WO1994007985A1 - Composition de detergent contenant un dispersant de savon de chaux et des lipases - Google Patents

Composition de detergent contenant un dispersant de savon de chaux et des lipases Download PDF

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Publication number
WO1994007985A1
WO1994007985A1 PCT/US1993/008877 US9308877W WO9407985A1 WO 1994007985 A1 WO1994007985 A1 WO 1994007985A1 US 9308877 W US9308877 W US 9308877W WO 9407985 A1 WO9407985 A1 WO 9407985A1
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Prior art keywords
weight
detergent composition
composition according
alkyl
detergent
Prior art date
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PCT/US1993/008877
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English (en)
Inventor
Beatrijs Lutgarde A. De Smet
Johan Gerwin L. Pluyter
Lynda Anne Jones
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The Procter & Gamble Company
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Priority claimed from GB929220343A external-priority patent/GB9220343D0/en
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to AT93922707T priority Critical patent/ATE211163T1/de
Priority to EP93922707A priority patent/EP0662119B1/fr
Priority to DE69331388T priority patent/DE69331388T2/de
Publication of WO1994007985A1 publication Critical patent/WO1994007985A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38627—Preparations containing enzymes, e.g. protease or amylase containing lipase
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/75—Amino oxides
    • 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
    • C11D3/0026—Low foaming or foam regulating 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds

Definitions

  • This invention relates to a machine dishwashing and rinsing detergent compositions containing lipolytic enzyme, a lime soap dispersant, and preferably water-soluble detergent builder compound.
  • the overall performance of a machine dishwashing detergent product is judged by not only its ability to remove soils, particularly greasy soils, but also by its ability to prevent the redeposition of the soils, or the breakdown products of the soils or of any insoluble salts, on the articles being washed.
  • the insoluble salts may be the calcium, magnesium or heavy metal ion - containing salts of the soils, or the breakdown products of the soils, or they may be purely inorganic in nature. Redeposition effects results in the articles being coated in an unseemly film, appearing streaked or being covered in visible spots which remain intact at the end of the wash process. Spotting, filming and streaking effects are visually most noticeable on glassware and on plastic articles.
  • rinsing (or rinse aid) product The performance of a rinsing (or rinse aid) product is judged largely on its ability to prevent the, spotting, filming and streaking of the articles being rinsed.
  • the ability to prevent the redeposition of soils which may have been carried over from the main wash step to the rinse step of the machine dishwashing process is therefore a key measure of the effectiveness of a rinse aid product.
  • Builder compounds are conventionally used in machine dishwashing and rinsing detergent products. Their
  • magnesium and calcium ions may, in the absence of builder compounds or in underbuilt conditions, form
  • insoluble salts which deposit as visible spots on the surfaces of the articles being washed. It is desirable that the builder compounds used in machine dishwashing detergent products are water-soluble since water insoluble builders compounds may also deposit on the articles being washed, remaining as visible spots at the end of the wash process.
  • machine dishwashing or rinsing detergent products are free from chlorine bleaches or phosphate builder compounds.
  • spotting and filming effects are known to be a particular problem for machine dishwashing and rinsing products containing no chlorine bleach and/or no phosphate builder compound.
  • Lipolytic enzymes are known to assist in the breakdown of triglyceride and fatty ester soils, and are therefore recognized as being of value as components of detergent compositions. Laundry detergent products
  • Machine dishwashing and rinsing detergent compositions containing lipolytic enzyme have been disclosed, for example, in EP-B-0271555 and EP-A-0346136.
  • EP-B-0271155 teaches that the addition of lipases to a dishwashing or rinsing composition reduces significantly the formation of film or spots on the
  • EP-A-0346136 teaches similar spotting and filming reductions for the inclusion of special lipases produced by cloning rDNA technologies into a machine dishwashing detergent composition.
  • 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. Some, but not all, lime soap dispersants also demonstrate surfactant capability. Conversely, not all surfactants may act as effective lime soap dispersants. It is, however, desirable in the detergent compositions of the invention that the lime soap dispersant also has surface active (surfactant) capability.
  • the machine dishwashing or rinsing detergent compositions of the present invention are of particular value when formulated as compositions containing no chlorine bleach and no phosphate builder compound since they provide the abovementioned mitigation of spotting and filming effects for these formulations where spotting and filming is known to be a particular problem.
  • the composition contains water-soluble
  • the detergent builder compound is a non-phosphate detergent builder compound.
  • the composition is free from chlorine bleach.
  • a machine dishwashing or rinsing process comprising 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 machine dishwashing or rinsing composition as described hereinabove.
  • an effective amount of the machine dishwashing composition it is meant from 8g to 60g of product, and by an effective amount of the rinsing composition it is meant from 0.5g to 15g 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 or rinsing processes.
  • the machine dishwashing or rinsing detergent compositions of the present invention preferably contain detergent builder compound present at a level of from 1% to 80% by weight, preferably from 10% to 70% by weight, most
  • the detergent builder compound is most preferably water-soluble.
  • Suitable water-soluble detergent builder compounds include, but are not restricted to monomeric polycarboxylates, 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 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 1 ) of less than 9, preferably of between 2 and 8.5, more preferably of between 4 and 7.5.
  • the logarithmic acidity constant is defined by reference to the equilibrium
  • A is the fully ionized carboxylate anion of the builder salt.
  • the carboxylate or polycarboxylate builder can be momomeric or oligomeric in type although monomeric polycarboxylates are generally preferred for reasons of cost and
  • Monomeric and oligomeric builders can be selected from acyclic, alicyclic, heterocyclic and aromatic carboxylates having the general formulae
  • R 1 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 1-4 alkyl, alkenyl or hydroxy alkyl, or alkaryl, sulfo, or phosphono groups
  • X represents a single bond; O; S; SO; SO 2 ; or NR 1 ;
  • Y represents H; carboxy;hydroxy; carboxymethyloxy; or
  • Z represents H; or carboxy
  • n 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 carboxyl 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
  • 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
  • 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
  • Aromatic polycarboxylates include mellitic acid
  • hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.
  • 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.
  • Other 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 phytic acid
  • silicates phytic acid
  • Borate builders as well as builders containing borate-forming materials that can produce borate under detergent storage or wash conditions can also be used but are not preferred at wash conditions less that about 50°C , especially less than about 40°C.
  • carbonate builders are the alkaline earth and alkali metal carbonates, including sodium carbonate and sesqui-carbonate and mixtures thereof with ultra-fine calcium carbonate as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973.
  • 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 phytii acid.
  • Suitable silicates include the water soluble sodium
  • 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.
  • compositions of the invention may also include less water soluble builders although preferably their levels of incorporation are minimized. 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
  • x in the general formula above has a value of 2 ,
  • M is sodium and y is 0 and preferred examples of this formula comprise the ⁇ - , ß -, ⁇ - and ⁇ - forms of Na 2 Si 2 O 5 .
  • the crystalline layered sodium silicate material is
  • a solid, water-soluble ionisable material 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
  • 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
  • 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 (Attorney's Docket No CM369F).
  • Suitable aluminosilicate zeolites have the unit cell formula Na z [(AlO 2 ) 2 (SiO 2 )y].
  • 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.
  • particle size diameter herein represents the average particle size diameter of a given ion exchange material as determined by conventional
  • 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 purpose 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
  • Zeolite A has the formula
  • the first essential component of the machine dishwashing or rinsing compositions of the invention is a lime soap dispersant compound, which has a lime soap dispersing power (LSDP), as defined hereinafter of no more than 8,
  • the lime soap dispersant compound is present at a level of from 0.1% to 40% by weight, more preferably 1% to 20% by weight, most preferably from 2% to 10% by weight of the compositions.
  • a lime soap dispersant is a material that prevents the precipitation of alkali metal, ammonium or amine salts of fatty acids by calcium or magnesium ions.
  • a numerical measure of the effectiveness of a lime soap dispersant is given by the lime soap dispersing power (LSDP) which is determined using the lime soap dispersion test as described in an article by H.C. Borghetty and CA. Bergman, J. Am. Oil. Chem. Soc, volume 27, pages 88-90, (1950).
  • This lime soap dispersion test method is widely used by practitioners in this art field being referred to , for example, in the following review articles; W.N. Linfield, Surfactant
  • the LSDP is the % weight ratio of
  • dispersing agent to sodium oleate required to disperse the lime soap deposits formed by 0.025g of sodium oleate in
  • CaCO 3 (Ca:Mg 3:2) equivalent hardness.
  • the lime soap dispersing power is then obtained as:
  • a material with a lower LSDP is a more effective lime soap dispersant than one with a higher LSDP.
  • a listing of suitable lime soap dispersants for use in accord with the invention is given in the above mentioned review by M. Linfield to be found in Tenside. Sust. Det., Volume 27, pages 159-161 (1990).
  • Polymeric lime soap dispersants suitable for use herein are described in the above mentioned article by M.K. Nagarajan and W.F. Masler, to be found in Cosmetics and Toiletries, Volume 104, pages 71-73, (1989).
  • Examples of such polymeric lime soap dispersants include certain water-soluble salts of copolymers of acrylic acid, methacrylic acid or mixtures thereof, and an acrylamide or substituted acrylamide, where such polymers typically have a molecular weight of from 5,000 to 20,000.
  • Surfactants having good lime soap dispersant capability will include certain amine oxides, betaines, sulfobetaines, alkyl ethoxysulfates and ethoxylated alcohols.
  • Exemplary surfactants having a LSDP of no more than 8 for use in accord with the invention include C 16 -C 18 dimethyl amine oxide, C 12 -C 18 alkyl ethoxysulfates with an average degree of ethoxylation of from 1-5, particularly C 12 -C 15 alkyl ethoxysulfate surfactant with a degree of
  • the second essential component of the machine dishwashing or rinsing detergent compositions in accord with the invention is lipolytic enzyme (lipase) present at levels of active lipolytic enzyme of from 0.001% to 2% by weight, preferably 0.001% to 1% by weight, most preferably from 0.001% to 0.5% by weight of the compositions.
  • lipase is preferably bacterial in origin being obtained from a lipase producing strain of Humicola sp.or
  • Lipase from chemically or genetically modified mutants of these strains are also included herein. Mixtures of lipase from various strains are included herein, though not preferred.
  • a preferred lipase is derived from Pseudomonas
  • Another preferred lipase herein is obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Aspergillus oryza. as host, as described in European Patent Application, EP-A-0258 068, which is commercially available from Novo Industri A/S, Bagsvaerd, Denmark, under the trade name Lipolase. This lipase is also described in U.S.
  • Lipases herein are preferably compatible with anionic (and nonionic) surfactants and have high activity at alkaline pH. They are preferably compatible with and stable in present compositions and improve cleaning when they are included in the present compositions.
  • Suitable lipases include those which show a positive immunological cross-reaction with the antibody of the lipase produced by Pseudomonas flluorescens. This lipases described in Japanese Patent Application 53-20487, laid open February 24, 1987. It is available under the trade name Lipase P Amano. A method for testing immunological cross-reaction with Amano P antibody is described in U.S. Patent 4,707,291, Thorn et al, issued November 17, 1987. A lipase unit (LU) is defined as the amound of lipase which produces 1 umol of titratable butyric acid per minute in a pH stat, where pH is 7.0, temperature is 30°C, and
  • substrate is an emulsion of ributyrin and gum arabic in the presence of Ca ++ and NaCl in phosphate buffer.
  • a highly preferred component of the machine dishwashing or rinsing compositions of the invention is a surfactant system comprising surfactant selected from anionic,
  • the surfactant system is present at a level of from 0.1% to 50% by weight, more preferably 1% to 25% by weight, most preferably from 2% to 20% by weight of the compositions.
  • the surfactant system is preferably formulated to be compatible with enzyme components present in the
  • the surfactant system is most preferably formulated such that it promotes, or at least does not degrade, the stability of enzyme in these compositions.
  • the anionic surfactant may be essentially any anionic surfactant, including anionic sulfate, sulfonate or
  • Highly preferred anionic surfactants herein are sodium or potassium salt-forms for which the corresponding calcium salt form has a low Krafft temperature of for example 30 deg. C or below, or, even better, 20 deg. C or lower.
  • anionic surfactants may act such as to complement the spotting/filming preventative action of the lime soap dispersant components of the compositions in accord with the present invention.
  • highly preferred anionic surfactants are the
  • alkyl (polyethoxy) sulfates alkyl (polyethoxy) sulfates.
  • the anionic sulfate surfactant may be any organic sulfate surfactant. It is preferably selected from the group consisting of C 6 -C 18 alkyl sulfate which has been
  • the anionic sulfate surfactant is a C 6 -C 18 alkyl sulfate which has been ethoxylated with from about 0.5 to about 20, preferably from about 0.5 to about 5, moles of ethylene oxide per molecule.
  • Preferred alkyl ethoxy sulfate surfactants comprise a primary alkyl ethoxy sulfate derived from the condensation product of a C 6 -C 18 alcohol with an average of from about
  • Blends can be made of material having different degrees of
  • Anionic sulfate surfactants include the C 5 -C 17 acyl-N-(C 1 -C 4 alkyl) and -N-(C 1 -C 2 hydroxyalkyl) glucamine sulfates, preferably those in which the C 5 -C 17 acyl group is derived from coconut or palm kernel oil. These materials can be prepared by the method disclosed in U.S. Patent 2,717,894, Schwartz, issued September 13, 1955.
  • the counterion for the anionic sulfate surfactant component is preferably selected from calcium, sodium, potassium, magnesium, ammonium, or alkanol-ammonium, and mixtures thereof.
  • Anionic sulfonate surfactant Anionic sulfonate surfactant
  • Anionic sulfonate surfactants suitable for use herein include essentially any sulfonate surfactants including, for example, the salts (eg : alkali metal salts) of C 5 -C 20 linear alkylbenzene sulfonates, C 6 -C 22 primary or secondary alkane sulfonates, C 6 -C 24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, paraffin sulfonates, and any mixtures thereof.
  • the salts eg : alkali metal salts
  • C 5 -C 20 linear alkylbenzene sulfonates C 6 -C 22 primary or secondary alkane sulfonates
  • Alkyl ethoxy carboxylates suitable for use herein include those with the fomula RO(CH 2 CH 2 O) x CH 2 COO-M + wherein R is a C 6 to C 18 alkyl group, x ranges from 0 to 10, and the ethoxylate distribution is such that, on a weight basis, the amount of material where x is 0 is less than about 20
  • the average x is from about 2 to 4 when the average R is C 13 or less, and the average x is from about 3 to 6 when the average R is greater than C 13 , and M is a cation,
  • alkali metal preferably chosen from alkali metal, alkaline earth metal, ammonium, mono-, di-, and tri-ethanol-ammonium, most preferably from sodium, potassium, ammonium and mixtures thereof with magnesium ions.
  • the preferred alkyl ethoxy carboxylates are those where R is a C 12 to C 18 alkyl group.
  • Alkyl polyethoxy polcarboxylate surfactants suitable for use herein include those having the formula :
  • R is a C 6 to C 18 alkyl group, x is from 1 to 25, R 1 and R 2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical, and mixtures thereof, wherein at least one R 1 or R 2 is a succinic acid radical or hydroxysuccinic acid radical, and R 3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof.
  • Alkali metal sarcosinate surfactant Other 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 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 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, etc.
  • 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
  • R 3 is C 10 -C 18 alkyl
  • R 4 is methyl, ethyl or isopropyl.
  • methyl ester sulfonates wherein R 3 is C 10 -C 18 alkyl.
  • Other anionic surfactants are Especially preferred.
  • anionic surfactants useful for detersive purposes can also be included in the compositions hereof. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of fatty oleyl glycerol
  • sulfates alkyl phenol ethylene oxide ether sulfates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of
  • sulfosuccinate especially saturated and unsaturated C 12 - C 18 monoesters
  • diesters of sulfosuccinate especially saturated and unsaturated C 8 -C 14 diesters
  • N-acyl especially saturated and unsaturated C 8 -C 14 diesters
  • sarcosinates sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described herein), branched primary alkyl sulfates, alkyl polyethoxy carboxylates such as those of the formula RO(CH 2 CH 2 O) k CH 2 COO-M + wherein R is a C 8 -C 22 alkyl, k is an integer from 0 to 10, and M is a soluble salt-forming cation, and fatty acids esterified with isethionic acid and neutralized with sodium hydroxide.
  • Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil. Further examples are given in "Surface Active Agents and Detergents” (Vol. I and II by Schwartz, Perry and
  • Nonionic surfactant Suitable nonionic detergent surfactants are generally disclosed in U.S. Patent 3,929,678, Laughlin et al., issued December 30, 1975, at column 13, line 14 through column 16, line 6, incorporated herein by reference. Exemplary, non- limiting classes of useful nonionic surfactants are listed below.
  • Nonionic polyhydrox ⁇ fatty acid amide surfactant Nonionic polyhydrox ⁇ fatty acid amide surfactant
  • Polyhydroxy fatty acid amides suitable for use herein are those having the structural formula :
  • R1 is H, C 1 -C 4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof, preferable C1-C4 alkyl, more preferably C 1 or C 2 alkyl, most preferably C 1 alkyl (i.e., methyl); and R 2 is a C 5 -C 31 hydrocarbyl, preferably straight-chain C 5 -C 19 alkyl or alkenyl, more preferably straight-chain C 9 -C 17 alkyl or alkenyl, most preferably straight-chain C 11 -C 17 alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative
  • 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 -CH2-OH 2 , -CH(CH 2 OH)-(CHOH) n -, -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
  • 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.
  • R2-CO-N ⁇ can be, for example, cocamide, stearamide,
  • Z can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl, 1-deoxygalactityl, 1-deoxymannityl, 1-deoxymaltotriotityl, etc.
  • the most preferred polyhydroxy fatty acid amide has the general formula :
  • R 2 is a straight chain C 11 -C 17 alkyl or alkenyl group.
  • polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols are suitable for use herein.
  • the polyethylene oxide condensates are
  • These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 18 carbon atoms in either a straight chain or branched chain configuration with the alkylene oxide.
  • the ethylene oxide is present in an amount equal to from about 5 to about 25 moles of ethylene oxide per mole of alkyl phenol.
  • nonionic surfactants of this type include IgepalTM CO-630, marketed by the GAF Corporation; and TritonTM X-45, X-114, X-100, and X-102, all marketed by the Rohm & Haas Company.
  • alkyl ethoxylate condensation products of aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide are suitable for use herein .
  • the alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms.
  • Particularly preferred are the condensation products of alcohols having an alkyl group containing from
  • nonionic surfactants of this type include TergitolTM 15-S-9 (the condensation product of C 11 -C 15 linear alcohol with 9 moles ethylene oxide), TergitolTM 24-L-6 NMW (the condensation product of C 12 -C 14 primary alcohol with 6 moles ethylene oxide with a narrow molecular weight distribution), both marketed by
  • NeodolTM 45-9 the condensation product of C 14 -C 15 linear alcohol with 9 moles of ethylene oxide
  • NeodolTM 23-6.5 the condensation product of C 12 - C 13 linear alcohol with 6.54 moles of ethylene oxide
  • NeodolTM 45-7 (the condensation product of C 14 -C 15 linear alcohol with 7 moles of ethylene oxide)
  • NeodolTM 45-4 the condensation product of C 14 -C 15 linear alcohol with 4 moles of ethylene oxide
  • KyroTM EOBN (the condensation product of C 13 -C 15 alcohol with 9 moles ethylene oxide), marketed by The Procter & Gamble Company.
  • the ethoxylated C 6 -C 18 fatty alcohols and C 6 -C 18 mixed ethoxylated/propoxylated fatty alcohols are suitable surfactants for use herein, particularly where water soluble.
  • the ethoxylated fatty alcohols are the C 10 -C 18 ethoxylated fatty alcohols with a degree of
  • ethoxylation of from 3 to 50, most preferably these are the C 12 -C 18 ethoxylated fatty alcohols with a degree of
  • ethoxylated/propoxylated fatty alcohols have an alkyl chain length of from 10 to 18 carbon atoms, a degree of
  • hydrophobic base formed by the condensation of propylene oxide with propylene glycol are suitable for use herein.
  • the hydrophobic portion of these compounds preferably has a molecular weight of from about 1500 to about 1800 and exhibits water insolubility.
  • polyoxyethylene moieties of this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of the product is retained up to the point where the polyoxyethylene content is about 50% of the total weight of the condensation product, which corresponds to condensation with up to about 40 moles of ethylene oxide.
  • Examples of compounds of this type include certain of the commercially-available PluronicTM
  • condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine are suitable for use herein.
  • hydrophobic moiety of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of from about 2500 to about 3000.
  • This hydrophobic moiety is condensed with ethylene oxide to the extent that the condensation product contains from about 40% to about 80% by weight of polyoxyethylene and has a molecular weight of from about 5,000 to about 11,000.
  • nonionic surfactant include certain of the commercially available TetronicTM compounds, marketed by BASF.
  • Suitable alkylpolysaccharides for use herein are disclosed in U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containng from about 1.3 to about 10, preferably from about 1.3 to about 3 , most preferably from about 1.3 to about 2.7 saccharide units. Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties. (Optionally the hydrophobic group is attached at the 2-, 3-, 4-, etc.
  • the intersaccharide bonds can be, e.g., between the one position of the additional saccharide units and the 2-, 3-, 4-, and/or 6- positions on the preceding saccharide units.
  • the preferred alkyleneoxide is ethylene oxide.
  • Typical hydrophobic groups include alkyl groups, either saturated or unsaturated, branched or unbranched containing from 8 to 18, preferably from 10 to 16, carbon atoms.
  • the alkyl group is a straight-chain saturated alkyl group.
  • the alkyl group can contain up to about 3 hydroxyl groups and/or the
  • polyalkyleneoxide chain can contain up to about 10, preferably less than 5, alkyleneoxide moieties.
  • Suitable alkyl polysaccharides are octyl, nonyldecyl,
  • Suitable mixtures include coconut alkyl, di-, tri-, tetra-, and
  • the preferred alkylpolyglycosides have the formula R 2 O(C n H 2n O)t(glycosyl) x wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18, preferably from 12 to 14, carbon atoms; n is 2 or 3, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7.
  • the glycosyl is preferably derived from glucose. To prepare these compounds, the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the 1-position). The additional glycosyl units can then be attached between their 1-position and the preceding glycosyl units 2-, 3-, 4- and/or 6-position, preferably predominantly the 2-position.
  • Nonionic fatty acid amide surfactant is selected from the group consist
  • Fatty acid amide surfactants suitable for use herein are those having the formula:
  • R 6 is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon atoms and each R 7 is selected from the group consisting of hydrogen, C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl, and
  • Ampholytic surfactants can be incorporated into the
  • detergent compositions herein These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical can be straight chain or branched.
  • One of the aliphatic substituents contains at least about 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one contains an anionic water-solubilizing group, e.g., carboxy, sulfonate, sulfate. See U.S. Patent No. 3,929/678 to Laughlin et al., issued December 30, 1975 at column 19, lines 18-35 for examples of ampholytic
  • Suitable amphoteric surfactants for use herein include the alkyl amphocarboxylic acids of the formula
  • R is a C 6 -C 18 alkyl group
  • R i is of the general formula
  • R 1 is a (CH 2 ) x COOM or CH 2 CH 2 OH, and x is 1 or 2 and
  • M is preferably chosen from alkali metal, alkaline earth metal, ammonium, mono-, di-, and tri-ethanolammonium, most preferably from sodium, potassium, ammonium and mixtures thereof with magnesium ions.
  • the preferred R alkyl chain length is a C 10 to C 14 alkyl group.
  • amphocarboxylic acid is produced from fatty imidazolines wherein the dicarboxylic acid functionality of the
  • amphodicarboxylic acid is diacetic acid and/or dipropionic acid.
  • Amine oxides useful in the present invention include those compounds having the formula :
  • R 3 is selected from an alkyl, hydroxyalkyl
  • R 4 is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, preferably 2 carbon atoms, or mixtures thereof;
  • x is from 0 to 5, preferably from 0 to 3; and each R 5 is an alkyl or
  • hydyroxyalkyl group containing from 1 to 3, preferably from 1 to 2 carbon atoms, or a polyethylene oxide group
  • R 5 groups can be attached to each other, e.g., through an oxygen or nitrogen atom, to form a ring
  • amine oxide surfactants in particular include C 10 -C 18 alkyl dimethyl amine oxides and C 6 -C 18 alkoxy ethyl
  • dihydroxyethyl amine oxides examples include dimethyloctylamine oxide, diethyldecylamine oxide, bis-(2-hydroxyethyl)dodecylamine oxide,
  • dimethyl-2-hydroxyoctadecylamine oxide Preferred are C 10 - C 18 alkyl dimethylamine oxide, and C 10-18 acylamido alkyl dimethylamine oxide.
  • Zwitterionic surfactants can also be incorporated into the detergent compositions hereof. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. See U.S.
  • betaine surfactant The betaines useful herein are those compounds having the formula R(R') 2 N + R 2 COO- wherein R is a C 6 -C 18 hydrocarbyl group, preferably a C 10- C 16 alkyl group or C 10-16 acylamido alkyl group, each R 1 is typically C 1 -C 3 alkyl, preferably methyl,m and R 2 is a C 1 -C 5 hydrocarbyl group, preferably a C 1 -C 3 alkylene group, more preferably a C 1 -C 2 alkylene group.
  • suitable betaines include coconut acylamidopropyldimethyl betaine; hexadecyl dimethyl
  • acylmethylamidodiethylammonio]-1-carboxybutane C 16-18 acylamidodimethylbetaine; C 12-16 acylamidopentanediethylbetaine; [C 12-16 acylmethylamidodimethylbetaine.
  • Preferred betaines are C 12-18 dimethyl-ammonio hexanoate and the C 10- 18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines.
  • the sultaines useful herein are those compounds having the formula (R(R 1 ) 2 N + R 2 SO 3 - wherein R is a C 6 -C 18 hydrocarbyl group, preferably a C 10- C 16 alkyl group, more preferably a
  • each R 1 is typically C 1 -C 3 alkyl, preferably methyl
  • R 2 is a C 1 -C 6 hydrocarbyl group, preferably a C 1 -C 3 alkylene or, preferably, hydroxyalkylene group.
  • suitable sultaines include C 12- C 14 dimethylammonio-2-hydroxypropyl sulfonate, C 12-14 amido propyl ammonio-2-hydroxypropyl sultaine, C 12-14
  • R is a hydrocarbon group having from 7 to 22 carbon atoms
  • A is the group (C(O))
  • n is 0 or 1
  • R 1 is hydrogen or a lower alkyl group
  • x is 2 or 3
  • y is an integer of 0 to 4
  • Q is the group -R 2 COOM wherein R 2 is an alkylene group having from 1 to 6 carbon atoms and M is hydrogen or an ion from the groups alkali metals, alkaline earth metals, ammonium and substituted ammonium
  • B is hydrogen or a group Q as defined.
  • Preferred amides are C 8 -C 20 alkyl mono- or di-C 2 -C 3
  • alkanolamides especially monoethanolamides
  • Ampholytic, amphoteric and zwitteronic surfactants are generally used in combination with one or more anionic and/or nonionic surfactants.
  • 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 C 10 N-alkyl or alkenyl ammonium surfactants wherein remaining N positions are substituted by methyl,
  • a hydrotrope is typically added to the compositions of the present invention, and may be present at levels of from 0.5% to 25%, preferably from 1% to 15%, by weight.
  • Useful hydrotropes include sodium, potassium, and ammonium xylene sulfonates, sodium, potassium, and ammonium toluene sulfonate, sodium potassium and ammonium cumene sulfonate, and mixtures thereof.
  • hydrotropes include polycarboxylates. Some polycarboxylates have calcium chelating properties as well as hydrotropic properties. Particularly useful hydrotropes are alkylpolyethoxy polycarboxylate surfactants of the type as previously described herein.
  • Another compound useful as a hydrotrope is alkyl
  • R is a C 8 to C 18 alkyl group
  • x is from 1 to 2
  • M is preferably chosen from alkali metal, alkaline earth metal, ammonium, mono-, di-, and tri-ethanolammonium, most preferably from sodium, potassium, ammonium, and mixtures thereof with magnesium ions.
  • the preferred alkyl chain length (R) is a C 10 to C 14 alkyl group and the dicarboxylic acid functionally is diacetic acid and/or dipropionic acid.
  • alkyl amphodicarboxylic acid is the amphoteric surfactant Miranol R 2CM Cone.manufactured by Miranol, Inc., Dayton, NJ.
  • the machine dishwashing or rinsing detergent compositions of the invention preferably comprise a suds suppressing system present at a level of from 0.01% to 15%, preferably from 0.05% to 10%, most preferably from 0.1% to 5% by weight of the composition.
  • Suitable suds suppressing systems for use herein may comprise essentially any known antifoam compound
  • silicone antifoam compounds including, for example silicone antifoam compounds, 2-alkyl alcanol antifoam compounds, and paraffin antifoam
  • antifoam compound any compound or mixtures of compounds which act such as to depress the foaming or sudsing produced by a solution of a detergent composition, particularly in the presence of agitation of that solution.
  • the suds suppressing system may be incorporated into the detergent compositions by essentially any process route.
  • One preferred suds suppressing system comprises in
  • Preferred spray-on components comprise in combination an antifoam compound and a carrier fluid and optionally a dispersant compound.
  • the antifoam compound is dissolved, dispersed, suspended or emulsified in said carrier fluid.
  • the carrier fluid should be inert in nature, that is it should not undergo undesirable chemical reaction with the antifoam compound, and also preferably be storage stable under normal atmospheric conditions and in the environment of a granular detergent matrix.
  • any spray-on component is incorporated into the granular detergent compositions of the invention by a spray-on process, that is a process whereby the fluid is sprayed on to some or all of the individual granular components of the composition.
  • a spray-on process that is a process whereby the fluid is sprayed on to some or all of the individual granular components of the composition.
  • the spray-on process will be such as to provide a uniform and sufficient application of the suds suppressing component to any granular
  • components of the composition which comprise a high sudsing surfactant.
  • a preferred composition for a spray-on component comprises
  • antifoam compound preferably silicone antifoam compound, most preferably a silicone antifoam compound comprising in combination
  • silica at a level of from 1% to 50%, preferably 5% to 25% by weight of the silicone/silica antifoam compound; wherein said silica/silicone antifoam compound is
  • a dispersant compound most preferably comprising a silicone glycol rake copolymer with a polyoxyalkylene content of 72-78% and an ethylene oxide to propylene oxide ratio of from 1:0.9 to 1:1.1, at a level of from 0.5% to 10%, preferably 1% tol0% by weight of the spray-on
  • silicone glycol rake copolymer of this type is DCO544, commercially available from DOW Corning;
  • an inert carrier fluid compound most preferably comprising a C 16 -C 18 ethoxylated alcohol with a degree of ethoxylation of from 5 to 50, preferably 8 to 15, at a level of from 5% to 80%, preferably 10% to 70%, by weight of the spray-on component;
  • any spray on component of the suds suppressing system may be incorporated as such, or in a preferred execution may be mixed with other components such as liquid nonionic
  • Particulate components of the suds suppressing system are particulate in form and incorporated into the compositions of the invention in this form.
  • particulate form it is meant essentially any of the particulate forms which may be typically adapted by a component of a granular detergent composition.
  • particulate component can therefore be, for example, in the form of granules, flakes, prills, marumes or noodles.
  • the particulate is granular in nature.
  • Granules themselves may be agglomerates formed by pan or drum agglomeration or by an in-line mixer, and also may be spray-dried particles produced by atomising an aqueous slurry of the ingredients in a hot air stream which removes most of the water.
  • the spray dried granules are then subjected to densification steps, eg : by high speed cutter mixers and/or compacting mills, to increase density before being reagglomerated.
  • Any particulate component of the suds suppressing system may comprise in combination antifoam compound, and a carrier material which is highly preferably water-soluble or water-dispersible in nature.
  • a suitable particulate antifoam component 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 gel formation 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.
  • 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.
  • 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 50m 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.
  • Suitable particulate antifoam components are disclosed in Bartollota et al. US Patent 3,933,672.
  • a highly preferred particulate antifoam component is described in EP-A-0210731 and comprises a silicone antifoam compound and an organic carrier material having a melting point in the range 50°C to 85°C, wherein the organic carrier 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 other preferred particulate antifoam components wherein the organic carrier material is a fatty acid or alcohol having a carbon chain containing from 12 to 20 carbon atoms, or a mixture
  • Copending European Application 91201342.0 also discloses highly preferred particulate antifoam components comprising silicone antifoam compound, a carrier material, an organic coating material and crystalline or amorphous
  • silicone antifoam compound of 1:3 to 3:1.
  • the preferred carrrier material in both of the above described highly preferred granular suds controlling agents is starch.
  • An exemplary particulate antifoam component for use herein is a particulate agglomerate component, made by an
  • silicone antifoam compound preferably comprising in combination polydimethyl siloxane and silica
  • agglomerate binder compound comprises a C 16 -C 18 ethoxylated alcohol with a degree of ethoxylation of from 50 to 100;
  • microcrystalline waxes and high MWt copolymers of ethylene oxide and propylene oxide which would otherwise adversely affect the despersibility of the matrix.
  • Techniques for forming such particulates are disclosed in US Patent No. 3,933,672.
  • a preferred suds suppressing system has the weight ratio of antifoam compound comprised in the spray-on component to antifoam compound comprised in the particulate component of from 5:1 to 1:1, most preferably from 4:1 to 2:1.
  • Particularly preferred antifoam compounds for use herein are silicone antifoam compounds defined herein as any antifoam compound including a silicone component. Such silicone antifoam compounds also typically contain a silica component.
  • silicone antifoam compounds also typically contain a silica component.
  • silica component The term "silicone” as used herein, and in general throughout the industry, encompasses a variety of relatively high molecular weight polymers containing siloxane units and hydrocarbyl group of various types.
  • Preferred silicone antifoam compounds are the siloxanes having the general structure :
  • each R independently can be an alkyl or an aryl radical.
  • substituents are methyl, ethyl, propyl, isobutyl, and phenyl.
  • polydiorganosiloxanes are polydimethylsiloxanes having trimethylsilyl endblocking units and having a viscosity at 25°C of from 5 ⁇ 10 -5 m 2 /s to 0.1m 2 /s i.e. a value on n in the range 40 to 1500. These are preferred because of their ready availability and their relatively low cost.
  • monocarboxylic fatty acids, and salts thereof, for use as suds suppressor typically have hydrocarbyl chains of 10 to about 24 carbon atoms, preferably 12 to 18 carbon atoms.
  • Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.
  • Suitable antifoam compounds include, for example, high molecular weight hydrocarbons such as paraffin, fatty esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C 18 -C 40 ketones (e.g. stearone) N-alkylated amino triazines such as tri- to hexaalkylmelamines or di- to tetra alkyldiamme chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, bis stearic acid amide and monostearyl di-alkali metal (e.g. sodium, potassium. lithium) phosphates and phosphate esters.
  • hydrocarbons such as paraffin, fatty esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C 18 -C 40 keto
  • hydrocarbons such as paraffin and haloparaffin
  • the liquid hydrocarbons will be liquid at room temperature and atmospheric pressure, and will have a pour point in the range of about -40°C and about 5°C, and a minimum boiling point not less than 110°C (atmospheric pressure). It is also known to utilize waxy hydrocarbons, preferably having a melting point below about 100°C. Hydrocarbon suds suppressors are described, for example, in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al. The hydrocarbons, thus, include
  • paraffin as used in this suds supressor dicussion, is intended to include mixtures of true paraffins and cyclic hydrocarbons.
  • the mixed ethoxylated/propoxylated fatty alcohols with 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, are also suitable antifoam compounds for use herein.
  • Suitable 2-alky-alcanols antifoam compounds for use herein have been described in DE 40 21 265.
  • the 2-alkyl-alcanols suitable for use herein consist of a C 6 to C 16 alkyl chain carrying a terminal hydroxy group, and said alkyl chain is substituted in the a position by a C 1 to C 10 alkyl chain.
  • the alkyl chain carrying the hydroxy group is a C 8 to C 12 alkyl chain, and the alkyl chain in the a
  • 2-hexyl-decanol and 2-butyl-decanol are particularly suitable for use herein.
  • 2-hexyl-decanol and 2-butyl- octanol are commercially available fron Condea under the trade names ISOFOL 16 and ISOFOL 12.
  • the suds suppressing system for use herein comprises from 0.01% to 15% by weight of the total composition of said 2-alkyl- alcanols, preferably from 0.05% to 10%, most preferably from 0.1% to 5%.
  • Mixtures of 2-alkyl-alcanols can be used in the compositions according to the present invention. Such mixtures are comprised in commercially available materials, for instance ISALCHEM 123 R from Enichem.
  • the machine dishwashing detergent compositions of the invention will preferably included bleaching agent selected from chlorine bleaches, inorganic perhydrate salts, peroxyacid bleach precursors and organic peryoxacids.
  • Chlorine bleaches include the alkali metal hypochlorites and chlorinated cyanuric acid salts.
  • the use of chlorine bleaches in the composition of the invention is preferably minimized, and more preferably the compositions contain no chlorine bleach.
  • the machine dishwashing detergent compositions in accord with the invention will generally include an inorganic perhydrate salt, normally 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 detergent compositions.
  • an inorganic perhydrate salt normally 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 detergent compositions.
  • the machine dishwashing detergent compositions of the present invention will also generally include peroxyacid bleach precursors (bleach activators).
  • the peroxyacid bleach precursors are normally incorporated at a level of from 1% to 20% by weight, more preferably from 1% to 10% by weight, most preferably from 1% to 7% by weight of the compositions.
  • the machine dishwashing detergent compositions may also contain organic peroxyacids at a level of from 1% to 15% by weight, more preferably from 1% to 10% by weight of the composition.
  • 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.
  • compositions in accordance with the invention 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 another preferred perhydrate for inclusion in detergent 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
  • the percarbonate is most preferably incorporated into such compositions in coated form.
  • the most preferred coating material comprises mixed salt of an alkali metal sulphate and
  • 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 :
  • 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 form 0.1 to 3, preferably n is from 0.3 to 1.0 and most preferably n is from 0.2 to 0.5.
  • Another suitable coating material is sodium silicate of SiO 2 : Na 2 O ratio from 1.6 : 1 to 3.4 : 1, preferably 2.8 :
  • silicate solids by weight of the percarbonate.
  • Magnesium silicate can also be included in the coating.
  • suitable coating materials include the alkali and alkaline earth metal sulphates and carbonates.
  • Potassium peroxymonopersulfate is another inorganic
  • Peroxyacid bleach precursors for inclusion in the machine dishwashing detergent compositions in accordance with the invention probably contain one or more N- or O- acyl groups, which precursors can be selected from a wide range of classes. Suitable classes include anhydrides, esters, imides and acylated derivatives of imidazoles and oximes, and examples of useful materials within these classes are disclosed in GB-A-1586789. The most preferred classes are esters such as are disclosed in GB-A-836988, 864798,
  • Particularly preferred precursor compounds are the
  • x can be 0 or an integer between 1 & 6.
  • TAMD tetra acetyl methylene diamine
  • TAED tetra acetyl ethylene diamine
  • TAHD tetraacetyl hexylene diamine
  • peroxyacid bleach activator compounds are the amide substituted compounds of the following general formulae: or
  • R 1 is an aryl or alkaryl group with from about 1 to about 14 carbon atoms
  • R 2 is an alkylene, arylene, and alkarylene group containing from about 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 about 6 to 12 carbon atoms.
  • R 2 preferably contains from about 4 to 8 carbon atoms.
  • R 1 may be straight chain or branched alkyl, substituted aryl or alkylaryl containing branching,
  • substitution can include alkyl, aryl, halogen, nitrogen, sulphur and other typical
  • R 5 is preferably H or methyl.
  • R 1 and R 5 should not contain more than 18 carbon atoms total.
  • Amide substituted bleach activator compounds of this type are described in EP-A-0170386.
  • peroxyacid bleach precursor compounds include sodium nonanoyloxy benzene sulfonate, sodium trimethyl hexanoyloxy benzene sulfonate, sodium acetoxy benzene sulfonate and sodium benzoyloxy benzene sulfonate as disclosed in, for example, EP-A-0341947.
  • the machine dishwashing detergent compositions of the invention may also contain organic peroxyacids of which a particularly preferred class are the amide substituted peroxyacids of general formulae: or
  • R 1 , R 2 and R 5 are as defined previously for the corresponding amide substituted peroxyacid bleach activator compounds.
  • organic peroxyacids include diperoxy dodecanedioc acid, diperoxy tetra decanedioc acid,
  • diperoxyhexadecanedioc acid mono- and diperazelaic acid, mono- and diperbrassylic acid, monoperoxy phthalic acid, perbenzoic acid, and their salts as disclosed in, for example, EP-A-0341 947.
  • Anti-redeposition and soil-suspension agents suitable herein include cellulose derivatives such as
  • Polymers of this type include the polyacrylates and copolymers of maleic anhydride with ethylene, methylvinyl ether or methacrylic acid, the maleic anhydride constituting at least 20 mole percent of the copolymer disclosed in detail in EP-A-137669.
  • Polyamino compounds such as those derived from aspartic acid are disclosed in EP-A-305282, EP-A-305283 and EP-A-351629. These materials are normally used at levels of from 0.5% to 10% by weight, more preferably; from 0.75% to 9%, most preferably from 1% to 8% by weight of the composition.
  • polyethylene glycols particularly those of molecular weight 1000-10000, more particularly 2000 to 8000 and most preferably about 4000. These are used at levels of from 0.2% to 5% by weight, more preferably from 0.25% to 2.5% by weight.
  • compositions is one or more enzymes.
  • Preferred additional enzymatic materials include the commercially available amylases, neutral and alkaline proteases, 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
  • amylases include for example,
  • Amylase enzyme may be incorporated into the composition in accordance with the invention at a level of from 0.001% to 2% active enzyme by weight of the composition.
  • an enzyme stabilizing system comprise from about 0.001% to about 10%, preferably from about 0.005% to about 8%,most preferably from about 0.01% to about 6%, by weight of an enzyme stabilizing system.
  • the enzyme stabilizing system can be any stabilizing system which is compatible with the detersive enzyme.
  • Such stabilizing systems can comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acid, boronic acid, and mixtures thereof.
  • compositions herein may further comprise from 0 to about 10%, preferably from about 0.01% to about 6% by weight, of chlorine bleach scavengers, added to prevent chlorine bleach species present in many water supplies from attacking and inactivating the enzymes, especially under alkaline conditions. While chlorine levels in water may be small, typically in the range from about 0.5 ppm to about 1.75 ppm, the available chlorine in the total volume of water that comes in contact with the enzyme during
  • dishwashing is usually large; accordingly, enzyme stability in-use can be problematic.
  • Suitable chlorine scavenger anions are widely available, indeed ubiquitous, and are illustrated by salts containing ammonium cations or sulfite, bisulfite, thiosulfite, thiosulfate, iodide, etc.
  • Antioxidants such as carbamate, ascorbate, etc., organic amines such as
  • ethylenediaminetetracetic acid or alkali metal salt thereof, monoethanolamine (MEA), and mixtures thereof can likewise be used.
  • Other conventional scavengers such as bisulfate, nitrate, chloride, sources of hydrogen peroxide such as sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate, as well as phosphate, condensed phosphate, acetate, benzoate, citrate, formate, lactate, malate, tartrate, salicylate, etc. and mixtures thereof can be used if desired.
  • the chlorine scavenger function can be performed by several of the ingredients separately listed under better recognized functions, (e.g., other components of the invention
  • formulation chemists generally recognize that combinations of reducing agents such as thiosulfate with strong oxidizers such as percarbonate are not wisely made unless the reducing agent is protected from the oxidizing agent in solid-form composition.
  • reducing agents such as thiosulfate
  • strong oxidizers such as percarbonate
  • ammonium salts such salts can be simply admixed with the detergent composition but are prone to adsorb water and/or liberate ammonia during storage. Accordingly, such materials, if present, are desirably protected in a particle such as that described in U.S. Patent 4,652,392, Baginski et al.
  • compositions may also contain corrosion inhibitor, preferably incorporated at a level of from 0.05% to 10%, preferably from 0.1% to 5% by weight of the total composition.
  • Suitable corrosion inhibitors include paraffin oil
  • Suitable corrosion inhibitor compounds include benzotriazole and any derivatives thereof, mercaptans and diols, especially mercaptans with 4 to 20 carbon atoms including lauryl mercaptan, thiophenol,
  • C 12 -C 20 fatty acids or their salts, especially aluminium tristearate.
  • the C 12 -C 20 hydroxy fatty acids, or their salts, are also suitable.
  • Phosphonated octa-decane and other anti-oxidants such as betahydroxytoluene (BHT) are also suitable.
  • Heavy metal ion sequestrant The detergent compositions of the invention may be formulated to contain as a non-essential component heavy metal ion sequestrant, incorporated at a level of from 0.005% to 3%, preferably 0.05 to 1%, most preferably 0.07% to 0.4%, by weight of the total composition.
  • Suitable heavy metal ion sequestrant for use herein include organic phosphonates, such as amino alkylene poly (alkylene phosphonate), alkali metal ethane 1-hydroxy disphosphonates, nitrilo trimethylene
  • 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 heavy metal ion sequestrant for use herein include nitrilotriacetic acid and
  • polyaminocarboxylic acids such as
  • ethylenediaminotetracetic acid ethylenetriamine pentacetic acid, ethylenediamine disuccinic acid or the water soluble alkali metal salts thereof.
  • EDDS ethylenediamine-N,N'-disuccinic acid
  • alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof Especially preferred.
  • Preferred EDDS ethylenediamine-N,N'-disuccinic acid
  • complexes of EDDS include MgEDDS and Mg 2 EDDS.
  • magnesium complexes are the most preferred for magnesium
  • the heavy metal ion sequestrant herein can consist of a mixture of the above described species.
  • compositions of the invention include perfumes, colours and filler salts, with sodium sulfate being a preferred filler salt.
  • the machine dishwashing or rinsing compositions of the invention can be formulated in any desirable form such as powders, granulates, pastes, liquids, gels and tablets.
  • detergent compositions 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 machine dishwashing compositions involves a combination of dry mixing and agglomeration techniques.
  • the bulk density of the granular detergent compositions in accordance with the present invention typically have a bulk density 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.
  • 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.
  • compositions 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.
  • MA/AA Copolymers of 1:4 maleic/acrylic acid
  • Silicate Amorphous Sodium Silicate (SiO 2 :Na 2 O ratio normally follows)
  • Proteolytic enzyme sold under the tradename
  • Amylase Amylolytic enzyme sold under the tradename
  • Nonionic C 13 -C 15 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
  • TAED Tetraacetyl ethylene diamine
  • compositions were prepared (parts by weight).
  • Product A contains phosphate builder compound and product B contains only non-phosphate builder compounds.
  • the 65°C wash setting was selected, the wash process comprising main wash and rinse cycles. 10 grams of product was employed in each case. The water hardness was 10° Clark Hardness (142.9 ppm CaCO 3 equivalent). In addition to the glass tumblers and plastic beakers a ballast load of clean crockery was also included in the wash load.
  • the tumblers and beakers were air-dried and then graded for spotting and filming.
  • the grading was performed using visual spotting and filming grading scales by 4 expert graders, and the spotting and filming grades averaged for each of the glass tumblers and plastic beakers. Grading scales of from 1 to 9 were employed where a grade of l on the filming scale indicates coverage with a dense, opaque film and 9 indicates no filming, and where a grade of 1 on the spotting scale indicates dense coverage with spots and 9 indicates no spotting.

Abstract

Compositions de lavage et de rinçage pour lave-vaisselle contenant une enzyme lipolytique active et un dispersant de savon de chaux dont le pouvoir de dispersion est inférieur ou égal à 8.
PCT/US1993/008877 1992-09-25 1993-09-20 Composition de detergent contenant un dispersant de savon de chaux et des lipases WO1994007985A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
AT93922707T ATE211163T1 (de) 1992-09-25 1993-09-20 Verwendung eines kalksteindispergiermittels in einer waschmittelzusammensetzung enthaltend lipase enzyme
EP93922707A EP0662119B1 (fr) 1992-09-25 1993-09-20 Utilisation d'un dispersant de savon de chaux dans une composition détergente contenant des lipases
DE69331388T DE69331388T2 (de) 1992-09-25 1993-09-20 Verwendung eines Kalksteindispergiermittels in einer Waschmittelzusammensetzung enthaltend Lipase Enzyme

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB9220343.9 1992-09-25
GB929220343A GB9220343D0 (en) 1992-09-25 1992-09-25 Detergent compositions
EP93870169 1993-08-13
EP93870169.5 1993-08-13

Publications (1)

Publication Number Publication Date
WO1994007985A1 true WO1994007985A1 (fr) 1994-04-14

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DE (1) DE69331388T2 (fr)
ES (1) ES2169726T3 (fr)
WO (1) WO1994007985A1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995004806A1 (fr) * 1993-08-10 1995-02-16 The Procter & Gamble Company Composition pour la vaisselle a la main comprenant des lipases et un dispersant des savons de chaux
US5772786A (en) * 1993-08-13 1998-06-30 The Procter & Gamble Company Detergent composition comprising lime soap dispersant and lipase enzymes
US5827264A (en) * 1992-10-01 1998-10-27 Chiron Technolas Gmbh Ophthalmologische Systeme Method of controlling apparatus for modifying the surface of the eye through large beam laser polishing
EP0846155B1 (fr) * 1995-08-25 2000-02-09 Henkel Kommanditgesellschaft auf Aktien Utilisation de lipase dans des agents faiblement alcalins pour le lavage de vaisselle en machine
EP1520908A1 (fr) * 2003-10-01 2005-04-06 Dalli-Werke GmbH & Co. KG Composition pour lave-vaisselle avec des propriétés de rinçage améliorées
US9138393B2 (en) 2013-02-08 2015-09-22 The Procter & Gamble Company Cosmetic compositions containing substituted azole and methods for improving the appearance of aging skin
US9144538B2 (en) 2013-02-08 2015-09-29 The Procter & Gamble Company Cosmetic compositions containing substituted azole and methods for alleviating the signs of photoaged skin
US20170175055A1 (en) * 2015-12-22 2017-06-22 The Procter & Gamble Company Automatic dishwashing composition
EP3034588B1 (fr) 2014-12-17 2019-04-24 The Procter and Gamble Company Composition de détergent

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WO1987000859A1 (fr) * 1985-08-09 1987-02-12 Gist-Brocades N.V. Nouveaux enzymes lipolytiques et leur utilisation dans des compositions de detergents
EP0271153A2 (fr) * 1986-12-10 1988-06-15 Unilever N.V. Composition détergente à base d'enzymes
US4797223A (en) * 1988-01-11 1989-01-10 Rohm And Haas Company Water soluble polymers for detergent compositions
EP0373850A1 (fr) * 1988-12-12 1990-06-20 Unilever Plc Compositions détergentes contenant des enzymes et leur utilisation
US4959179A (en) * 1989-01-30 1990-09-25 Lever Brothers Company Stabilized enzymes liquid detergent composition containing lipase and protease
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WO1987000859A1 (fr) * 1985-08-09 1987-02-12 Gist-Brocades N.V. Nouveaux enzymes lipolytiques et leur utilisation dans des compositions de detergents
EP0271153A2 (fr) * 1986-12-10 1988-06-15 Unilever N.V. Composition détergente à base d'enzymes
US5078898A (en) * 1987-11-02 1992-01-07 Novo Nordisk A/S Detergent compositions comprising pseudomonas lipase and a specific protease
US4797223A (en) * 1988-01-11 1989-01-10 Rohm And Haas Company Water soluble polymers for detergent compositions
US5069809A (en) * 1988-05-09 1991-12-03 Lever Brothers Company, Division Of Conopco, Inc. Enzymatic detergent and bleaching composition containing a specific rdna technique cloned lipase
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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5827264A (en) * 1992-10-01 1998-10-27 Chiron Technolas Gmbh Ophthalmologische Systeme Method of controlling apparatus for modifying the surface of the eye through large beam laser polishing
WO1995004806A1 (fr) * 1993-08-10 1995-02-16 The Procter & Gamble Company Composition pour la vaisselle a la main comprenant des lipases et un dispersant des savons de chaux
US5772786A (en) * 1993-08-13 1998-06-30 The Procter & Gamble Company Detergent composition comprising lime soap dispersant and lipase enzymes
EP0846155B1 (fr) * 1995-08-25 2000-02-09 Henkel Kommanditgesellschaft auf Aktien Utilisation de lipase dans des agents faiblement alcalins pour le lavage de vaisselle en machine
EP1520908A1 (fr) * 2003-10-01 2005-04-06 Dalli-Werke GmbH & Co. KG Composition pour lave-vaisselle avec des propriétés de rinçage améliorées
EP1524313A1 (fr) * 2003-10-01 2005-04-20 Dalli-Werke GmbH & Co. KG Composition pour lave-vaisselle avec des proprietes de rincage ameliorees
US9138393B2 (en) 2013-02-08 2015-09-22 The Procter & Gamble Company Cosmetic compositions containing substituted azole and methods for improving the appearance of aging skin
US9144538B2 (en) 2013-02-08 2015-09-29 The Procter & Gamble Company Cosmetic compositions containing substituted azole and methods for alleviating the signs of photoaged skin
EP3034588B1 (fr) 2014-12-17 2019-04-24 The Procter and Gamble Company Composition de détergent
US20170175055A1 (en) * 2015-12-22 2017-06-22 The Procter & Gamble Company Automatic dishwashing composition
EP3184622A1 (fr) * 2015-12-22 2017-06-28 The Procter and Gamble Company Composition pour lave-vaisselle automatique
WO2017112500A1 (fr) * 2015-12-22 2017-06-29 The Procter & Gamble Company Composition pour lave-vaisselle automatique

Also Published As

Publication number Publication date
DE69331388D1 (de) 2002-01-31
DE69331388T2 (de) 2002-08-14
ES2169726T3 (es) 2002-07-16
ATE211163T1 (de) 2002-01-15

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