WO2002008370A2 - Cleaning composition - Google Patents

Cleaning composition Download PDF

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Publication number
WO2002008370A2
WO2002008370A2 PCT/US2000/019619 US0019619W WO0208370A2 WO 2002008370 A2 WO2002008370 A2 WO 2002008370A2 US 0019619 W US0019619 W US 0019619W WO 0208370 A2 WO0208370 A2 WO 0208370A2
Authority
WO
WIPO (PCT)
Prior art keywords
automatic dishwashing
composition
organic solvent
cookware
tableware
Prior art date
Application number
PCT/US2000/019619
Other languages
French (fr)
Other versions
WO2002008370A3 (en
Original Assignee
The Procter & Gamble Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=21741603&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2002008370(A2) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to PCT/US2000/019619 priority Critical patent/WO2002008370A2/en
Priority to PCT/US2000/020255 priority patent/WO2002008371A2/en
Priority to DE60035902T priority patent/DE60035902T2/en
Priority to PCT/US2000/032533 priority patent/WO2001060966A1/en
Priority to AT00980871T priority patent/ATE369417T1/en
Priority to MXPA02008065A priority patent/MXPA02008065A/en
Priority to EP00980871A priority patent/EP1255807B1/en
Priority to BRPI0017112-3A priority patent/BR0017112B1/en
Priority to CA002397241A priority patent/CA2397241C/en
Priority to ES00980871T priority patent/ES2290059T3/en
Priority to AU2001218076A priority patent/AU2001218076A1/en
Priority to JP2001560338A priority patent/JP2005507432A/en
Priority to CNB008190615A priority patent/CN1225537C/en
Priority to EP00986684A priority patent/EP1305389B1/en
Priority to MXPA03000492A priority patent/MXPA03000492A/en
Priority to PCT/US2000/034907 priority patent/WO2002008373A1/en
Priority to MXPA03000491A priority patent/MXPA03000491A/en
Priority to MXPA03000490A priority patent/MXPA03000490A/en
Priority to DE60044979T priority patent/DE60044979D1/en
Priority to AT00988267T priority patent/ATE395405T1/en
Priority to AT00986682T priority patent/ATE481471T1/en
Priority to ES00986682T priority patent/ES2352670T3/en
Priority to AT00986684T priority patent/ATE342336T1/en
Priority to JP2002514259A priority patent/JP2004515569A/en
Priority to AU2001222875A priority patent/AU2001222875A1/en
Priority to AU2001222876A priority patent/AU2001222876A1/en
Priority to CA002414140A priority patent/CA2414140C/en
Priority to AU2001222873A priority patent/AU2001222873A1/en
Priority to EP00986683A priority patent/EP1305383B1/en
Priority to MXPA03000493A priority patent/MXPA03000493A/en
Priority to DE60031309T priority patent/DE60031309T2/en
Priority to PCT/US2000/034906 priority patent/WO2002008374A1/en
Priority to ES00986684T priority patent/ES2273742T3/en
Priority to AU2001224494A priority patent/AU2001224494A1/en
Priority to EP00988267A priority patent/EP1305390B1/en
Priority to PCT/US2000/034910 priority patent/WO2002008509A1/en
Priority to EP00986682A priority patent/EP1305388B1/en
Priority to ES00988267T priority patent/ES2306676T3/en
Priority to CA002414133A priority patent/CA2414133C/en
Priority to AT00986683T priority patent/ATE455836T1/en
Priority to CA002416326A priority patent/CA2416326A1/en
Priority to DE60043751T priority patent/DE60043751D1/en
Priority to DE60038906T priority patent/DE60038906D1/en
Priority to CA002416327A priority patent/CA2416327C/en
Priority to AU2001222874A priority patent/AU2001222874A1/en
Priority to JP2002513861A priority patent/JP2004509175A/en
Priority to JP2002514258A priority patent/JP3962327B2/en
Priority to PCT/US2000/034909 priority patent/WO2002008376A1/en
Priority to PCT/US2000/034908 priority patent/WO2002008375A1/en
Priority to ES00986683T priority patent/ES2339420T3/en
Priority to JP2002514260A priority patent/JP2004509176A/en
Priority to CN01805165A priority patent/CN1401030A/en
Priority to MXPA02008067A priority patent/MXPA02008067A/en
Priority to BR0108441-0A priority patent/BR0108441A/en
Priority to AU2001238240A priority patent/AU2001238240A1/en
Priority to PCT/US2001/004694 priority patent/WO2001061099A1/en
Priority to CA002396931A priority patent/CA2396931A1/en
Priority to EP01910655A priority patent/EP1255887A2/en
Priority to JP2001559930A priority patent/JP5000060B2/en
Priority to US10/204,259 priority patent/US7351683B2/en
Priority to ARP010100705A priority patent/AR028508A1/en
Priority to ARP010100706A priority patent/AR035167A1/en
Priority to US09/906,491 priority patent/US6750187B2/en
Priority to US09/906,480 priority patent/US6740628B2/en
Priority to US09/906,295 priority patent/US20020142931A1/en
Priority to US09/906,479 priority patent/US6557732B2/en
Priority to CA002415302A priority patent/CA2415302A1/en
Priority to AU2001280606A priority patent/AU2001280606A1/en
Priority to MXPA03000488A priority patent/MXPA03000488A/en
Priority to AT01959008T priority patent/ATE350453T1/en
Priority to MXPA03000487A priority patent/MXPA03000487A/en
Priority to AU2001280605A priority patent/AU2001280605A1/en
Priority to EP01959009A priority patent/EP1305394A1/en
Priority to PCT/US2001/022708 priority patent/WO2002006437A1/en
Priority to AU2001280607A priority patent/AU2001280607A1/en
Priority to JP2002512332A priority patent/JP2004506749A/en
Priority to AT01959010T priority patent/ATE278764T1/en
Priority to EP04023010A priority patent/EP1493803B1/en
Priority to DE60106272T priority patent/DE60106272T2/en
Priority to JP2002512331A priority patent/JP4185360B2/en
Priority to MXPA03000489A priority patent/MXPA03000489A/en
Priority to ES01959010T priority patent/ES2225589T3/en
Priority to AT04023010T priority patent/ATE328996T1/en
Priority to JP2002512330A priority patent/JP2004519527A/en
Priority to PCT/US2001/022706 priority patent/WO2002006436A1/en
Priority to PCT/US2001/022707 priority patent/WO2002006438A1/en
Priority to CA002415308A priority patent/CA2415308A1/en
Priority to DE60125775T priority patent/DE60125775T2/en
Priority to ES04023010T priority patent/ES2265133T3/en
Priority to CA002415304A priority patent/CA2415304A1/en
Priority to DE60120517T priority patent/DE60120517T2/en
Priority to EP01959010A priority patent/EP1305392B1/en
Priority to EP01959008A priority patent/EP1305391B1/en
Priority to ES01959008T priority patent/ES2280389T3/en
Priority to US09/910,281 priority patent/US20020037822A1/en
Priority to US09/909,403 priority patent/US6683036B2/en
Priority to US09/909,233 priority patent/US20020037817A1/en
Publication of WO2002008370A2 publication Critical patent/WO2002008370A2/en
Publication of WO2002008370A3 publication Critical patent/WO2002008370A3/en
Priority to US10/764,931 priority patent/US20040157763A1/en
Priority to US11/151,027 priority patent/US20050233925A1/en
Priority to US11/192,563 priority patent/US7304023B2/en
Priority to US11/212,221 priority patent/US7229955B2/en
Priority to JP2012238209A priority patent/JP2013067802A/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
    • C23G1/19—Iron or steel
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0043—For use with aerosol devices
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/1266—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite in liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
    • 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
    • C11D3/43—Solvents
    • 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
    • C11D3/50—Perfumes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/261—Alcohols; Phenols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/263—Ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/264—Aldehydes; Ketones; Acetals or ketals
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3227—Ethers thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • C11D7/5004—Organic solvents
    • C11D2111/14—
    • C11D2111/16—

Definitions

  • the present invention is in the field of dishwashing, in particular it relates to dishwashing and automatic dishwashing products, auxiliaries and methods suitable for the removal of cooked-, baked- and burnt-on soils from cookware and tableware.
  • Cooked-, baked- and burnt-on soils are amongst the most severe types of soils to remove from surfaces. Traditionally, the removal of cooked-, baked- and burnt-on soils from cookware and tableware requires soaking the soiled object prior to a mechanical action. Consequently, the automatic dishwashing process alone does not provide a satisfactory removal of cooked-, baked- and burnt-on soils.
  • US-A-5, 102,573 provides a method for treating hard surfaces soiled with cooked-on, baked-on or dried-on food residues comprising applying a pre-spotting composition to the soiled article.
  • the composition applied comprises surfactant, builder, amine and solvent.
  • WO-A-94/28108 discloses an aqueous cleaner concentrate composition, that can be diluted to form a more viscous use solution comprising an effective thickening amount of a rod micelle thickener composition, lower alkyl glycol ether solvent and hardness sequestering agent.
  • the application also describes a method of cleaning a food preparation unit having at least one substantially vertical surface having a baked food soil coating.
  • JP-A- 10,017,900 discloses an automatic dishwashing auxiliary composition comprising non- ionic low foaming surfactant, organic solvent and water. The composition delivers detergency and drying benefits.
  • JP-A-11,117,000 discloses a cleaning assistant composition for automatic dishwashing machines comprising surfactant, organic high- molecular polyelectrolyte, water-soluble solvent and water. The claimed assistant composition helps in the cleaning of stubborn dirt such as that due to oil or lipstick.
  • a method of removing cooked-, baked-, or burnt-on food soil such as grease, meat, dairy, fruit, pasta and any other food especially difficult to remove after the cooking process
  • cookware and tableware including stainless steel, glass, plastic, wood and ceramic objects.
  • the method comprises washing the cookware/tableware in an automatic dishwashing machine in the presence of an organic solvent system (comprising a single solvent compound or a mixture of solvent compounds) having a volatile organic content above 1 mm Hg of less than about 50%, preferably less than about 20% and more preferably less than about 10% by weight of the solvent system.
  • volatile organic content of the solvent system is defined as the content of organic components in the solvent system having a vapor pressure higher than the prescribed limit at 25 °C and atmospheric pressure.
  • the optimum concentration of the solvent in the wash liquor is from about 100 ppm to about 10000 ppm, preferably from about 200 to about 8000 and more preferably from about 500 to about 5000 ppm.
  • the organic solvent system is preferably used in combination with a surfactant, especially a low foaming non-ionic surfactant and a detergency builder.
  • another embodiment of the invention provides a method of removing cooked-, baked-, or burnt-on food soil from cookware and tableware comprising washing the cookware/tableware in an automatic dishwashing machine in the presence of surfactant, detergency builder and an organic solvent system wherein the surfactant has a wash liquor concentration of from about 10 to about 1000, preferably from about 100 to about 600 ppm, the detergency builder has a wash liquor concentration of about 100 to about 5000, preferably from about 1000 to about 3000 ppm and the organic solvent system has a wash liquor concentration of from about 100 to about 10000 ppm, preferably from about 200 to about 8000 ppm and more preferably from about 500 to about 5000 ppm.
  • the surfactant has a wash liquor concentration of from about 10 to about 1000, preferably from about 100 to about 600 ppm
  • the detergency builder has a wash liquor concentration of about 100 to about 5000, preferably from about 1000 to about 3000 ppm
  • the organic solvent system has
  • the pH of the wash liquor will generally be in the alkaline range, preferably at least 10.5 or more preferably at least 11.0, this pH being provided by means of an alkalinity source or sources in one or more compositions used for delivery of the solvent, surfactant and builder.
  • the removal of cooked-, baked-, or burnt-on food soil from cookware and tableware can be carried out by the use of one or more (generally unbuilt) organic solvent compositions (wherein "solvent composition” is understood to comprise the organic solvent system and optional additional active ingredients and diluents) and one or more (generally built) automatic dishwashing detergent compositions.
  • solvent composition is understood to comprise the organic solvent system and optional additional active ingredients and diluents
  • automatic dishwashing detergent compositions one or more (generally built) automatic dishwashing detergent compositions.
  • the solvent compositions and automatic dishwashing detergent compositions can be delivered either at the same or at different points of the dishwashing cycle, for example: i) solvent composition and automatic dishwashing detergent composition are independently delivered in the pre- wash cycle and in the main-wash cycle, respectively; ii) a solvent composition and a first automatic dishwashing detergent composition are delivered in the pre-wash cycle and a second automatic dishwashing detergent composition in the main-wash cycle; iii) a first solvent composition and a first automatic dishwashing detergent composition are delivered in the pre-wash cycle and a second solvent composition and a second automatic dishwashing detergent composition in the main-wash cycle; iv) a solvent composition and an automatic dishwashing detergent composition are delivered simultaneously in the main-wash cycle; and v) a solvent composition and an automatic dishwashing detergent composition are delivered in the pre-wash and in the main-wash cycle.
  • Another embodiment provides a method of removing cooked-, baked-, or burnt-on food soil from cookware and tableware comprising washing the cookware/tableware in the pre-wash cycle of an automatic dishwashing machine in the presence of an organic solvent composition and thereafter rinsing the cookware/tableware in the rinse cycle of the automatic dishwashing machine in the presence of an automatic dishwashing rinse composition.
  • the organic solvent composition and the automatic dishwashing detergent composition are delivered either i) from separate storage means (e.g. different bottles in the case of liquid compositions, different pouches, etc.) into the same cycle of an automatic dishwashing machine to provide a wash liquor concentration of organic solvent as prescribed herein and preferably in the range from about 100 to about 10000 ppm, preferably from about 500 to about 5000; or ii) from separate zones of a multi-zone storage means (e.g. multi-compartment bottle in the case of liquid compositions) into the same or different cycles of an automatic dishwashing machine.
  • separate storage means e.g. different bottles in the case of liquid compositions, different pouches, etc.
  • a wash liquor concentration of organic solvent as prescribed herein and preferably in the range from about 100 to about 10000 ppm, preferably from about 500 to about 5000
  • a multi-zone storage means e.g. multi-compartment bottle in the case of liquid compositions
  • the organic solvent composition and the automatic dishwashing detergent composition are delivered from separate zones of a multi-zone storage means at a feed ratio (solvent composition: detergent composition) in the range from about 5:1 to about 1:50, preferably from about 2:1 to about 1:5 and more preferably from about 1:1 to about 1 :3 to provide a wash liquor concentration of organic solvent in the range preferably from about 100 to about 10000, more preferably from about 500 to about 5000 ppm.
  • the organic solvent composition and the automatic dishwashing detergent composition are delivered from separate zones of a multi-zone storage means sequentially into the pre-wash and main wash cycle, respectively. This can be valuable in the case of product incompatibility to reduce interaction between the organic solvent composition and the automatic dishwashing detergent composition.
  • the organic solvent composition and the automatic dishwashing detergent composition are delivered simultaneously from separate zones of a multi-zone storage means
  • the physical form of the organic solvent composition and/or automatic dishwashing detergent composition is preferably such as to prevent intimate mixing of the compositions prior to contact thereof with the wash liquor.
  • the invention can be also reduced to practice using multi-phase, "all-in-one" products.
  • a method of removing cooked-, baked-, or burnt-on food soil from cookware and tableware comprising delivering separate portions of a multi-phase detergent composition into the same or different cycles of an automatic dishwashing machine, wherein the multi-phase detergent composition comprises at least a first phase containing an organic solvent composition and at least a second phase containing an automatic dishwashing detergent composition.
  • the multiphase detergent composition for example could take the form of a multi-layer liquid (e.g. coacervate) or gel contained in a bottle, or a multiphase tablet incorporating the solvent composition in the form of a gel contained within a preformed cavity or recess within the main tablet body.
  • the level of solvent delivered to the wash process should be such as to deliver the benefits on cooked-, baked- or burnt-on food soils.
  • the present invention also envisages the use of multiple organic solvent compositions.
  • a method of removing cooked-, baked-, or burnt-on food soil from cookware and tableware comprising delivering a plurality of organic solvent compositions of different solvent characteristics into the same or different cycles of an automatic dishwashing machine, for example, a first solvent composition in the pre-wash cycle and a second solvent composition in the main-wash cycle.
  • the different organic solvent compositions are designed to be specific to different soil and/or substrates.
  • They can be delivered into different cycles of a dishwashing machine, with or without different automatic dishwashing detergent compositions, such that, for example, a first solvent composition and a first automatic dishwashing detergent composition are delivered into the pre-wash cycle and a second solvent composition and a second automatic dishwashing detergent composition are delivered into the main-wash cycle.
  • the organic solvent composition can be in a unit dose form allowing controlled release (for example delayed, sustained, triggered or slow release) of the composition during one or more repeated washing cycles.
  • the solvent composition is contained in a single or multi-compartment pouch.
  • a method of removing cooked-, baked-, or burnt-on food soil from cookware and tableware comprises washing the cookware/tableware in an automatic dishwashing machine with an automatic dishwashing detergent composition comprising surfactant (preferably comprising low-foaming nonionic surfactant), detergency builder and organic solvent system in levels sufficient to provide a wash liquor concentration of from about 10 ppm to about 1000 ppm surfactant, from about 100 ppm to about 5000 ppm detergency builder, and about' 100 ppm to about 10,000, preferably from about 500 ppm to about 5000 ppm of organic solvent.
  • surfactant preferably comprising low-foaming nonionic surfactant
  • detergency builder preferably comprising low-foaming nonionic surfactant
  • organic solvent system in levels sufficient to provide a wash liquor concentration of from about 10 ppm to about 1000 ppm surfactant, from about 100 ppm to about 5000 ppm detergency builder,
  • the organic solvent composition can be in the form of a liquid, paste, cream or gel and can be optionally encapsulated, packaged in a single- or multi-compartment pouch, or absorbed onto a porous carrier material.
  • the solvent composition can be aqueous but preferably is anhydrous.
  • Preferred pouches for use herein are water-soluble, solvent-resistant partially hydrolysed PVA pouches.
  • the optimum organic solvent systems for use herein are characterised by extremely low liquid surface tensions and contact angles on polymerised grease-coated substrates. Moreover, they generally consist of mixed solvent systems displaying synergistic contact angle and low surface tension.
  • the organic solvent system herein preferably has a liquid surface tension at 25 °C of less than about 27 mN/m.
  • compositions containing the solvent system preferably display an advancing contact angle on a polymerised grease-coated substrate at 25°C of less than 20°, preferably less than 10° and more preferably less than 5°.
  • the advancing contact angle for compositions based on mixed solvent systems should be less than that of any of the corresponding compositions containing the individual components of the solvent system.
  • Such solvent systems and compositions are found to be optimum for the removal of burnt-on soils having a high carbon content from cookware and tableware. It is a feature of the invention that these solvent systems also display excellent performance in dried application to soiled cookware and tableware.
  • a method of removing cooked-, baked-, or burnt-on food soil from cookware and tableware comprising treating the cookware/tableware with a hard surface cleaning composition comprising an organic solvent system.
  • the organic solvent system desirably has a liquid surface tension of less than about 27 mN/m, preferably less than about 26 mN/m.
  • the hard surface cleaning composition on the other hand desirably display an advancing contact angle on a polymerised grease-coated substrate at 25 °C of less than 20°, preferably less than 10° and more preferably less than 5°.
  • the above method comprises the step of pre- treating the cookware/tableware with the hard surface cleaning composition prior to manual or automatic dishwashing.
  • organic solvents are suitable for use herein but preferably the organic solvent is selected from alcohols, amines, esters, glycol ethers, glycols, terpenes and mixtures thereof.
  • the organic solvent system is preferably formulated to meet the constraints on volatile solvent components described above and in highly preferred embodiments the solvent system will contain less than about 50%, preferably less than 20% and more preferably less than 10% of solvent components having a vapor pressure above about 0.1 mm Hg at 25°C and atmospheric pressure.
  • the solvent is essentially free (contains less than about 5% by weight) of solvent components having a boiling point below about 150°C, flash point below about 100°C or a vapor pressure above about 1 mm Hg at 25 °C and atmospheric pressure.
  • the organic solvent system is preferably selected from organoamine solvents, inclusive of alkanolamines, alkylamines, alkyleneamines and mixtures thereof; alcoholic solvents inclusive of aromatic, aliphatic (preferably C 4 -C 10 ) and cycloaliphatic alcohols and mixtures thereof; glycols and glycol derivatives inclusive of C 2 -C 3 (poly)alkylene glycols, glycol ethers, glycol esters and mixtures thereof; and mixtures selected from organoamine solvents, alcoholic solvents, glycols and glycol derivatives.
  • organoamine solvents inclusive of alkanolamines, alkylamines, alkyleneamines and mixtures thereof
  • alcoholic solvents inclusive of aromatic, aliphatic (preferably C 4 -C 10 ) and cycloaliphatic alcohols and mixtures thereof
  • glycols and glycol derivatives inclusive of C 2 -C 3 (poly)alkylene glycols, glycol ethers, glycol esters and mixtures thereof
  • the organic solvent comprises organoamine (especially alkanolamine) solvent and glycol ether solvent, preferably in a weight ratio of from about 3:1 to about 1:3, and wherein the glycol ether solvent is selected from ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monobutyl ether, and mixtures thereof.
  • the glycol ether is a mixture of diethylene glycol monobutyl ether and propylene glycol butyl ether, especially in a weight ratio of from about 1:2 to about 2:1.
  • suitable organic solvents include one or more water-soluble or dispersible, preferably hydroxylated organoamine solvents, especially alkanolamine solvents having a pKa of at least 8.8, preferably at least 9.3 and more preferably at least 9.8.
  • the organic solvent system preferably comprises a mixture of a first organoamine solvent having a pKa of about 9.5 or less and a second organoamine solvent having a pKa greater than about 9.5.
  • organic solvents comprising salts of organoamines which are introduced into the wash liquor of the automatic dishwashing machine at a wash liquor pH above the highest pKa of the organoamine and which thereby act as a source of organoamine solvent.
  • Suitable salt counterions include halides such as chloride and bromide, oxyanions such as sulphate, borate, phosphate, pyrophosphate and polyphosphate and surfactant anions.
  • the organic solvent system is used in conjunction with a wetting agent effective in lowering the surface tension of the solvent system, preferably to at least 1 mN/m less than that of the wetting agent, the wetting agent preferably being selected from organic surfactants having a surface tension less than about 30 mN/m, more preferably less than about 28 mN/m and specially less than about 26 mN/m.
  • a wetting agent for use herein are silicone polyether copolymers, especially silicone poly(alkyleneoxide) copolymers wherein alkylene is selected from ethylene, propylene and mixtures thereof.
  • the organic solvent can be selected from: a) polar, hydrogen-bonding solvents having a Hansen solubility parameter of at least 20 (Mpa) 1/2 , a polarity parameter of at least 7 (Mpa) 1/2 , preferably at least 12 (Mpa) 1/2 and a hydrogen bonding parameter of at least 10 (Mpa) 1 2 b) polar non-hydrogen bonding solvents having a Hansen solubility parameter of at least 20 (Mpa) 1/2 , a polarity parameter of at least 7 (Mpa) 1 2 , preferably at least 12 (Mpa) 1 2 and a hydrogen bonding parameter of less than 10 (Mpa) 1 2 c) amphiphilic solvents having a Hansen solubility parameter below 20 (Mpa) 1 2 , a polarity parameter of at least 7 (Mpa) 1 2 and a hydrogen bonding parameter of at least 10 (Mpa) 1 2 d) non-polar solvents having a polarity
  • the invention also relates to detergent packs and multi-component products suitable for use in an automatic dishwashing machine or dishwashing pretreatment to provide baked and burnt-on soil removal and other cleaning benefits.
  • an automatic dishwashing detergent pack comprising two or more automatic dishwashing detergent and/or auxiliary products, storage means comprising separate but associated portions of the two or more products and means, for example electric pump means, for delivering quantities of the two or more products into the same or different cycles of an automatic dishwashing machine.
  • the pack can also comprise means for controlling the relative dispensing rate of the two or more products from the storage means.
  • the pack preferably comprises an organic solvent composition and an automatic dishwashing detergent composition and is used for removing cooked-, baked-, and burnt- on food soil from cookware and tableware.
  • the two or more automatic dishwashing detergent or auxiliary products are in rheology-matched gel-form.
  • Compositions are considered to be rheology-matched if they have similar yield values (differing by less than about 50%, preferably by less than about 20%) and/or similar viscosities (differing by less than about 50%, preferably by less than about 20%) under the same shear conditions.
  • an organic solvent composition comprises about 1% to about 99%, preferably from about 5% to about 90% of an organic solvent system for removing cooked-, baked-, or burnt-on food soil from cookware and tableware, from about 0.5% to about 50%, preferably from about 5% to about 25% of bleach and from about 0.0001% to about 10%> of detergency enzyme.
  • the compositions preferably are in gel-fo ⁇ n and contain a thickener such as methylcellulose or other nonionic cellulosic thickener.
  • the solvent compositions are preferably anhydrous (containing less than about 5%, preferably less than about 1% of water) and comprise bleach in the form of a particulate suspension having an average particle size in the range from about 10 to about lOO ⁇ m, preferably from about 25 to about 75 ⁇ m.
  • the compositions are also builder free or generally builder free. It is a feature of the invention that a broad range of solvents, including organoamine solvents can be incorporated in the solvent compositions of the invention with acceptable bleach stability provided the water content of the composition is carefully controlled.
  • an automatic dishwashing detergent composition comprises from about 0.05% to about 10% by weight of a low- foaming non-ionic surfactant, from about 1% to about 30% of an organoamine, preferably alkanolamine (especially monoethanolamine) solvent and at least about 5% by weight of a detergency builder.
  • the automatic dishwashing detergent composition is in the form of a gel comprising from about 2% to about 20%, preferably from 5% to 15% by weight of an alkanolamine, at least about 5% by weight of detergency builder, and from about 0.1% to about 5% by weight of a low foaming non-ionic surfactant.
  • compositions also preferably have a pH (1% aqueous solution) in excess of about 9.0, preferably in excess of about 10.5 and more preferably greater than about 11.
  • an automatic dishwashing detergent composition comprises from about 0.05% to about 10% by weight of a low-foaming non-ionic surfactant, from about 1% to about 30% of an organic solvent, preferably alkanolamine solvent, at least about 5% by weight of a detergency builder and a wetting agent, preferably a silicone- poly(alkyleneoxide) copolymers.
  • an automatic dishwashing detergent pack comprising: i) an organic solvent composition suitable for use in automatic dishwashing comprising from about 1% to about 99%>, preferably from about 5% to about 90%, especially from about 40% to about 80% of an organic solvent system for removing cooked-, baked-, or burnt-on food soil from cookware and tableware, from about 0.5% to about 50%, preferably from about 5% to about 25% of bleach, from about 0.0001% to about 10% of detergency enzyme, and wherein the composition is in the form of an anhydrous gel comprising bleach in the form of a particulate suspension; and ii) an automatic dishwashing detergent composition comprising from about 0.05% to about 10% by weight of a low-foaming non-ionic surfactant, optionally from about 1% to about 30% of an organoamine, preferably alkanolamine solvent, and at least about 5% by weight of a detergency builder.
  • an organic solvent composition suitable for use in automatic dishwashing comprising from about 1% to about 99%
  • the automatic dishwashing detergent composition is in the form of a gel comprising from about 2% to about 20%, preferably from about 5% to about 15% by weight of the composition of an alkanolamine, at least about 5% by weight of detergency builder (such as sodium potassium tripolyphosphate), and from about 0.1% to about 5% by weight of the composition of a low foaming nonionic surfactant.
  • detergency builder such as sodium potassium tripolyphosphate
  • compositions comprising the herein defined solvent systems for direct application to burnt-on and baked-on food soiled cookware and tableware.
  • compositions comprising an organic solvent system having a liquid surface tension of less than about 27 mN/m.
  • Preferred compositions contain from about 1% to about 99% preferably from about 5% to about 50% of organic solvent as herein defined, highly preferred being a mixed solvent system based on alkanolamine and a mixed glycol ether solvent system as described hereinabove.
  • the present invention also provides a hard-surface cleaning or dishwashing pretreatment composition for removing cooked-, baked-, or burnt-on food soil from cookware and tableware, the composition comprising an organic solvent system having an advancing contact angle on a polymerised grease-coated substrate of less than 20°, preferably less than 10° and more preferably less than 5°.
  • the hard-surface cleaning composition comprises an organic solvent system comprising a plurality of solvent components in levels such that the composition has an advancing contact angle on polymerised grease of less than that of any of the corresponding compositions containing the individual components of the solvent system.
  • the method for determining contact angle is as follows.
  • a sample plate (prepared as described below) is dipped into and pulled out of a liquid and contact angles calculated after Wilhelmy Method.
  • the force exerted on the sample according to the immersion depth is measured (using a Kruss K12 tensiometer and System K121 software) and is proportional to the contact angle of the liquid on the solid surface.
  • the sample plate is prepared as follows: Spray 30-50 grams of Canola Oil into a beaker. Dip a glass slide (3x9x0.1 cm) into the Oil and thoroughly coat the surface. This results in an evenly dispersed layer of oil on the surface. Adjust the weight of product on the slide's surface until approximately 0.5 g of oil has been delivered and evenly distributed. At this point, bake the slides at 450F for 20 minutes, and allow to cool to room temperature.
  • compositions of the invention are also characterised by having a low volatile organic content, preferably with a volatile organic content less than about 20%>, preferably less than about 10% and more preferably less than about 5%.
  • the compositions of the invention designed for hard surface cleaning or dishwashing pretreatment use should also meet certain rheological and other performance parameter including both the ability to be sprayed and the ability to cling to surfaces.
  • the product sprayed on a vertical stainless steel surface has a flow velocity less than about 1 cm sec, preferably less than about 0.1 cm s.
  • the product is in the form of a shear thinning fluid having a shear index from about 0.3 to about 0.7, preferably from about 0.4 to about 0.6 and a consistency index from about 0.20 to about 0.15, preferably from about 0.175 to about 0.160 kg/(m s 2"n ).
  • the product preferably has a viscosity from about 0.1 to about 200 Pa s, preferably from about 0.3 to about 20 Pa s as measured with a Brookfield cylinder viscometer (model LVDII) using 10 ml sample, a spindle S-31 and a speed of 3 rpm.
  • a Brookfield cylinder viscometer model LVDII
  • compositions suitable for inclusion in pouches will normally comprise a major proportion of solvent system components, preferably at least 50% by weight, more preferably at least 70% by weight or even higher.
  • the present invention envisages the use of solvent compositions as additives for conventional automatic dishwashing detergent compositions. It also envisages multi- component dishwashing products containing purpose-designated combination of solvent compositions and dishwashing detergent compositions.
  • the invention also envisages so called "all-in-one" detergent and hard surface cleaning products having both an alkaline detergent and a solvent functionality.
  • the invention does not require the two compositions to be in the same physical form.
  • the organic solvent composition can be in any physical form, e.g. liquid, paste, cream, gel, powder, granules or tablets and similarly the automatic dishwashing detergent composition can be in any of these forms.
  • both compositions are in the form of liquids or gels or the organic solvent composition is in the form of liquid or gel and the automatic dishwashing detergent composition is in the form of powder, granules or tablet.
  • the compositions used herein can be dispensed from any suitable device, such as bottles (pump assisted bottles, squeeze bottles), paste dispensers, capsules, multi-compartment bottles, multi-compartment capsules, pouches, and multi- compartment pouches, etc.
  • the solvent compositions herein comprise one or more organic solvents and can additionally comprises surfactant, bleach, enzyme, enzyme stabilising components, thickener, etc.
  • the organic solvents should be selected so as to be compatible with the tableware/cookware as well as with the different parts of an automatic dishwashing machine. Furthermore, the solvent system should be effective and safe to use having a volatile organic content above 1 mm Hg (and preferably above 0.1 mm Hg) of less than about 50%), preferably less than about 30%, more preferably less than about 10% by weight of the solvent system. Also they should have very mild pleasant odours.
  • the individual organic solvents used herein generally have a boiling point above about 150°C, flash point above about 100°C and vapor pressure below about 1 mm Hg, preferably below 0.1 mm Hg at 25°C and atmospheric pressure.
  • Solvents that can be used herein include: i) alcohols, such as benzyl alcohol, 1,4- cyclohexanedimethanol, 2-ethyl-l-hexanol, furfuryl alcohol, 1,2-hexanediol and other similar materials; ii) amines, such as alkanolamines (e.g.
  • primary alkanolamines monoethanolamine, monoisopropanolamine, diethylethanolamine, ethyl diethanolamine
  • secondary alkanolamines diethanolamine, diisopropanolamine, 2-(methylamino)ethanol
  • ternary alkanolamines triethanolamine, triisopropanolamine
  • alkylamines e.g.
  • primary alkylamines monomethylamine, monoethylamine, monopropylamine, monobutylamine, monopentylamine, cyclohexylamine), secondary alkylamines: (dimethylamine), alkylene amines (primary alkylene amines: ethylenediamine, propylenediamine) and other similar materials; iii) esters, such as ethyl lactate, methyl ester, ethyl acetoacetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate and other similar materials; iv) glycol ethers, such as ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol
  • Preferred solvent systems to be used herein are systems comprising alkanolamines, especially monoethanolamine and combinations of monoethanolamine and 2- (methylamino)ethanol.
  • the detergent and cleaning compositions herein can comprise traditional detergency components and can also comprise organic solvents having a cleaning function and organic solvents having a carrier or diluent function or some other specialised function.
  • the compositions will generally be built and comprise one or more detergent active components which may be selected from colorants, bleaching agents, surfactants, alkalinity sources, enzymes, thickeners (in the case of liquid, paste, cream or gel compositions) and disrupting and binding agents (in the case of powder, granules or tablets).
  • Highly preferred detergent components include a builder compound, an alkalinity source, a surfactant, an enzyme and a bleaching agent.
  • the components described hereinbelow can be incorporated either in the organic solvent compositions and/or the detergent or cleaning compositions.
  • the detergent surfactant is preferably low foaming by itself or in combination with other components (i.e. suds suppressers).
  • the detergent surfactant is preferably foamable in direct application but low foaming in automatic dishwashing use.
  • Surfactants suitable herein include anionic surfactants such as alkyl sulfates, alkyl ether sulfates, alkyl benzene sulfonates, alkyl glyceryl sulfonates, alkyl and alkenyl sulphonates, alkyl ethoxy carboxylates, N-acyl sarcosinates, N-acyl taurates and alkyl succinates and sulfosuccinates, wherein the alkyl, alkenyl or acyl moiety is C5-C20 , preferably CiQ-Cjg linear or branched; cationic surfactants such as chlorine esters (US-A-4228042, US-A-4239660 and US-A-4260529) and mono C6-C16
  • Surfactants suitable herein are disclosed, for example, in US- A-3, 929,678 , US-A- 4,259,217, EP-A-0414 549, WO-A-93/08876 and WO-A-93/08874.
  • Surfactants are typically present at a level of from about 0.2% to about 30% by weight, more preferably from about 0.5% to about 10%> by weight, most preferably from about 1%> to about 5% by weight of composition.
  • Preferred surfactant for use herein are low foaming and include low cloud point nonionic surfactants and mixtures of higher foaming surfactants with low cloud point nonionic surfactants which act as suds suppresser therefor.
  • Builders suitable for use in detergent and cleaning compositions herein include water- soluble builders such as citrates, carbonates and polyphosphates e.g. sodium tripolyphosphate and sodium tripolyphosphate hexahydrate, potassium tripolyphosphate and mixed sodium and potassium tripolyphosphate salts; and partially water-soluble or insoluble builders such as crystalline layered silicates (EP-A-0164514 and EP-A- 0293640) and aluminosilicates inclusive of Zeolites A, B, P, X, HS and MAP.
  • the builder is typically present at a level of from about 1% to about 80%> by weight, preferably from about 10% to about 70% by weight, most preferably from about 20% to about 60%) by weight of composition.
  • Amo hous sodium silicates having an SiO2:Na2O ratio of from 1.8 to 3.0, preferably from 1.8 to 2.4, most preferably 2.0 can also be used herein although highly preferred from the viewpoint of long term storage stability are compositions containing less than about 22%, preferably less than about 15% total (amorphous and crystalline) silicate.
  • Enzymes suitable herein include bacterial and fungal cellulases such as Carezyme and Celluzyme (Novo Nordisk A/S); peroxidases; lipases such as Amano-P (Amano Pharmaceutical Co.), Ml Lipase R and Lipomax R (Gist-Brocades) and Lipolase R and Lipolase Ultra R (Novo); cutinases; proteases such as Esperase R , Alcalase R , Durazym R and Savinase R (Novo) and Maxatase R , Maxacal R , Properase R and Maxapem R (Gist-Brocades); and and ⁇ amylases such as Purafect Ox Am R (Genencor) and Termamyl R , Ban R , Fungamyl R , Duramyl R , and Natalase R (Novo); and mixtures thereof. Enzymes are preferably added herein as prills, granulates, or cogranulates at levels typically
  • Bleaching agents suitable herein include chlorine and oxygen bleaches, especially inorganic perhydrate salts such as sodium perborate mono-and tetrahydrates and sodium percarbonate optionally coated to provide controlled rate of release (see, for example, GB-A- 1466799 on sulfate/carbonate coatings), preformed organic peroxyacids and mixtures thereof with organic peroxyacid bleach precursors and or transition metal- containing bleach catalysts (especially manganese or cobalt).
  • Inorganic perhydrate salts are typically incorporated at levels in the range from about 1% to about 40% by weight, preferably from about 2% to about 30% by weight and more preferably from abut 5% to about 25% by weight of composition.
  • Peroxyacid bleach precursors preferred for use herein include precursors of perbenzoic acid and substituted perbenzoic acid; cationic peroxyacid precursors; peracetic acid precursors such as TAED, sodium acetoxybenzene sulfonate and pentaacetylglucose; pernonanoic acid precursors such as sodium 3,5,5- trimethylhexanoyloxybenzene sulfonate (iso-NOBS) and sodium nonanoyloxybenzene sulfonate (NOBS); amide substituted alkyl peroxyacid precursors (EP-A-0170386); and benzoxazin peroxyacid precursors (EP-A-0332294 and EP-A-0482807).
  • Bleach precursors are typically incorporated at levels in the range from about 0.5% to about 25%, preferably from about 1% to about 10% by weight of composition while the preformed organic peroxyacids themselves are typically incorporated at levels in the range from 0.5% to 25% by weight, more preferably from 1% to 10% by weight of composition.
  • Bleach catalysts preferred for use herein include the manganese triazacyclononane and related complexes (US-A-4246612, US-A-5227084); Co, Cu, Mn and Fe bispyridylamine and related complexes (US-A-5114611); and pentamine acetate cobalt(III) and related complexes(US-A-4810410).
  • the suds suppressers suitable for use herein include nonionic surfactants having a low cloud point.
  • Cloud point is a well known property of nonionic surfactants which is the result of the surfactant becoming less soluble with increasing temperature, the temperature at which the appearance of a second phase is observable is referred to as the “cloud point” (See Kirk Othmer, pp. 360-362).
  • a “low cloud point” nonionic surfactant is defined as a nonionic surfactant system ingredient having a cloud point of less than 30° C, preferably less than about 20° C, and even more preferably less than about 10° C, and most preferably less than about 7.5° C.
  • Typical low cloud point nonionic surfactants include nonionic alkoxylated surfactants, especially ethoxylates derived from primary alcohol, and polyoxypropylene/polyoxyethylene/polyoxypropylene (PO/EO/PO) reverse block polymers.
  • low cloud point nonionic surfactants include, for example, ethoxylated-propoxylated alcohol (e.g., Olin Corporation's Poly-Tergent® SLF18) and epoxy-capped poly(oxyalkylated) alcohols (e.g., Olin Corporation's Poly-Tergent® SLF18B series of nonionics, as described, for example, in US-A-5,576,281).
  • Preferred low cloud point surfactants are the ether-capped poly(oxyalkylated) suds suppresser having the formula:
  • R ! is a linear, alkyl hydrocarbon having an average of from about 7 to about 12 carbon atoms
  • R 2 is a linear, alkyl hydrocarbon of about 1 to about 4 carbon atoms
  • R 3 is a linear, alkyl hydrocarbon of about 1 to about 4 carbon atoms
  • x is an integer of about 1 to about 6
  • y is an integer of about 4 to about 15
  • z is an integer of about 4 to about 25.
  • low cloud point nonionic surfactants are the ether-capped poly(oxyalkylated) having the formula:
  • R I O(R II O) n CH(CH 3 )OR III
  • R r is selected from the group consisting of linear or branched, saturated or unsaturated, substituted or unsubstituted, aliphatic or aromatic hydrocarbon radicals having from about 7 to about 12 carbon atoms
  • R relieve may be the same or different, and is independently selected from the group consisting of branched or linear C 2 to C 7 alkylene in any given molecule
  • n is a number from 1 to about 30
  • R m is selected from the group consisting of:
  • R 2 is (ii) then either: (A) at least one of R 1 is other than C 2 to C 3 alkylene; or (B) R 2 has from 6 to 30 carbon atoms, and with the further proviso that when R 2 has from 8 to 18 carbon atoms, R is other than C, to C 5 alkyl.
  • suitable components herein include organic polymers having dispersant, anti- redeposition, soil release or other detergency properties invention in levels of from about 0.1% to about 30%, preferably from about 0.5% to about 15%>, most preferably from about 1%) to about 10% by weight of composition.
  • Preferred anti-redeposition polymers herein include acrylic acid containing polymers such as Sokalan PA30, PA20, PA15, PA10 and Sokalan CP10 (BASF GmbH), Acusol 45N, 480N, 460N (Rohm and Haas), acrylic acid/maleic acid copolymers such as Sokalan CP5 and acrylic/methacrylic copolymers.
  • Preferred soil release polymers herein include alkyl and hydroxyalkyl celluloses (US-A-4,000,093), polyoxyethylenes, polyoxypropylenes and copolymers thereof, and nonionic and anionic polymers based on terephthalate esters of ethylene glycol, propylene glycol and mixtures thereof.
  • Heavy metal sequestrants and crystal growth inhibitors are suitable for use herein in levels generally from about 0.005% to about 20%, preferably from about 0.1% to about 10%, more preferably from about 0.25%> to about 7.5% and most preferably from about 0.5% to about 5% by weight of composition, for example diethylenetriamine penta (methylene phosphonate), ethylenediamine tetra(methylene phosphonate) hexamethylenediamine tetra(methylene phosphonate), ethylene diphosphonate, hydroxy- ethylene- 1 , 1 -diphosphonate, nitrilotriacetate, ethylenediaminotetracetate, ethylenediamine-N,N'-disuccinate in their salt and free acid forms.
  • diethylenetriamine penta methylene phosphonate
  • ethylene diphosphonate hydroxy
  • compositions herein can contain a corrosion inhibitor such as organic silver coating agents in levels of from about 0.05% to about 10%>, preferably from about 0.1% to about 5% by weight of composition (especially paraffins such as Winog 70 sold by Wintershall, Salzbergen, Germany), nitrogen-containing corrosion inhibitor compounds (for example benzotriazole and benzimadazole - see GB-A-1137741) and Mn(II) compounds, particularly Mn(II) salts of organic ligands in levels of from about 0.005% to about 5%, preferably from about 0.01%> to about 1%, more preferably from about 0.02%> to about 0.4% by weight of the composition.
  • a corrosion inhibitor such as organic silver coating agents in levels of from about 0.05% to about 10%>, preferably from about 0.1% to about 5% by weight of composition (especially paraffins such as Winog 70 sold by Wintershall, Salzbergen, Germany), nitrogen-containing corrosion inhibitor compounds (for example benzotriazole and benzimadazole - see
  • Suitable components herein include colorants, water-soluble bismuth compounds such as bismuth acetate and bismuth citrate at levels of from about 0.01%> to about 5%, enzyme stabilizers such as calcium ion, boric acid, propylene glycol and chlorine bleach scavengers at levels of from about 0.01% to about 6%, lime soap dispersants (see WO-A- 93/08877), suds suppressors (see WO-93/08876 and EP-A-0705324), polymeric dye transfer inhibiting agents, optical brighteners, perfumes, fillers and clay.
  • enzyme stabilizers such as calcium ion, boric acid, propylene glycol and chlorine bleach scavengers at levels of from about 0.01% to about 6%
  • lime soap dispersants see WO-A- 93/08877
  • suds suppressors see WO-93/08876 and EP-A-0705324
  • polymeric dye transfer inhibiting agents such as optical brighteners, perfumes
  • Liquid detergent compositions can contain water and other volatile solvents as carriers.
  • Low quantities of low molecular weight primary or secondary alcohols such as methanol, ethanol, propanol and isopropanol can be used in the liquid detergent of the present invention.
  • Other suitable carrier solvents used in low quantities includes glycerol, propylene glycol, ethylene glycol, 1,2-propanediol, sorbitol and mixtures thereof.
  • Examples 1 to 5 A combination of solvent compositions and automatic dishwashing detergents are used to wash a load of tableware and cookware having cooked-on, baked-on and burnt-on food soils.
  • the load comprises different soils and different substrates: lasagne baked for 2 hours at 140°C on Pyrex, lasagne cooked for 2 hours at 150°C on stainless steel, potato and cheese cooked for 2 hours at 150°C on stainless steel, egg yolk cooked for 2 hours at 150°C on stainless steel and sausage cooked for 1 hour at 120°C followed by 1 hour at 180°C.
  • the load is washed in a 5 litre liquor capacity Bosch 6032 dishwashing machine, at 55°C without prewash, using the compositions given in Examples 1 to 5.
  • Examples 1 to 5 illustrate the use of a combination of a two-phase automatic dishwashing detergent tablet and an organic solvent composition added separately to the main- ash cycle of the dishwashing machine.
  • the two-component compositions of examples 1 to 5 provided excellent removal of cooked-on, baked-on and burnt-on food soils.
  • Examples 6 to 10 illustrate the use of a combination of an automatic dishwashing liquid detergent and an organic solvent composition for removing cooked-, baked- and burnt-on soils.
  • the two-component compositions of examples 6 to 10 are used to wash a load of cookware and tableware according to the procedure described hereinabove (Examples 1 to 5).
  • 30 ml of the dishwashing detergent and the 10 ml of the solvent composition are separately delivered to the main-wash cycle of a 5 litre liquor capacity Bosch 6032 dishwashing machine, at 55°C without prewash.
  • the compositions of examples 6 to 10 provide excellent removal of cooked-on, baked-on and burnt-on food soils.
  • Examples 11 to 15 further illustrate the use of a combination of an automatic dishwashing liquid detergent and an organic solvent composition for removing cooked-, baked- and burnt-on soils.
  • the two-component compositions of examples 11 to 15 are used to wash a load of cookware and tableware according to the procedure described hereinabove (Examples 1 to 5).
  • the automatic dishwashing liquid detergent and the organic solvent composition are delivered in separate compartments of a unit dose (30 ml of the dishwashing detergent and the 10 ml of the solvent composition) partially hydrolysed PVA water-soluble pouch.
  • the pouch is delivered to the main-wash cycle of a Bosch 6032 dishwashing machine, at 55°C without prewash.
  • the two-component compositions of examples 11 to 15 provide excellent removal of cooked-on, baked-on and burnt-on food soils. At the same time, they provide excellent compatibility with the PVA pouch material.
  • Examples 16 to 19 illustrate the use of a combination of an automatic dishwashing liquid detergent and an organic solvent composition for removing cooked-, baked- and burnt-on soils.
  • the two-component compositions are stored in a dual-compartment bottle having an electrically operated pump and delivered at a feed ratio (dishwashing liquid detergent: organic solvent composition) of 3:1.
  • the compositions of examples 16 to 19 are used to wash a dishware load according to the procedure described hereinabove (Examples 1 to 5). 30 ml of the dishwashing detergent and 10 ml of the solvent composition are separately delivered from the dual-compartment bottle to the main- wash cycle of a Bosch 6032 dishwashing machine, at 55°C without prewash.
  • the two-component compositions of examples 16 to 19 provide excellent removal of cooked-on, baked-on and burnt-on food soils.
  • Examples 20 to 24 illustrate "all-in-one" solvent-containing automatic dishwashing detergent compositions.
  • the compositions of examples 20 to 24 are used to wash a dishware load following the procedure described hereinabove (Examples 1 to 5). 40 ml of the dishwashing composition are delivered to the main-wash cycle of a Bosch 6032 dishwashing machine, at 55°C without prewash.
  • the "all-in-one" compositions of examples 20 to 24 provide excellent removal of baked-on soils.
  • Examples 25 to 28 illustrate pre-treatment compositions used to facilitate the removal of cooked-on, baked-on and burnt-on food soils prior to the dishwashing process.
  • the compositions of examples 25 to 28 are applied to a dishware load having the soils described hereinabove (Examples 1 to 5).
  • the dishware load is allowed to soak for 10 minutes, then the dishware is rinsed under cold tap water.
  • the dishware load is thereafter washed either manually or in an automatic dishwashing machine, for example in a Bosch 6032 dishwashing machine, at 55°C without prewash, using the dishwashing detergent compositions of examples 1 to 5.
  • the dishware load treated with compositions of examples 25 to 28 and thereafter washed in the dishwashing machines present excellent removal of cooked-on, baked-on and burnt-on food soils.

Abstract

A method of removing cooked-, baked-, or burnt-on food soil from cookware and tableware comprising washing the cookware/tableware in an automatic dishwashing machine in the presence of an organic solvent system having a wash liquor concentration of from about 100 to about 5000 ppmm. The method includes the storage and delivery of organic solvent compositions and dishwashing detergent composition from multi-compartment containers. The method provides excellent removal of stubborn soils which are very difficult to remove in a conventional automatic dishwashing process. Automatic detergent dishwashing compositions and hard-surface detergent compositions comprising organic solvent systems for the removal of cooked-, baked-, or burnt-on food soil from cookware and tableware are also disclosed.

Description

CLEANING COMPOSITION
Technical field
The present invention is in the field of dishwashing, in particular it relates to dishwashing and automatic dishwashing products, auxiliaries and methods suitable for the removal of cooked-, baked- and burnt-on soils from cookware and tableware.
Background of the invention
Cooked-, baked- and burnt-on soils are amongst the most severe types of soils to remove from surfaces. Traditionally, the removal of cooked-, baked- and burnt-on soils from cookware and tableware requires soaking the soiled object prior to a mechanical action. Apparently, the automatic dishwashing process alone does not provide a satisfactory removal of cooked-, baked- and burnt-on soils.
The use of cleaning compositions containing solvent for helping in the removal of cooked-, baked- and burnt-on solids is known in the art. For example, US-A-5, 102,573 provides a method for treating hard surfaces soiled with cooked-on, baked-on or dried-on food residues comprising applying a pre-spotting composition to the soiled article. The composition applied comprises surfactant, builder, amine and solvent. WO-A-94/28108 discloses an aqueous cleaner concentrate composition, that can be diluted to form a more viscous use solution comprising an effective thickening amount of a rod micelle thickener composition, lower alkyl glycol ether solvent and hardness sequestering agent. The application also describes a method of cleaning a food preparation unit having at least one substantially vertical surface having a baked food soil coating.
The use of solvents in the automatic dishwashing context is also known. JP-A- 10,017,900 discloses an automatic dishwashing auxiliary composition comprising non- ionic low foaming surfactant, organic solvent and water. The composition delivers detergency and drying benefits. JP-A-11,117,000 discloses a cleaning assistant composition for automatic dishwashing machines comprising surfactant, organic high- molecular polyelectrolyte, water-soluble solvent and water. The claimed assistant composition helps in the cleaning of stubborn dirt such as that due to oil or lipstick.
There is still the need of a method and products for the removal of cooked-, baked- and burnt-on soils from cookware and tableware using an automatic dishwashing machine and avoiding the use of a pre-treatment step. There is also a need for detergent, hard- surface cleaning and dishwashing pretreatment products providing improved cleaning performance, especially on burnt-on food soils having a high carbon content.
Summary of the invention
According to a first aspect of the present invention, there is provided a method of removing cooked-, baked-, or burnt-on food soil (such as grease, meat, dairy, fruit, pasta and any other food especially difficult to remove after the cooking process) from cookware and tableware (including stainless steel, glass, plastic, wood and ceramic objects). The method comprises washing the cookware/tableware in an automatic dishwashing machine in the presence of an organic solvent system (comprising a single solvent compound or a mixture of solvent compounds) having a volatile organic content above 1 mm Hg of less than about 50%, preferably less than about 20% and more preferably less than about 10% by weight of the solvent system. Herein volatile organic content of the solvent system is defined as the content of organic components in the solvent system having a vapor pressure higher than the prescribed limit at 25 °C and atmospheric pressure.
The optimum concentration of the solvent in the wash liquor is from about 100 ppm to about 10000 ppm, preferably from about 200 to about 8000 and more preferably from about 500 to about 5000 ppm. The organic solvent system is preferably used in combination with a surfactant, especially a low foaming non-ionic surfactant and a detergency builder. Thus another embodiment of the invention provides a method of removing cooked-, baked-, or burnt-on food soil from cookware and tableware comprising washing the cookware/tableware in an automatic dishwashing machine in the presence of surfactant, detergency builder and an organic solvent system wherein the surfactant has a wash liquor concentration of from about 10 to about 1000, preferably from about 100 to about 600 ppm, the detergency builder has a wash liquor concentration of about 100 to about 5000, preferably from about 1000 to about 3000 ppm and the organic solvent system has a wash liquor concentration of from about 100 to about 10000 ppm, preferably from about 200 to about 8000 ppm and more preferably from about 500 to about 5000 ppm. The pH of the wash liquor will generally be in the alkaline range, preferably at least 10.5 or more preferably at least 11.0, this pH being provided by means of an alkalinity source or sources in one or more compositions used for delivery of the solvent, surfactant and builder. Thus, according to another aspect of the invention, the removal of cooked-, baked-, or burnt-on food soil from cookware and tableware can be carried out by the use of one or more (generally unbuilt) organic solvent compositions (wherein "solvent composition" is understood to comprise the organic solvent system and optional additional active ingredients and diluents) and one or more (generally built) automatic dishwashing detergent compositions. By "generally unbuilt" is meant that the composition contains less than about 5% by weight of detergency builder and "generally built" is interpreted accordingly.
According to different embodiments of the present invention, the solvent compositions and automatic dishwashing detergent compositions can be delivered either at the same or at different points of the dishwashing cycle, for example: i) solvent composition and automatic dishwashing detergent composition are independently delivered in the pre- wash cycle and in the main-wash cycle, respectively; ii) a solvent composition and a first automatic dishwashing detergent composition are delivered in the pre-wash cycle and a second automatic dishwashing detergent composition in the main-wash cycle; iii) a first solvent composition and a first automatic dishwashing detergent composition are delivered in the pre-wash cycle and a second solvent composition and a second automatic dishwashing detergent composition in the main-wash cycle; iv) a solvent composition and an automatic dishwashing detergent composition are delivered simultaneously in the main-wash cycle; and v) a solvent composition and an automatic dishwashing detergent composition are delivered in the pre-wash and in the main-wash cycle. Another embodiment provides a method of removing cooked-, baked-, or burnt-on food soil from cookware and tableware comprising washing the cookware/tableware in the pre-wash cycle of an automatic dishwashing machine in the presence of an organic solvent composition and thereafter rinsing the cookware/tableware in the rinse cycle of the automatic dishwashing machine in the presence of an automatic dishwashing rinse composition.
In preferred embodiments, the organic solvent composition and the automatic dishwashing detergent composition are delivered either i) from separate storage means (e.g. different bottles in the case of liquid compositions, different pouches, etc.) into the same cycle of an automatic dishwashing machine to provide a wash liquor concentration of organic solvent as prescribed herein and preferably in the range from about 100 to about 10000 ppm, preferably from about 500 to about 5000; or ii) from separate zones of a multi-zone storage means (e.g. multi-compartment bottle in the case of liquid compositions) into the same or different cycles of an automatic dishwashing machine. Suitably, the organic solvent composition and the automatic dishwashing detergent composition are delivered from separate zones of a multi-zone storage means at a feed ratio (solvent composition: detergent composition) in the range from about 5:1 to about 1:50, preferably from about 2:1 to about 1:5 and more preferably from about 1:1 to about 1 :3 to provide a wash liquor concentration of organic solvent in the range preferably from about 100 to about 10000, more preferably from about 500 to about 5000 ppm. Alternatively, the organic solvent composition and the automatic dishwashing detergent composition are delivered from separate zones of a multi-zone storage means sequentially into the pre-wash and main wash cycle, respectively. This can be valuable in the case of product incompatibility to reduce interaction between the organic solvent composition and the automatic dishwashing detergent composition. Where, the organic solvent composition and the automatic dishwashing detergent composition are delivered simultaneously from separate zones of a multi-zone storage means, the physical form of the organic solvent composition and/or automatic dishwashing detergent composition is preferably such as to prevent intimate mixing of the compositions prior to contact thereof with the wash liquor. The invention can be also reduced to practice using multi-phase, "all-in-one" products. Thus, according to another embodiment of the invention, there is provided a method of removing cooked-, baked-, or burnt-on food soil from cookware and tableware comprising delivering separate portions of a multi-phase detergent composition into the same or different cycles of an automatic dishwashing machine, wherein the multi-phase detergent composition comprises at least a first phase containing an organic solvent composition and at least a second phase containing an automatic dishwashing detergent composition. The multiphase detergent composition, for example could take the form of a multi-layer liquid (e.g. coacervate) or gel contained in a bottle, or a multiphase tablet incorporating the solvent composition in the form of a gel contained within a preformed cavity or recess within the main tablet body. In either instance, the level of solvent delivered to the wash process should be such as to deliver the benefits on cooked-, baked- or burnt-on food soils.
The present invention also envisages the use of multiple organic solvent compositions. Thus according to a further aspect of the invention, there is provided a method of removing cooked-, baked-, or burnt-on food soil from cookware and tableware comprising delivering a plurality of organic solvent compositions of different solvent characteristics into the same or different cycles of an automatic dishwashing machine, for example, a first solvent composition in the pre-wash cycle and a second solvent composition in the main-wash cycle. For optimum performance, the different organic solvent compositions are designed to be specific to different soil and/or substrates. They can be delivered into different cycles of a dishwashing machine, with or without different automatic dishwashing detergent compositions, such that, for example, a first solvent composition and a first automatic dishwashing detergent composition are delivered into the pre-wash cycle and a second solvent composition and a second automatic dishwashing detergent composition are delivered into the main-wash cycle.
In another embodiment of the invention the organic solvent composition can be in a unit dose form allowing controlled release (for example delayed, sustained, triggered or slow release) of the composition during one or more repeated washing cycles. In preferred unit dose forms, the solvent composition is contained in a single or multi-compartment pouch.
The invention can also be applied to single-phase "all-in-one" products. According to this aspect, a method of removing cooked-, baked-, or burnt-on food soil from cookware and tableware comprises washing the cookware/tableware in an automatic dishwashing machine with an automatic dishwashing detergent composition comprising surfactant (preferably comprising low-foaming nonionic surfactant), detergency builder and organic solvent system in levels sufficient to provide a wash liquor concentration of from about 10 ppm to about 1000 ppm surfactant, from about 100 ppm to about 5000 ppm detergency builder, and about' 100 ppm to about 10,000, preferably from about 500 ppm to about 5000 ppm of organic solvent.
In the methods of the invention the organic solvent composition can be in the form of a liquid, paste, cream or gel and can be optionally encapsulated, packaged in a single- or multi-compartment pouch, or absorbed onto a porous carrier material. The solvent composition can be aqueous but preferably is anhydrous. Preferred pouches for use herein are water-soluble, solvent-resistant partially hydrolysed PVA pouches.
The optimum organic solvent systems for use herein are characterised by extremely low liquid surface tensions and contact angles on polymerised grease-coated substrates. Moreover, they generally consist of mixed solvent systems displaying synergistic contact angle and low surface tension. The organic solvent system herein preferably has a liquid surface tension at 25 °C of less than about 27 mN/m. In tenns of contact angle, compositions containing the solvent system preferably display an advancing contact angle on a polymerised grease-coated substrate at 25°C of less than 20°, preferably less than 10° and more preferably less than 5°. Furthermore, the advancing contact angle for compositions based on mixed solvent systems should be less than that of any of the corresponding compositions containing the individual components of the solvent system. Such solvent systems and compositions are found to be optimum for the removal of burnt-on soils having a high carbon content from cookware and tableware. It is a feature of the invention that these solvent systems also display excellent performance in dried application to soiled cookware and tableware. Thus, according to another aspect of the invention, there is provided a method of removing cooked-, baked-, or burnt-on food soil from cookware and tableware comprising treating the cookware/tableware with a hard surface cleaning composition comprising an organic solvent system. The organic solvent system desirably has a liquid surface tension of less than about 27 mN/m, preferably less than about 26 mN/m. The hard surface cleaning composition on the other hand desirably display an advancing contact angle on a polymerised grease-coated substrate at 25 °C of less than 20°, preferably less than 10° and more preferably less than 5°. Preferably, the above method comprises the step of pre- treating the cookware/tableware with the hard surface cleaning composition prior to manual or automatic dishwashing.
A broad range of organic solvents are suitable for use herein but preferably the organic solvent is selected from alcohols, amines, esters, glycol ethers, glycols, terpenes and mixtures thereof. The organic solvent system is preferably formulated to meet the constraints on volatile solvent components described above and in highly preferred embodiments the solvent system will contain less than about 50%, preferably less than 20% and more preferably less than 10% of solvent components having a vapor pressure above about 0.1 mm Hg at 25°C and atmospheric pressure. In highly preferred embodiments, the solvent is essentially free (contains less than about 5% by weight) of solvent components having a boiling point below about 150°C, flash point below about 100°C or a vapor pressure above about 1 mm Hg at 25 °C and atmospheric pressure.
The organic solvent system is preferably selected from organoamine solvents, inclusive of alkanolamines, alkylamines, alkyleneamines and mixtures thereof; alcoholic solvents inclusive of aromatic, aliphatic (preferably C4-C10) and cycloaliphatic alcohols and mixtures thereof; glycols and glycol derivatives inclusive of C2-C3 (poly)alkylene glycols, glycol ethers, glycol esters and mixtures thereof; and mixtures selected from organoamine solvents, alcoholic solvents, glycols and glycol derivatives. In one preferred embodiment the organic solvent comprises organoamine (especially alkanolamine) solvent and glycol ether solvent, preferably in a weight ratio of from about 3:1 to about 1:3, and wherein the glycol ether solvent is selected from ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monobutyl ether, and mixtures thereof. Preferably, the glycol ether is a mixture of diethylene glycol monobutyl ether and propylene glycol butyl ether, especially in a weight ratio of from about 1:2 to about 2:1. In other preferred embodiments, suitable organic solvents include one or more water-soluble or dispersible, preferably hydroxylated organoamine solvents, especially alkanolamine solvents having a pKa of at least 8.8, preferably at least 9.3 and more preferably at least 9.8. In these embodiments, the organic solvent system preferably comprises a mixture of a first organoamine solvent having a pKa of about 9.5 or less and a second organoamine solvent having a pKa greater than about 9.5. Also preferred for use herein are organic solvents comprising salts of organoamines which are introduced into the wash liquor of the automatic dishwashing machine at a wash liquor pH above the highest pKa of the organoamine and which thereby act as a source of organoamine solvent. Suitable salt counterions include halides such as chloride and bromide, oxyanions such as sulphate, borate, phosphate, pyrophosphate and polyphosphate and surfactant anions.
The effect of the solvent system can be further improved by the addition of certain wetting agents. Preferably, the organic solvent system is used in conjunction with a wetting agent effective in lowering the surface tension of the solvent system, preferably to at least 1 mN/m less than that of the wetting agent, the wetting agent preferably being selected from organic surfactants having a surface tension less than about 30 mN/m, more preferably less than about 28 mN/m and specially less than about 26 mN/m. Preferred wetting agents for use herein are silicone polyether copolymers, especially silicone poly(alkyleneoxide) copolymers wherein alkylene is selected from ethylene, propylene and mixtures thereof.
In terms of solvent parameters, the organic solvent can be selected from: a) polar, hydrogen-bonding solvents having a Hansen solubility parameter of at least 20 (Mpa)1/2, a polarity parameter of at least 7 (Mpa)1/2, preferably at least 12 (Mpa)1/2 and a hydrogen bonding parameter of at least 10 (Mpa)1 2 b) polar non-hydrogen bonding solvents having a Hansen solubility parameter of at least 20 (Mpa)1/2, a polarity parameter of at least 7 (Mpa)1 2, preferably at least 12 (Mpa)1 2 and a hydrogen bonding parameter of less than 10 (Mpa)1 2 c) amphiphilic solvents having a Hansen solubility parameter below 20 (Mpa)1 2, a polarity parameter of at least 7 (Mpa)1 2 and a hydrogen bonding parameter of at least 10 (Mpa)1 2 d) non-polar solvents having a polarity parameter below 7 (Mpa)1 2 and a hydrogen bonding parameter below 10 (Mpa)1/2 and e) mixtures thereof.
The invention also relates to detergent packs and multi-component products suitable for use in an automatic dishwashing machine or dishwashing pretreatment to provide baked and burnt-on soil removal and other cleaning benefits. In one embodiment, there is provided an automatic dishwashing detergent pack comprising two or more automatic dishwashing detergent and/or auxiliary products, storage means comprising separate but associated portions of the two or more products and means, for example electric pump means, for delivering quantities of the two or more products into the same or different cycles of an automatic dishwashing machine. The pack can also comprise means for controlling the relative dispensing rate of the two or more products from the storage means. The pack preferably comprises an organic solvent composition and an automatic dishwashing detergent composition and is used for removing cooked-, baked-, and burnt- on food soil from cookware and tableware. In a preferred embodiment the two or more automatic dishwashing detergent or auxiliary products are in rheology-matched gel-form. Compositions are considered to be rheology-matched if they have similar yield values (differing by less than about 50%, preferably by less than about 20%) and/or similar viscosities (differing by less than about 50%, preferably by less than about 20%) under the same shear conditions.
The invention also relates to organic solvent compositions suitable for use in automatic dishwashing or dishwashing pretreatment. In one embodiment, an organic solvent composition comprises about 1% to about 99%, preferably from about 5% to about 90% of an organic solvent system for removing cooked-, baked-, or burnt-on food soil from cookware and tableware, from about 0.5% to about 50%, preferably from about 5% to about 25% of bleach and from about 0.0001% to about 10%> of detergency enzyme. The compositions preferably are in gel-foπn and contain a thickener such as methylcellulose or other nonionic cellulosic thickener. The solvent compositions are preferably anhydrous (containing less than about 5%, preferably less than about 1% of water) and comprise bleach in the form of a particulate suspension having an average particle size in the range from about 10 to about lOOμm, preferably from about 25 to about 75 μm. The compositions are also builder free or generally builder free. It is a feature of the invention that a broad range of solvents, including organoamine solvents can be incorporated in the solvent compositions of the invention with acceptable bleach stability provided the water content of the composition is carefully controlled.
The invention also relates to detergent compositions suitable for use in automatic dishwashing or dishwashing pretreatment. In one embodiment, an automatic dishwashing detergent composition comprises from about 0.05% to about 10% by weight of a low- foaming non-ionic surfactant, from about 1% to about 30% of an organoamine, preferably alkanolamine (especially monoethanolamine) solvent and at least about 5% by weight of a detergency builder. Preferably, the automatic dishwashing detergent composition is in the form of a gel comprising from about 2% to about 20%, preferably from 5% to 15% by weight of an alkanolamine, at least about 5% by weight of detergency builder, and from about 0.1% to about 5% by weight of a low foaming non-ionic surfactant. Although any non-ionic low foaming surfactant (or combination of non-ionic surfactants and suds suppressers) can be used herein, capped nonionic surfactants and combinations or amine oxide and capped non-ionic surfactants are preferred. The compositions also preferably have a pH (1% aqueous solution) in excess of about 9.0, preferably in excess of about 10.5 and more preferably greater than about 11.
In one embodiment, an automatic dishwashing detergent composition comprises from about 0.05% to about 10% by weight of a low-foaming non-ionic surfactant, from about 1% to about 30% of an organic solvent, preferably alkanolamine solvent, at least about 5% by weight of a detergency builder and a wetting agent, preferably a silicone- poly(alkyleneoxide) copolymers. In a preferred embodiment an automatic dishwashing detergent pack is provided, comprising: i) an organic solvent composition suitable for use in automatic dishwashing comprising from about 1% to about 99%>, preferably from about 5% to about 90%, especially from about 40% to about 80% of an organic solvent system for removing cooked-, baked-, or burnt-on food soil from cookware and tableware, from about 0.5% to about 50%, preferably from about 5% to about 25% of bleach, from about 0.0001% to about 10% of detergency enzyme, and wherein the composition is in the form of an anhydrous gel comprising bleach in the form of a particulate suspension; and ii) an automatic dishwashing detergent composition comprising from about 0.05% to about 10% by weight of a low-foaming non-ionic surfactant, optionally from about 1% to about 30% of an organoamine, preferably alkanolamine solvent, and at least about 5% by weight of a detergency builder. Preferably, the automatic dishwashing detergent composition is in the form of a gel comprising from about 2% to about 20%, preferably from about 5% to about 15% by weight of the composition of an alkanolamine, at least about 5% by weight of detergency builder (such as sodium potassium tripolyphosphate), and from about 0.1% to about 5% by weight of the composition of a low foaming nonionic surfactant.
The invention also relates to hard-surface cleaning and dishwashing pretreatment compositions comprising the herein defined solvent systems for direct application to burnt-on and baked-on food soiled cookware and tableware. Preferred are compositions comprising an organic solvent system having a liquid surface tension of less than about 27 mN/m. Also preferred are compositions in the form of a liquid or gel and having a pH of greater than about 10.5, preferably greater than about 11. Preferred compositions contain from about 1% to about 99% preferably from about 5% to about 50% of organic solvent as herein defined, highly preferred being a mixed solvent system based on alkanolamine and a mixed glycol ether solvent system as described hereinabove.
The present invention also provides a hard-surface cleaning or dishwashing pretreatment composition for removing cooked-, baked-, or burnt-on food soil from cookware and tableware, the composition comprising an organic solvent system having an advancing contact angle on a polymerised grease-coated substrate of less than 20°, preferably less than 10° and more preferably less than 5°. Preferably, the hard-surface cleaning composition comprises an organic solvent system comprising a plurality of solvent components in levels such that the composition has an advancing contact angle on polymerised grease of less than that of any of the corresponding compositions containing the individual components of the solvent system.
The method for determining contact angle is as follows. A sample plate (prepared as described below) is dipped into and pulled out of a liquid and contact angles calculated after Wilhelmy Method. The force exerted on the sample according to the immersion depth is measured (using a Kruss K12 tensiometer and System K121 software) and is proportional to the contact angle of the liquid on the solid surface. The sample plate is prepared as follows: Spray 30-50 grams of Canola Oil into a beaker. Dip a glass slide (3x9x0.1 cm) into the Oil and thoroughly coat the surface. This results in an evenly dispersed layer of oil on the surface. Adjust the weight of product on the slide's surface until approximately 0.5 g of oil has been delivered and evenly distributed. At this point, bake the slides at 450F for 20 minutes, and allow to cool to room temperature.
The compositions of the invention are also characterised by having a low volatile organic content, preferably with a volatile organic content less than about 20%>, preferably less than about 10% and more preferably less than about 5%.
Apart from the solvent parameters described above, the compositions of the invention designed for hard surface cleaning or dishwashing pretreatment use should also meet certain rheological and other performance parameter including both the ability to be sprayed and the ability to cling to surfaces. For example, it is desirable that the product sprayed on a vertical stainless steel surface has a flow velocity less than about 1 cm sec, preferably less than about 0.1 cm s. For this purpose, the product is in the form of a shear thinning fluid having a shear index from about 0.3 to about 0.7, preferably from about 0.4 to about 0.6 and a consistency index from about 0.20 to about 0.15, preferably from about 0.175 to about 0.160 kg/(m s2"n). The product preferably has a viscosity from about 0.1 to about 200 Pa s, preferably from about 0.3 to about 20 Pa s as measured with a Brookfield cylinder viscometer (model LVDII) using 10 ml sample, a spindle S-31 and a speed of 3 rpm.
It is a feature of the invention that many of the solvent systems and compositions of the invention that are optimum for cleaning also demonstrate improved compatibility with partially hydrolysed PVA pouch materials of known construction and type. This is particularly surprising given that many well-known polar/or hydrolysed bonding solvent materials (for example the organoamines) in themselves have low compatibility with PVA materials and present serious issues for product stability. Solvent systems comprising mixtures of polar hydrogen bonding solvents (such as the organoamines) with a cosolvent selected from polar non-hydrogen bonding, amphiphilic and non-polar solvents and mixtures thereof are particularly valuable in this respect. Also valuable for improved PVA compatibility are organoamines present in composition in the form of amine salt. Compositions suitable for inclusion in pouches will normally comprise a major proportion of solvent system components, preferably at least 50% by weight, more preferably at least 70% by weight or even higher.
Finally, there is also disclosed the use of an organic solvent system in an automatic dishwashing machine to remove cooked-, baked-, or burnt-on food soil from cookware and tableware.
Detailed description of the invention
The present invention envisages the use of solvent compositions as additives for conventional automatic dishwashing detergent compositions. It also envisages multi- component dishwashing products containing purpose-designated combination of solvent compositions and dishwashing detergent compositions. The invention also envisages so called "all-in-one" detergent and hard surface cleaning products having both an alkaline detergent and a solvent functionality. In the case of additive and multi-component products, the invention does not require the two compositions to be in the same physical form. The organic solvent composition can be in any physical form, e.g. liquid, paste, cream, gel, powder, granules or tablets and similarly the automatic dishwashing detergent composition can be in any of these forms. Preferably, however, both compositions are in the form of liquids or gels or the organic solvent composition is in the form of liquid or gel and the automatic dishwashing detergent composition is in the form of powder, granules or tablet. The compositions used herein can be dispensed from any suitable device, such as bottles (pump assisted bottles, squeeze bottles), paste dispensers, capsules, multi-compartment bottles, multi-compartment capsules, pouches, and multi- compartment pouches, etc.
The solvent compositions herein comprise one or more organic solvents and can additionally comprises surfactant, bleach, enzyme, enzyme stabilising components, thickener, etc.
The organic solvents should be selected so as to be compatible with the tableware/cookware as well as with the different parts of an automatic dishwashing machine. Furthermore, the solvent system should be effective and safe to use having a volatile organic content above 1 mm Hg (and preferably above 0.1 mm Hg) of less than about 50%), preferably less than about 30%, more preferably less than about 10% by weight of the solvent system. Also they should have very mild pleasant odours. The individual organic solvents used herein generally have a boiling point above about 150°C, flash point above about 100°C and vapor pressure below about 1 mm Hg, preferably below 0.1 mm Hg at 25°C and atmospheric pressure.
Solvents that can be used herein include: i) alcohols, such as benzyl alcohol, 1,4- cyclohexanedimethanol, 2-ethyl-l-hexanol, furfuryl alcohol, 1,2-hexanediol and other similar materials; ii) amines, such as alkanolamines (e.g. primary alkanolamines: monoethanolamine, monoisopropanolamine, diethylethanolamine, ethyl diethanolamine; secondary alkanolamines: diethanolamine, diisopropanolamine, 2-(methylamino)ethanol; ternary alkanolamines: triethanolamine, triisopropanolamine); alkylamines (e.g. primary alkylamines: monomethylamine, monoethylamine, monopropylamine, monobutylamine, monopentylamine, cyclohexylamine), secondary alkylamines: (dimethylamine), alkylene amines (primary alkylene amines: ethylenediamine, propylenediamine) and other similar materials; iii) esters, such as ethyl lactate, methyl ester, ethyl acetoacetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate and other similar materials; iv) glycol ethers, such as ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol butyl ether and other similar materials; v) glycols, such as propylene glycol, diethylene glycol, hexylene glycol (2- methyl-2, 4 pentanediol), triethylene glycol, composition and dipropylene glycol and other similar materials; and mixtures thereof.
Preferred solvent systems to be used herein are systems comprising alkanolamines, especially monoethanolamine and combinations of monoethanolamine and 2- (methylamino)ethanol.
The detergent and cleaning compositions herein can comprise traditional detergency components and can also comprise organic solvents having a cleaning function and organic solvents having a carrier or diluent function or some other specialised function. The compositions will generally be built and comprise one or more detergent active components which may be selected from colorants, bleaching agents, surfactants, alkalinity sources, enzymes, thickeners (in the case of liquid, paste, cream or gel compositions) and disrupting and binding agents (in the case of powder, granules or tablets). Highly preferred detergent components include a builder compound, an alkalinity source, a surfactant, an enzyme and a bleaching agent.
Unless otherwise specified, the components described hereinbelow can be incorporated either in the organic solvent compositions and/or the detergent or cleaning compositions.
Surfactant
In compositions and methods of the present invention for use in automatic dishwashing the detergent surfactant is preferably low foaming by itself or in combination with other components (i.e. suds suppressers). In compositions and methods of the present invention for use in hard surface cleaning or pretreatment prior to dishwashing, the detergent surfactant is preferably foamable in direct application but low foaming in automatic dishwashing use. Surfactants suitable herein include anionic surfactants such as alkyl sulfates, alkyl ether sulfates, alkyl benzene sulfonates, alkyl glyceryl sulfonates, alkyl and alkenyl sulphonates, alkyl ethoxy carboxylates, N-acyl sarcosinates, N-acyl taurates and alkyl succinates and sulfosuccinates, wherein the alkyl, alkenyl or acyl moiety is C5-C20 , preferably CiQ-Cjg linear or branched; cationic surfactants such as chlorine esters (US-A-4228042, US-A-4239660 and US-A-4260529) and mono C6-C16
N-alkyl or alkenyl ammonium surfactants wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups; low and high cloud point nonionic surfactants and mixtures thereof including nonionic alkoxylated surfactants (especially ethoxylates derived from C6-Cι g primary alcohols), ethoxylated- propoxylated alcohols (e.g., Olin Corporation's Poly-Tergent® SLF18), epoxy-capped poly(oxyalkylated) alcohols (e.g., Olin Corporation's Poly-Tergent® SLF18B - see WO- A-94/22800), ether-capped poly(oxyalkylated) alcohol surfactants, and block polyoxyethylene-polyoxypropylene polymeric compounds such as PLURONIC®, REVERSED PLURONIC®, and TETRONIC® by the BASF-Wyandotte Corp., Wyandotte, Michigan; amphoteric surfactants such as the C12-C20 alkyl amine oxides (preferred amine oxides for use herein include lauryldimethyl amine oxide and hexadecyl dimethyl amine oxide), and alkyl amphocarboxylic surfactants such as Miranol™ C2M; and zwitterionic surfactants such as the betaines and sultaines; and mixtures thereof. Surfactants suitable herein are disclosed, for example, in US- A-3, 929,678 , US-A- 4,259,217, EP-A-0414 549, WO-A-93/08876 and WO-A-93/08874. Surfactants are typically present at a level of from about 0.2% to about 30% by weight, more preferably from about 0.5% to about 10%> by weight, most preferably from about 1%> to about 5% by weight of composition. Preferred surfactant for use herein are low foaming and include low cloud point nonionic surfactants and mixtures of higher foaming surfactants with low cloud point nonionic surfactants which act as suds suppresser therefor.
Builder
Builders suitable for use in detergent and cleaning compositions herein include water- soluble builders such as citrates, carbonates and polyphosphates e.g. sodium tripolyphosphate and sodium tripolyphosphate hexahydrate, potassium tripolyphosphate and mixed sodium and potassium tripolyphosphate salts; and partially water-soluble or insoluble builders such as crystalline layered silicates (EP-A-0164514 and EP-A- 0293640) and aluminosilicates inclusive of Zeolites A, B, P, X, HS and MAP. The builder is typically present at a level of from about 1% to about 80%> by weight, preferably from about 10% to about 70% by weight, most preferably from about 20% to about 60%) by weight of composition.
Amo hous sodium silicates having an SiO2:Na2O ratio of from 1.8 to 3.0, preferably from 1.8 to 2.4, most preferably 2.0 can also be used herein although highly preferred from the viewpoint of long term storage stability are compositions containing less than about 22%, preferably less than about 15% total (amorphous and crystalline) silicate.
Enzyme
Enzymes suitable herein include bacterial and fungal cellulases such as Carezyme and Celluzyme (Novo Nordisk A/S); peroxidases; lipases such as Amano-P (Amano Pharmaceutical Co.), Ml LipaseR and LipomaxR (Gist-Brocades) and LipolaseR and Lipolase UltraR (Novo); cutinases; proteases such as EsperaseR, AlcalaseR, DurazymR and SavinaseR (Novo) and MaxataseR, MaxacalR, ProperaseR and MaxapemR (Gist-Brocades); and and β amylases such as Purafect Ox AmR (Genencor) and TermamylR, BanR, FungamylR, DuramylR, and NatalaseR (Novo); and mixtures thereof. Enzymes are preferably added herein as prills, granulates, or cogranulates at levels typically in the range from about 0.0001% to about 2%> pure enzyme by weight of composition.
Bleaching agent
Bleaching agents suitable herein include chlorine and oxygen bleaches, especially inorganic perhydrate salts such as sodium perborate mono-and tetrahydrates and sodium percarbonate optionally coated to provide controlled rate of release (see, for example, GB-A- 1466799 on sulfate/carbonate coatings), preformed organic peroxyacids and mixtures thereof with organic peroxyacid bleach precursors and or transition metal- containing bleach catalysts (especially manganese or cobalt). Inorganic perhydrate salts are typically incorporated at levels in the range from about 1% to about 40% by weight, preferably from about 2% to about 30% by weight and more preferably from abut 5% to about 25% by weight of composition. Peroxyacid bleach precursors preferred for use herein include precursors of perbenzoic acid and substituted perbenzoic acid; cationic peroxyacid precursors; peracetic acid precursors such as TAED, sodium acetoxybenzene sulfonate and pentaacetylglucose; pernonanoic acid precursors such as sodium 3,5,5- trimethylhexanoyloxybenzene sulfonate (iso-NOBS) and sodium nonanoyloxybenzene sulfonate (NOBS); amide substituted alkyl peroxyacid precursors (EP-A-0170386); and benzoxazin peroxyacid precursors (EP-A-0332294 and EP-A-0482807). Bleach precursors are typically incorporated at levels in the range from about 0.5% to about 25%, preferably from about 1% to about 10% by weight of composition while the preformed organic peroxyacids themselves are typically incorporated at levels in the range from 0.5% to 25% by weight, more preferably from 1% to 10% by weight of composition. Bleach catalysts preferred for use herein include the manganese triazacyclononane and related complexes (US-A-4246612, US-A-5227084); Co, Cu, Mn and Fe bispyridylamine and related complexes (US-A-5114611); and pentamine acetate cobalt(III) and related complexes(US-A-4810410).
Low cloud point non-ionic surfactants and suds suppressers
The suds suppressers suitable for use herein include nonionic surfactants having a low cloud point. "Cloud point", as used herein, is a well known property of nonionic surfactants which is the result of the surfactant becoming less soluble with increasing temperature, the temperature at which the appearance of a second phase is observable is referred to as the "cloud point" (See Kirk Othmer, pp. 360-362). As used herein, a "low cloud point" nonionic surfactant is defined as a nonionic surfactant system ingredient having a cloud point of less than 30° C, preferably less than about 20° C, and even more preferably less than about 10° C, and most preferably less than about 7.5° C. Typical low cloud point nonionic surfactants include nonionic alkoxylated surfactants, especially ethoxylates derived from primary alcohol, and polyoxypropylene/polyoxyethylene/polyoxypropylene (PO/EO/PO) reverse block polymers. Also, such low cloud point nonionic surfactants include, for example, ethoxylated-propoxylated alcohol (e.g., Olin Corporation's Poly-Tergent® SLF18) and epoxy-capped poly(oxyalkylated) alcohols (e.g., Olin Corporation's Poly-Tergent® SLF18B series of nonionics, as described, for example, in US-A-5,576,281).
Preferred low cloud point surfactants are the ether-capped poly(oxyalkylated) suds suppresser having the formula:
R1O-(CH2 -CH -O)x- (CH2 -CH2 -O)y - (CH2 - CH— O)z— H i L
R2 R3
wherein R! is a linear, alkyl hydrocarbon having an average of from about 7 to about 12 carbon atoms, R2 is a linear, alkyl hydrocarbon of about 1 to about 4 carbon atoms, R3 is a linear, alkyl hydrocarbon of about 1 to about 4 carbon atoms, x is an integer of about 1 to about 6, y is an integer of about 4 to about 15, and z is an integer of about 4 to about 25.
Other low cloud point nonionic surfactants are the ether-capped poly(oxyalkylated) having the formula:
RIO(RIIO)nCH(CH3)ORIII wherein, Rr is selected from the group consisting of linear or branched, saturated or unsaturated, substituted or unsubstituted, aliphatic or aromatic hydrocarbon radicals having from about 7 to about 12 carbon atoms; R„ may be the same or different, and is independently selected from the group consisting of branched or linear C2 to C7 alkylene in any given molecule; n is a number from 1 to about 30; and Rm is selected from the group consisting of:
(i) a 4 to 8 membered substituted, or unsubstituted heterocyclic ring containing from 1 to 3 hetero atoms; and
(ii) linear or branched, saturated or unsaturated, substituted or unsubstituted, cyclic or acyclic, aliphatic or aromatic hydrocarbon radicals having from about 1 to about 30 carbon atoms;
(b) provided that when R2 is (ii) then either: (A) at least one of R1 is other than C2 to C3 alkylene; or (B) R2 has from 6 to 30 carbon atoms, and with the further proviso that when R2 has from 8 to 18 carbon atoms, R is other than C, to C5 alkyl.
Other suitable components herein include organic polymers having dispersant, anti- redeposition, soil release or other detergency properties invention in levels of from about 0.1% to about 30%, preferably from about 0.5% to about 15%>, most preferably from about 1%) to about 10% by weight of composition. Preferred anti-redeposition polymers herein include acrylic acid containing polymers such as Sokalan PA30, PA20, PA15, PA10 and Sokalan CP10 (BASF GmbH), Acusol 45N, 480N, 460N (Rohm and Haas), acrylic acid/maleic acid copolymers such as Sokalan CP5 and acrylic/methacrylic copolymers. Preferred soil release polymers herein include alkyl and hydroxyalkyl celluloses (US-A-4,000,093), polyoxyethylenes, polyoxypropylenes and copolymers thereof, and nonionic and anionic polymers based on terephthalate esters of ethylene glycol, propylene glycol and mixtures thereof.
Heavy metal sequestrants and crystal growth inhibitors are suitable for use herein in levels generally from about 0.005% to about 20%, preferably from about 0.1% to about 10%, more preferably from about 0.25%> to about 7.5% and most preferably from about 0.5% to about 5% by weight of composition, for example diethylenetriamine penta (methylene phosphonate), ethylenediamine tetra(methylene phosphonate) hexamethylenediamine tetra(methylene phosphonate), ethylene diphosphonate, hydroxy- ethylene- 1 , 1 -diphosphonate, nitrilotriacetate, ethylenediaminotetracetate, ethylenediamine-N,N'-disuccinate in their salt and free acid forms.
The compositions herein can contain a corrosion inhibitor such as organic silver coating agents in levels of from about 0.05% to about 10%>, preferably from about 0.1% to about 5% by weight of composition (especially paraffins such as Winog 70 sold by Wintershall, Salzbergen, Germany), nitrogen-containing corrosion inhibitor compounds (for example benzotriazole and benzimadazole - see GB-A-1137741) and Mn(II) compounds, particularly Mn(II) salts of organic ligands in levels of from about 0.005% to about 5%, preferably from about 0.01%> to about 1%, more preferably from about 0.02%> to about 0.4% by weight of the composition. Other suitable components herein include colorants, water-soluble bismuth compounds such as bismuth acetate and bismuth citrate at levels of from about 0.01%> to about 5%, enzyme stabilizers such as calcium ion, boric acid, propylene glycol and chlorine bleach scavengers at levels of from about 0.01% to about 6%, lime soap dispersants (see WO-A- 93/08877), suds suppressors (see WO-93/08876 and EP-A-0705324), polymeric dye transfer inhibiting agents, optical brighteners, perfumes, fillers and clay.
Liquid detergent compositions can contain water and other volatile solvents as carriers. Low quantities of low molecular weight primary or secondary alcohols such as methanol, ethanol, propanol and isopropanol can be used in the liquid detergent of the present invention. Other suitable carrier solvents used in low quantities includes glycerol, propylene glycol, ethylene glycol, 1,2-propanediol, sorbitol and mixtures thereof.
Examples
Abbreviations used in Examples
In the examples, the abbreviated component identifications have the following meanings:
Carbonate Anhydrous sodium carbonate STPP Sodium tripolyphosphate SKTP Sodium potassium tripolyphosphate Silicate 3.2 Amorphous Sodium Silicate (SiO2:Na2O ratio = 3:2)
Silicate Amorphous Sodium Silicate (Siθ2:Na2θ ratio = 2.0)
SKS-6 Crystalline layered silicate of formula δ-Na2Si2θ5
KOH Potassium hydroxide
H2SO4 Sulphuric acid
HEDP Ethane l-hydroxy-l,l-diphosphonic acid PB1 Sodium perborate monohydrate average particle size
770 μm
PB1-50 Sodium perborate monohydrate average particle size 50 μm
Termamyl α-amylase available from Novo Nordisk A/S
FN3 protease available from Genencor
Savinase protease available from Novo Nordisk A/S
LF404 low foaming surfactant available from Olin Corporation
SLF18 low foaming surfactant available from Olin Corporation
ACNI alkyl capped non-ionic surfactant of formula C9/π Hι9/23
EO8-cyclohexyl acetal
C16AO hexadecyl dimethyl amine oxide PA30 Polyacrylate homo-polymer of molecular weight approximately 8,000 available from BASF
Proxel GXL preservative(l,2-benzisothiazolin-3-one) available from
Zeneca, Inc
Polygel premix 5% active Polygel DKP in water available from 3V Inc.
CaC12 Calcium chlorine
CHDM Cyclohexane dimethanol
BTA Benzotriazole
Winog Paraffin oil sold by Wintershall.
Vivapur Microcrystalline cellulose of average particle size 0.18 mm
Triacetate Sodium acetate trihydrate Duramyl α-amylase available from Novo Nordisk A/S Sulphate Anhydrous sodium sulphate. Citric Acid Anhydrous Citric acid Bicarbonate Sodium hydrogen carbonate PEG 400 Polyethylene Glycol molecular weight approximately
400 available from Hoechst PEG 4000 Polyethylene Glycol molecular weight approximately
4000 available from Hoechst
PVPVI Polyvinylpyrrolidone vinylimidazole copolymer molecular weight approximately 15,000 available from
BASF
MEA Monoethanolamine MAE 2-(methylamino)ethanol SF1488 Polydimethylsiloxane copolymer Dowanol PNB Propylene glycol butyl ether
In the following examples all levels are quoted as parts by weight.
Examples 1 to 5 A combination of solvent compositions and automatic dishwashing detergents are used to wash a load of tableware and cookware having cooked-on, baked-on and burnt-on food soils. The load comprises different soils and different substrates: lasagne baked for 2 hours at 140°C on Pyrex, lasagne cooked for 2 hours at 150°C on stainless steel, potato and cheese cooked for 2 hours at 150°C on stainless steel, egg yolk cooked for 2 hours at 150°C on stainless steel and sausage cooked for 1 hour at 120°C followed by 1 hour at 180°C. The load is washed in a 5 litre liquor capacity Bosch 6032 dishwashing machine, at 55°C without prewash, using the compositions given in Examples 1 to 5. Examples 1 to 5 illustrate the use of a combination of a two-phase automatic dishwashing detergent tablet and an organic solvent composition added separately to the main- ash cycle of the dishwashing machine. The two-component compositions of examples 1 to 5 provided excellent removal of cooked-on, baked-on and burnt-on food soils.
Figure imgf000024_0001
Figure imgf000025_0001
Figure imgf000026_0001
Examples 6 to 10
Examples 6 to 10 illustrate the use of a combination of an automatic dishwashing liquid detergent and an organic solvent composition for removing cooked-, baked- and burnt-on soils. The two-component compositions of examples 6 to 10 are used to wash a load of cookware and tableware according to the procedure described hereinabove (Examples 1 to 5). 30 ml of the dishwashing detergent and the 10 ml of the solvent composition are separately delivered to the main-wash cycle of a 5 litre liquor capacity Bosch 6032 dishwashing machine, at 55°C without prewash. The compositions of examples 6 to 10 provide excellent removal of cooked-on, baked-on and burnt-on food soils.
Figure imgf000026_0002
Figure imgf000027_0001
Examples 11 to 15
Examples 11 to 15 further illustrate the use of a combination of an automatic dishwashing liquid detergent and an organic solvent composition for removing cooked-, baked- and burnt-on soils. The two-component compositions of examples 11 to 15 are used to wash a load of cookware and tableware according to the procedure described hereinabove (Examples 1 to 5). The automatic dishwashing liquid detergent and the organic solvent composition are delivered in separate compartments of a unit dose (30 ml of the dishwashing detergent and the 10 ml of the solvent composition) partially hydrolysed PVA water-soluble pouch. The pouch is delivered to the main-wash cycle of a Bosch 6032 dishwashing machine, at 55°C without prewash. The two-component compositions of examples 11 to 15 provide excellent removal of cooked-on, baked-on and burnt-on food soils. At the same time, they provide excellent compatibility with the PVA pouch material.
Figure imgf000028_0001
Examples 16 to 19 Examples 16 to 19 illustrate the use of a combination of an automatic dishwashing liquid detergent and an organic solvent composition for removing cooked-, baked- and burnt-on soils. The two-component compositions are stored in a dual-compartment bottle having an electrically operated pump and delivered at a feed ratio (dishwashing liquid detergent: organic solvent composition) of 3:1. The compositions of examples 16 to 19 are used to wash a dishware load according to the procedure described hereinabove (Examples 1 to 5). 30 ml of the dishwashing detergent and 10 ml of the solvent composition are separately delivered from the dual-compartment bottle to the main- wash cycle of a Bosch 6032 dishwashing machine, at 55°C without prewash. The two-component compositions of examples 16 to 19 provide excellent removal of cooked-on, baked-on and burnt-on food soils.
Figure imgf000029_0001
Figure imgf000030_0001
Examples 20 to 24
Examples 20 to 24 illustrate "all-in-one" solvent-containing automatic dishwashing detergent compositions. The compositions of examples 20 to 24 are used to wash a dishware load following the procedure described hereinabove (Examples 1 to 5). 40 ml of the dishwashing composition are delivered to the main-wash cycle of a Bosch 6032 dishwashing machine, at 55°C without prewash. The "all-in-one" compositions of examples 20 to 24 provide excellent removal of baked-on soils.
Figure imgf000030_0002
Figure imgf000031_0001
Examples 25 to 28
Examples 25 to 28 illustrate pre-treatment compositions used to facilitate the removal of cooked-on, baked-on and burnt-on food soils prior to the dishwashing process. The compositions of examples 25 to 28 are applied to a dishware load having the soils described hereinabove (Examples 1 to 5). The dishware load is allowed to soak for 10 minutes, then the dishware is rinsed under cold tap water. The dishware load is thereafter washed either manually or in an automatic dishwashing machine, for example in a Bosch 6032 dishwashing machine, at 55°C without prewash, using the dishwashing detergent compositions of examples 1 to 5. The dishware load treated with compositions of examples 25 to 28 and thereafter washed in the dishwashing machines present excellent removal of cooked-on, baked-on and burnt-on food soils.
Figure imgf000031_0002

Claims

Claims:
1. A method of removing cooked-, baked-, or burnt-on food soil from cookware and tableware comprising washing the cookware/tableware in an automatic dishwashing machine in the presence of an organic solvent system having a volatile organic content of less than about 50% by weight and a wash liquor concentration of from about 100 to about 5000 ppm.
2. A method of removing cooked-, baked-, or burnt-on food soil from cookware and tableware comprising washing the cookware/tableware in an automatic dishwashing machine in the presence of surfactant, detergency builder and an organic solvent system having a volatile organic content of less than about 50% by weight, wherein the surfactant, detergency builder and organic solvent system have a wash liquor concentration of from about 10 to about 1000, about 100 to about 5000 and about 100 to about 5000 ppm respectively.
3. A method of removing cooked-, baked-, or burnt-on food soil from cookware and tableware in an automatic dishwashing machine comprising delivering an organic solvent composition in the pre-wash cycle of an automatic dishwashing machine and thereafter delivering an automatic dishwashing detergent composition in the main- wash cycle of the automatic dishwashing machine.
4. A method of removing cooked-, baked-, or burnt-on food soil from cookware and tableware in an automatic dishwashing machine comprising delivering an organic solvent composition and a first automatic dishwashing detergent composition in the pre-wash cycle of an automatic dishwashing machine and thereafter delivering a second automatic dishwashing detergent composition in the main-wash cycle of the automatic dishwashing machine.
5. A method of removing cooked-, baked-, or burnt-on food soil from cookware and tableware in an automatic dishwashing machine comprising delivering an organic solvent composition and an automatic dishwashing detergent composition in the main- wash cycle of an automatic dishwashing machine.
6. A method of removing cooked-, baked-, or burnt-on food soil from cookware and tableware in an automatic dishwashing machine comprising delivering an organic solvent composition and an automatic dishwashing detergent composition in the prewash and thereafter in the main- wash cycle of an automatic dishwashing machine.
7. A method of removing cooked-, baked-, or burnt-on food soil from cookware and tableware comprising washing the cookware/tableware in the pre-wash cycle of an automatic dishwashing machine in the presence of an organic solvent composition and thereafter rinsing the cookware/tableware in the rinse cycle of the automatic dishwashing machine in the presence of an automatic dishwashing rinse composition.
8. A method of removing cooked-, baked-, or burnt-on food soil from cookware and tableware comprising delivering an organic solvent composition and an automatic dishwashing detergent composition from separate storage means into the same cycle of an automatic dishwashing machine wherein the wash liquor concentration of organic solvent is in the range from about 100 to about 5000 ppm.
9. A method of washing cookware/tableware comprising delivering one or both of an organic solvent composition and an automatic dishwashing detergent composition contained in separate zones of a multi-zone storage means into the same or different cycles of an automatic dishwashing machine.
10. A method according to claim 9 for the removal of cooked-, baked-, or burnt-on food soil, the method comprising simultaneously delivering the organic solvent composition and automatic dishwashing detergent composition into the main wash cycle of the automatic dishwashing machine at a feed ratio (solvent composition: detergent composition) in the range from about 5:1 to about 1:50 to provide a wash liquor concentration of organic solvent in the range from about 100 to about 5000 ppm.
11. A method according to claim 9 for the removal of cooked-, baked-, or burnt-on food soil, the method comprising sequentially delivering the organic solvent composition and automatic dishwashing detergent composition into the pre-wash and main-wash cycles respectively.
12. A method according to claim 9 wherein the multi-zone storage means is a multi- compartment container and wherein the physical form of the organic solvent composition and/or automatic dishwashing detergent compositions is such as to prevent intimate mixing of the compositions prior to contact thereof with the wash liquor.
13. A method of removing cooked-, baked-, or burnt-on food soil from cookware and tableware comprising delivering separate portions of a multi-phase detergent composition into the same or different cycles of an automatic dishwashing machine, wherein the multi-phase detergent composition comprises at least a first phase containing an organic solvent composition and at least a second phase containing an automatic dishwashing detergent composition.
14. A method of removing cooked-, baked-, or burnt-on food soil from cookware and tableware comprising delivering a plurality of organic solvent compositions of different solvent characteristics into the same or different cycles of an automatic dishwashing machine.
15. A method according to claim 14 comprising delivering a first organic solvent composition into the pre-wash cycle of the automatic dishwashing machine and a second organic solvent composition into the main wash cycle of the automatic dishwashing machine, and wherein the first and second organic solvent compositions have differing soil and/or substrate specificities.
16. A method according to claim 14 or 15 comprising delivering a first organic solvent composition and a first automatic dishwashing detergent composition in the pre-wash cycle and a second solvent composition and a second automatic dishwashing detergent composition in the main- wash cycle of the automatic dishwashing machine.
17. A method of removing cooked-, baked-, or burnt-on food soil from cookware and tableware comprising washing the cookware/tableware in an automatic dishwashing machine in the presence of an organic solvent composition and wherein the organic solvent composition is in a unit dose form adapted to provide controlled release of organic solvent during one or more repeated washing cycles.
18. A method of removing cooked-, baked-, or burnt-on food soil from cookware and tableware comprising washing the cookware/tableware in an automatic dishwashing machine with an automatic dishwashing detergent composition comprising surfactant
(preferably comprising low-foaming nonionic surfactant), detergency builder and organic solvent system in levels sufficient to provide a wash liquor concentration of from about 10 ppm to about 1000 ppm surfactant, from about 100 ppm to about 5000 ppm detergency builder, and about 100 ppm to about 10,000, preferably from about 200 ppm to about 5000 ppm of organic solvent.
19. A method according to any preceding claim wherein the organic solvent composition is in the form of a liquid, paste, cream or gel which is optionally encapsulated, packaged in a single- or multi-compartment pouch, or absorbed onto a porous carrier material.
20. A method according to any preceding claim wherein the organic solvent system has a liquid surface tension of less than about 27 mN/m, preferably less than about 25 mN/m, or wherein the organic solvent system comprises a plurality of solvent components in levels such that the solvent system has a surface tension less than, and preferably at least 1 mN/m less than that of any of the individual solvent components.
21. A method according to any preceding claim wherein the composition comprising the organic solvent composition has an advancing contact angle on a polymerised grease- coated glass substrate of less than 20°, preferably less than 10° and more preferably less than 5°, and for mixed solvent systems is less than the advancing contact angle of any of the corresponding compositions containing the individual components of the solvent system.
22. A method of removing cooked-, baked-, or burnt-on food soil from cookware and tableware comprising treating the cookware/tableware with a hard surface cleaning composition comprising an organic solvent system having a liquid surface tension of less than about 27 mN/m.
23. A method according to claim 22 comprising the step of pre-treating the cookware/tableware with the hard surface cleaning composition prior to manual or automatic dishwashing.
24. A method according to any preceding claim wherein the organic solvent system is selected from alcohols, amines, esters, glycol ethers, glycols, terpenes and mixtures thereof.
25. A method according to any preceding claim wherein the organic solvent system is selected from organoamine solvents, inclusive of alkanolamines, alkylamines, alkyleneamines and mixtures thereof; alcoholic solvents inclusive of aromatic, aliphatic (preferably C4-C10) and cycloaliphatic alcohols and mixtures thereof; glycols and glycol derivatives inclusive of C2-C3 (poly)alkylene glycols, glycol ethers, glycol esters and mixtures thereof; and mixtures selected from organoamine solvents, alcoholic solvents, glycols and glycol derivatives.
26. A method according to claim 24 or 25 wherein the organic solvent comprises organoamine (especially alkanolamine) solvent and glycol ether solvent, preferably in a weight ratio of from about 3:1 to about 1:3, and wherein the glycol ether solvent is selected from ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, ethylene glycol phenyl ether and mixtures thereof.
27. A method according to any of claims 24 to 26 wherein the glycol ether is a mixture of diethylene glycol monobutyl ether and propylene glycol butyl ether, preferably in a weight ratio of from about 1:2 to about 2:1.
28. A method according to any of claims 24 to 27 wherein the organic solvent system comprises an organoamine solvent having a pKa of at least 8.8, preferably at least 9.3, more preferably at least 9.8.
29. A method according to any of claims 24 to 28 wherein the organic solvent system comprises a mixture of a first organoamine solvent having a pKa of 9.5 or less and a second organoamine solvent having a pKa greater than 9.5.
30. A method according to any of claims 24 to 29 wherein the organic solvent comprises one or more organoamines which is/are introduced into the wash liquor of an automatic dishwashing machine in the form their ammonium salt at a wash liquor pH above the highest pKa of the organoamine/s.
31. A method according to any preceding claim wherein the organic solvent system is used in conjunction with a wetting agent effective in lowering the surface tension of the solvent system, the wetting agent preferably being selected from organic surfactants having a surface tension less than about 30 mN/m, preferably less than about 28 mN/m, more preferably less than about 26 mN/m.
32. A method according to claim 31 wherein the wetting agent is selected from silicone polyether copolymers, especially silicone-poly(alkyleneoxide) copolymers.
33. A method according to any preceding claim wherein the organic solvent is essentially free of solvent components having a boiling point below about 150°C, flash point below about 100°C or vapor pressure above about 1 mm Hg.
34. A method according to any preceding claim wherein the organic solvent is selected from: a) polar, hydrogen-bonding solvents having a Hansen solubility parameter of at least 20 (Mpa)1 2, a polarity parameter of at least 7 (Mpa)1/2, preferably at least 12 (Mpa)1/2 and a hydrogen bonding parameter of at least 10 (Mpa)1/2 b) polar non-hydrogen bonding solvents having a Hansen solubility parameter parameter of at least 20 (Mpa)1 2, a polarity parameter of at least 7 (Mpa)1 2, preferably at least 12
(Mpa)1 2 and a hydrogen bonding parameter of less than 10 (Mpa)1/2 c) amphiphilic solvents having a Hansen solubility parameter below 20 (Mpa)1 2, a polarity parameter of at least 7 (Mpa)1 2 and a hydrogen bonding parameter of at least 10 (Mpa)1/2 d) non-polar solvents having a polarity parameter below 7 (Mpa)1 2 and a hydrogen bonding parameter below 10 (Mpa)1/2 and e) mixtures thereof.
35. An automatic dishwashing detergent pack comprising two or more automatic dishwashing detergent or auxiliary products, storage means comprising separate but associated portions of the two or more products and means for delivering quantities of the two or more products into the same or different cycles of an automatic dishwashing machine.
36. An automatic dishwashing detergent pack comprising two or more automatic dishwashing detergent or auxiliary products, storage means comprising separate but associated portions of the two or more products, means for dispensing quantities of the two or more products, and means for controlling the relative dispensing rate of the two or more products from the storage means.
37. A pack according to claim 35 or 36 comprising an organic solvent composition and an automatic dishwashing detergent composition.
38. A pack according to any of claims 35 to 37 wherein the two or more automatic dishwashing detergent or auxiliary products are in rheology-matched gel-form.
39. A pack according to any of claims 35 to 38 for use in the method according to any of claims 1 to 34.
40. An organic solvent composition suitable for use in automatic dishwashing comprising from about 1% to about 99%>, preferably from about 5%> to about 90%, especially from about 40%> to about 80% of an organic solvent system for removing cooked-, baked-, or burnt-on food soil from cookware and tableware, from about 0.5% to about 50%, preferably from about 5%> to about 25% of bleach, from about 0.000 l%o to about 10%> of detergency enzyme, and wherein the composition is in the form of an anhydrous gel comprising bleach in the form of a particulate suspension.
41. An automatic dishwashing detergent composition comprising from about 0.05% to about 10%) by weight of a low-foaming non-ionic surfactant, from about 1% to about 30% of an organoamine, preferably alkanolamine solvent and at least about 5% by weight of a detergency builder.
42. An automatic dishwashing detergent composition in the form of a gel comprising from about 2% to about 20%, preferably from about 5%> to about 15% by weight of the composition of an alkanolamine, at least about 5% by weight of detergency builder, and from about 0.1% to about 5% by weight of the composition of a low foaming nonionic surfactant.
43. An automatic dishwashing detergent composition comprising from about 0.05% to about 10%) by weight of a low-foaming non-ionic surfactant, from about 1% to about 30% of an organic solvent, preferably alkanolamine solvent, at least about 5% by weight of a detergency builder and a wetting agent, preferably a silicone- poly(alkyleneoxide) copolymers.
44. An automatic dishwashing detergent pack according to any of claims 35 to 39 comprising the organic solvent composition of claim 40 and the automatic dishwashing detergent composition of any of claims 41 to 43.
45. A hard-surface cleaning or dishwashing pretreatment composition for removing cooked-, baked-, or burnt-on food soil from cookware and tableware, the composition comprising an organic solvent system having a liquid surface tension of less than about 27 mN/m, preferably less than about 26 mN/m, the composition being in the form of a liquid or gel having a pH of greater than about 10.5, preferably greater than about 11.
46. A hard-surface cleaning or dishwashing pretreatment composition for removing cooked-, baked-, or burnt-on food soil from cookware and tableware, the composition comprising an organic solvent system having an advancing contact angle on polymerised grease-coated glass substrate of less than 20°, preferably less than 10° and more preferably less than 5°.
47. A hard-surface cleaning or dishwashing pretreatment composition for removing cooked-, baked-, or burnt-on food soil from cookware and tableware, the composition comprising an organic solvent system comprising a plurality of solvent components in levels such that the solvent system has an advancing contact angle on polymerised grease-coated glass substrate of less than that of corresponding compositions containing the individual components of the solvent system.
48. A hard-surface cleaning or dishwashing pretreatment composition for removing cooked-, baked-, or burnt-on food soil from cookware and tableware according to any of claims 45 to 47 wherein the composition is in the form of a shear thinning fluid having a shear index from about 0.3 to about 0.7, preferably from about 0.4 to about 0.6 and a consistency index from about 0.20 to about 0.15, preferably from about
0.175 to about 0.160 kg/(m s2"n).
49. A composition according to any of claims 40 to 48, the composition having a volatile organic content above 0.1 mm Hg of less than about 20%>, preferably less than about 10% and more preferably less than about 5% by weight of the composition.
0. Use of an organic solvent system in an automatic dishwashing machine to remove cooked-, baked-, or burnt-on food soil from cookware and tableware.
PCT/US2000/019619 2000-02-17 2000-07-19 Cleaning composition WO2002008370A2 (en)

Priority Applications (102)

Application Number Priority Date Filing Date Title
PCT/US2000/019619 WO2002008370A2 (en) 2000-07-19 2000-07-19 Cleaning composition
PCT/US2000/020255 WO2002008371A2 (en) 2000-02-17 2000-07-25 Cleaning composition
DE60035902T DE60035902T2 (en) 2000-02-17 2000-11-29 WASH PRODUCE
PCT/US2000/032533 WO2001060966A1 (en) 2000-02-17 2000-11-29 Detergent product
AT00980871T ATE369417T1 (en) 2000-02-17 2000-11-29 DETERGENT PRODUCT
MXPA02008065A MXPA02008065A (en) 2000-02-17 2000-11-29 Detergent product.
EP00980871A EP1255807B1 (en) 2000-02-17 2000-11-29 Detergent product
BRPI0017112-3A BR0017112B1 (en) 2000-02-17 2000-11-29 Water soluble bag composition and use of the composition.
CA002397241A CA2397241C (en) 2000-02-17 2000-11-29 Pouched compositions comprising peracid
ES00980871T ES2290059T3 (en) 2000-02-17 2000-11-29 DETERGENT PRODUCT.
AU2001218076A AU2001218076A1 (en) 2000-02-17 2000-11-29 Detergent product
JP2001560338A JP2005507432A (en) 2000-02-17 2000-11-29 Detergent products
CNB008190615A CN1225537C (en) 2000-02-17 2000-11-29 Betengent product
EP00986684A EP1305389B1 (en) 2000-07-19 2000-12-21 Cleaning composition
MXPA03000492A MXPA03000492A (en) 2000-07-19 2000-12-21 Cleaning composition.
PCT/US2000/034907 WO2002008373A1 (en) 2000-07-19 2000-12-21 Cleaning composition
MXPA03000491A MXPA03000491A (en) 2000-07-19 2000-12-21 Cleaning composition.
MXPA03000490A MXPA03000490A (en) 2000-07-19 2000-12-21 Cleaning composition.
DE60044979T DE60044979D1 (en) 2000-07-19 2000-12-21 CLEANING SUPPLIES
AT00988267T ATE395405T1 (en) 2000-07-19 2000-12-21 CLEANING SUPPLIES
AT00986682T ATE481471T1 (en) 2000-07-19 2000-12-21 CLEANING SUPPLIES
ES00986682T ES2352670T3 (en) 2000-07-19 2000-12-21 CLEANING COMPOSITION.
AT00986684T ATE342336T1 (en) 2000-07-19 2000-12-21 CLEANING SUPPLIES
JP2002514259A JP2004515569A (en) 2000-07-19 2000-12-21 Detergent composition
AU2001222875A AU2001222875A1 (en) 2000-07-19 2000-12-21 Cleaning composition
AU2001222876A AU2001222876A1 (en) 2000-07-19 2000-12-21 Detergent pack
CA002414140A CA2414140C (en) 2000-07-19 2000-12-21 Automatic dishwashing method employing an organic solvent system
AU2001222873A AU2001222873A1 (en) 2000-07-19 2000-12-21 Cleaning composition
EP00986683A EP1305383B1 (en) 2000-07-19 2000-12-21 Cleaning composition
MXPA03000493A MXPA03000493A (en) 2000-07-19 2000-12-21 Cleaning composition.
DE60031309T DE60031309T2 (en) 2000-07-19 2000-12-21 CLEANING SUPPLIES
PCT/US2000/034906 WO2002008374A1 (en) 2000-07-19 2000-12-21 Cleaning composition
ES00986684T ES2273742T3 (en) 2000-07-19 2000-12-21 CLEANING COMPOSITION.
AU2001224494A AU2001224494A1 (en) 2000-07-19 2000-12-21 Cleaning composition
EP00988267A EP1305390B1 (en) 2000-07-19 2000-12-21 Cleaning composition
PCT/US2000/034910 WO2002008509A1 (en) 2000-07-19 2000-12-21 Detergent pack
EP00986682A EP1305388B1 (en) 2000-07-19 2000-12-21 Cleaning composition
ES00988267T ES2306676T3 (en) 2000-07-19 2000-12-21 CLEANING COMPOSITION.
CA002414133A CA2414133C (en) 2000-07-19 2000-12-21 Automatic dishwashing method employing an organic solvent system
AT00986683T ATE455836T1 (en) 2000-07-19 2000-12-21 CLEANING SUPPLIES
CA002416326A CA2416326A1 (en) 2000-07-19 2000-12-21 Low surface tension, alkaline hard surface cleaner comprising a soil welling agent and a spreading auxiliary
DE60043751T DE60043751D1 (en) 2000-07-19 2000-12-21 CLEANING SUPPLIES
DE60038906T DE60038906D1 (en) 2000-07-19 2000-12-21 CLEANING SUPPLIES
CA002416327A CA2416327C (en) 2000-07-19 2000-12-21 Low surface tension, alkaline hard surface cleaner containing an organoamine
AU2001222874A AU2001222874A1 (en) 2000-07-19 2000-12-21 Cleaning composition
JP2002513861A JP2004509175A (en) 2000-07-19 2000-12-21 Detergent composition
JP2002514258A JP3962327B2 (en) 2000-07-19 2000-12-21 Detergency composition
PCT/US2000/034909 WO2002008376A1 (en) 2000-07-19 2000-12-21 Cleaning composition
PCT/US2000/034908 WO2002008375A1 (en) 2000-07-19 2000-12-21 Cleaning composition
ES00986683T ES2339420T3 (en) 2000-07-19 2000-12-21 CLEANING COMPOSITION.
JP2002514260A JP2004509176A (en) 2000-07-19 2000-12-21 Detergent composition
CN01805165A CN1401030A (en) 2000-02-17 2001-02-13 Laundry additive sachet
MXPA02008067A MXPA02008067A (en) 2000-02-17 2001-02-13 Laundry additive sachet.
BR0108441-0A BR0108441A (en) 2000-02-17 2001-02-13 Additive laundry sachet
AU2001238240A AU2001238240A1 (en) 2000-02-17 2001-02-13 Laundry additive sachet
PCT/US2001/004694 WO2001061099A1 (en) 2000-02-17 2001-02-13 Laundry additive sachet
CA002396931A CA2396931A1 (en) 2000-02-17 2001-02-13 Laundry additive sachet
EP01910655A EP1255887A2 (en) 2000-02-17 2001-02-13 Laundry additive sachet
JP2001559930A JP5000060B2 (en) 2000-02-17 2001-02-13 Laundry additive pouch
US10/204,259 US7351683B2 (en) 2000-02-17 2001-02-13 Laundry additive sachet
ARP010100705A AR028508A1 (en) 2000-02-17 2001-02-16 ADDITIVE SACHET FOR LAUNDRY WASHING AND PROCESS TO TREAT FABRICS USING SACHET.
ARP010100706A AR035167A1 (en) 2000-02-17 2001-02-16 DETERGENT PRODUCT
US09/906,491 US6750187B2 (en) 2000-07-19 2001-07-16 Cleaning composition
US09/906,480 US6740628B2 (en) 2000-07-19 2001-07-16 Cleaning composition
US09/906,295 US20020142931A1 (en) 2000-07-19 2001-07-16 Gel form automatic dishwashing compositions, methods of preparation and use thereof
US09/906,479 US6557732B2 (en) 2000-07-19 2001-07-16 Detergent pack
CA002415302A CA2415302A1 (en) 2000-07-19 2001-07-18 Hard surface cleaning composition comprising soil swelling agent and thickening system
AU2001280606A AU2001280606A1 (en) 2000-07-19 2001-07-18 Gel form automatic dishwashing compositions, methods of preparation and use thereof
MXPA03000488A MXPA03000488A (en) 2000-07-19 2001-07-18 Gel form automatic dishwashing compositions, methods of preparation and use thereof.
AT01959008T ATE350453T1 (en) 2000-07-19 2001-07-18 CLEANING SUPPLIES
MXPA03000487A MXPA03000487A (en) 2000-07-19 2001-07-18 Cleaning compositions.
AU2001280605A AU2001280605A1 (en) 2000-07-19 2001-07-18 Cleaning compositions
EP01959009A EP1305394A1 (en) 2000-07-19 2001-07-18 Gel form automatic dishwashing compositions, methods of preparation and use thereof
PCT/US2001/022708 WO2002006437A1 (en) 2000-07-19 2001-07-18 Cleaning compositions
AU2001280607A AU2001280607A1 (en) 2000-07-19 2001-07-18 Cleaning compositions
JP2002512332A JP2004506749A (en) 2000-07-19 2001-07-18 Gelled automatic dishwashing compositions, their preparation method and their use
AT01959010T ATE278764T1 (en) 2000-07-19 2001-07-18 CLEANING AGENT COMPOSITIONS
EP04023010A EP1493803B1 (en) 2000-07-19 2001-07-18 Cleaning compositions
DE60106272T DE60106272T2 (en) 2000-07-19 2001-07-18 CLEANING COMPOSITIONS
JP2002512331A JP4185360B2 (en) 2000-07-19 2001-07-18 Detergency composition
MXPA03000489A MXPA03000489A (en) 2000-07-19 2001-07-18 Cleaning compositions.
ES01959010T ES2225589T3 (en) 2000-07-19 2001-07-18 CLEANING COMPOSITIONS.
AT04023010T ATE328996T1 (en) 2000-07-19 2001-07-18 CLEANING AGENT COMPOSITIONS
JP2002512330A JP2004519527A (en) 2000-07-19 2001-07-18 Detergent composition
PCT/US2001/022706 WO2002006436A1 (en) 2000-07-19 2001-07-18 Cleaning compositions
PCT/US2001/022707 WO2002006438A1 (en) 2000-07-19 2001-07-18 Gel form automatic dishwashing compositions, methods of preparation and use thereof
CA002415308A CA2415308A1 (en) 2000-07-19 2001-07-18 A hard-surface cleaning composition comprising an odor masking perfume
DE60125775T DE60125775T2 (en) 2000-07-19 2001-07-18 CLEANING SUPPLIES
ES04023010T ES2265133T3 (en) 2000-07-19 2001-07-18 CLEANING COMPOSITIONS.
CA002415304A CA2415304A1 (en) 2000-07-19 2001-07-18 Gel form automatic dishwashing compositions, methods of preparation and use thereof
DE60120517T DE60120517T2 (en) 2000-07-19 2001-07-18 Detergent compositions
EP01959010A EP1305392B1 (en) 2000-07-19 2001-07-18 Cleaning compositions
EP01959008A EP1305391B1 (en) 2000-07-19 2001-07-18 Cleaning compositions
ES01959008T ES2280389T3 (en) 2000-07-19 2001-07-18 CLEANING COMPOSITIONS.
US09/910,281 US20020037822A1 (en) 2000-07-19 2001-07-19 Cleaning composition
US09/909,403 US6683036B2 (en) 2000-07-19 2001-07-19 Cleaning composition
US09/909,233 US20020037817A1 (en) 2000-07-19 2001-07-19 Cleaning composition
US10/764,931 US20040157763A1 (en) 2000-07-19 2004-01-26 Cleaning composition
US11/151,027 US20050233925A1 (en) 2000-07-19 2005-06-13 Cleaning composition
US11/192,563 US7304023B2 (en) 2000-02-17 2005-07-29 Detergent product
US11/212,221 US7229955B2 (en) 2000-02-17 2005-08-26 Detergent product
JP2012238209A JP2013067802A (en) 2000-02-17 2012-10-29 Detergent product

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PCT/US2000/034907 WO2002008373A1 (en) 2000-07-19 2000-12-21 Cleaning composition
PCT/US2000/034906 WO2002008374A1 (en) 2000-07-19 2000-12-21 Cleaning composition
PCT/US2000/034908 WO2002008375A1 (en) 2000-07-19 2000-12-21 Cleaning composition
PCT/US2000/034910 WO2002008509A1 (en) 2000-07-19 2000-12-21 Detergent pack
PCT/US2000/034909 WO2002008376A1 (en) 2000-07-19 2000-12-21 Cleaning composition

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PCT/US2000/034908 WO2002008375A1 (en) 2000-07-19 2000-12-21 Cleaning composition
PCT/US2000/034910 WO2002008509A1 (en) 2000-07-19 2000-12-21 Detergent pack
PCT/US2000/034909 WO2002008376A1 (en) 2000-07-19 2000-12-21 Cleaning composition

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EP (5) EP1305389B1 (en)
JP (4) JP2004509176A (en)
AT (4) ATE455836T1 (en)
AU (5) AU2001222875A1 (en)
CA (4) CA2414133C (en)
DE (1) DE60031309T2 (en)
ES (6) ES2352670T3 (en)
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US8367599B2 (en) * 2001-03-16 2013-02-05 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Dishwashing composition with particles
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