  • the extent of dye oxidation was compared between a composition containing imidazole as amine base catalyst and a system without amine base catalyst.
  • Composition A A detergent solution (lOOmL) containing dyes (40 ppm final concentration), glucose (0.1% by weight) and a ferric tetrasulfonated tetraphenylporphin catalyst (l x 10" 5 M) was prepared and its pH value adjusted to 8.0.
  • Composition B A detergent solution (lOOmL) containing dyes (40 ppm final concentration), glucose (0.1% by weight), and ferric tetrasulfonated tetraphenylporphin catalyst (2.5 x 10 ⁇ 6 M) and imidazole (10 mM) was prepared and its pH value adjusted to pH 8.0.
  • the absorbance spectrum was recorded (350-750 nm) . This region encompasses the wavelength maximum of the dyes (as noted in the table below) and the Soret band of the catalyst (414 nm) . Glucose oxidase (final concentration O.lU/mL) was then added to the stirred solution to initiate the reaction. After 30 min the absorbance spectrum was recorded and the decrease in the absorbance maximum of the dyes noted.
  • Acid Blue 9 Direct blue 98 Direct blue 120 Acid blue 113 FD&C Red 40 Acid Yellow 40
  • composition B Even though a lower level of iron porphin catalyst is present in composition B, dyes are oxidized to a much bigger extent compared to composition A containing 4 times the iron porphin catalyst level.
  • a detergent solution (lOOmL) of glucose (0.1% by weight) and different metallo catalysts (10 x 10 ⁇ 5 M) was prepared and the pH adjusted to 8.0. To initiate the reaction, different levels of glucose oxidase were added. The destruction of the catalyst was measured in each case by quantifying the decrease in absorption of the Soret band (414 nm) .
  • the catalyst destruction was compared with and without imidazole at different time intervals.
  • A, B and C are granular machine dishwashing detergent compositions for use in a dishwashing method in accord with the invention.
  • Tri-Sodium citrate dihydrate MA/AA Copolymers of 1:4 maleic/acrylic acid, average molecular weight about 80,000
  • Silicate Amorphous Sodium Silicate (Si0 2 :Na 2 0 ratio normally follows)
  • Proteolytic enzyme sold under the trade name
  • Amylase Amylolytic enzyme sold under the trade name
  • Nonionic C1 3 -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 trade name Plurafac LF404 by BASF GmbH.
  • compositions A, B and C were added 250 units/gram of composition of glucose oxidase enzyme.
  • compositions A, B and C were used in a machine dishwashing method employing a conventional dishwasher machine with a product dosage of 20g of product to 5 litres of wash solution.
  • the level of glucose oxidase enzyme in the wash solution was hence 1,000 U/l, and that of the ferric tetrasulfonated porphin was 400 ppm.
  • Polypropylene is commonly employed in the manufacture of food containers, which are often used to store fruits and other foodstuffs.
  • a sample of clear polypropylene (a section from a resealable polypropylene lid of a food container) was immersed in a concentrated solution of blackcurrant juice at 65°C for 6 hours. The extent of discoloration of the sample was determined by visual comparison with a sample, which had not been immersed in the blackcurrant juice solution.
  • a 1.7% solution of blackcurrant cordial was made up by dilution of blackcurrant concentrate with distilled water.
  • Six 100 ml samples (A-F) of this solution were added to individual glass beakers. Samples A-C were buffered to pH 7, and samples D-F were buffered to ph 10. (Manual dishwashing methods are typically carried out at neutral pH, whereas in machine dishwashing more alkaline conditions are typical) .
  • To beakers B, C and E, F were added, with stirring, glucose oxidase, iron porphin (FePPTS) and glucose such that the concentrations by weight of each of these components in the solutions was:
  • the colour of the samples was graded visually at set time intervals from addition of the decolourising agents.

Abstract

La présente invention concerne un procédé de lavage de vaisselle, en particulier de lavage de vaisselle en machine, dans lequel les articles à laver sont traités avec une quantité efficace d'une composition détergente contenant: A. un catalyseur organo-métallique choisi parmi a) les métallo-porphines et leurs dérivés hydrosolubles ou pouvant se disperser dans l'eau; b) les métalloporphyrines et leurs dérivés hydrosolubles ou pouvant se disperser dans l'eau; c) les métallo-phtalocyanines et leurs dérivés hydrosolubles ou pouvant se disperser dans l'eau; et B. un système enzymatique capable de générer du peroxyde d'hydrogène.
EP94913945A 1993-04-09 1994-03-23 Procede de lavage en lave-vaisselle utilisant un catalyseur organometallique et une enzyme pour produire du peroxyde d'hydrogene Ceased EP0692947A4 (fr)

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EP94913945A EP0692947A4 (fr) 1993-04-09 1994-03-23 Procede de lavage en lave-vaisselle utilisant un catalyseur organometallique et une enzyme pour produire du peroxyde d'hydrogene

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EP93870066 1993-04-09
EP93870066 1993-04-09
EP94913945A EP0692947A4 (fr) 1993-04-09 1994-03-23 Procede de lavage en lave-vaisselle utilisant un catalyseur organometallique et une enzyme pour produire du peroxyde d'hydrogene
PCT/US1994/003169 WO1994023637A1 (fr) 1993-04-09 1994-03-23 Procede de lavage en lave-vaisselle utilisant un catalyseur organometallique et une enzyme pour produire du peroxyde d'hydrogene

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US5968881A (en) * 1995-02-02 1999-10-19 The Procter & Gamble Company Phosphate built automatic dishwashing compositions comprising catalysts
DE69617209T2 (de) * 1995-02-02 2002-07-25 Procter & Gamble Verfahren zur entfernung von teeflecken in geschirrspülern mit zusammensetzungen enthaltend kobalt (iii)- katalysator
EP0807159B1 (fr) * 1995-02-02 2000-05-24 The Procter & Gamble Company Compositions pour lave-vaisselles automatiques comprenant des catalyseurs chelates au cobalt
CA2224559A1 (fr) * 1995-06-16 1997-01-03 The Procter & Gamble Company Compositions d'agents de blanchiment comprenant des catalyseurs au cobalt
CA2224558C (fr) * 1995-06-16 2003-07-15 The Procter & Gamble Company Compositions detergentes pour lave-vaisselle automatiques, contenant des catalyseurs au cobalt
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WO2021073901A1 (fr) * 2019-10-15 2021-04-22 Unilever Ip Holdings B.V. Composition détergente
CN113430063B (zh) * 2020-03-23 2024-02-23 上海新阳半导体材料股份有限公司 用于选择性移除硬遮罩的清洗液、其制备方法及应用

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EP0327927A2 (fr) * 1988-02-06 1989-08-16 Henkel Kommanditgesellschaft auf Aktien Additif pour détergents
EP0369678A2 (fr) * 1988-11-11 1990-05-23 Unilever Plc Composition de blanchiment
EP0384503B1 (fr) * 1989-02-22 1995-06-28 Unilever N.V. Métalloporphyrines pour l'utilisation comme catalyseur de blanchiment
WO1991005839A1 (fr) * 1989-10-13 1991-05-02 Novo Nordisk A/S Inhibition de transfert de colorant
EP0530870A1 (fr) * 1991-08-23 1993-03-10 Unilever N.V. Composition pour le lavage de la vaisselle en machine

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WO1994023637A1 (fr) 1994-10-27
CA2160231A1 (fr) 1994-10-27
EP0692947A4 (fr) 1996-03-13
CA2160231C (fr) 1999-09-21

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