EP1497404A2 - Elimination de coloration tenace de moisissure - Google Patents

Elimination de coloration tenace de moisissure

Info

Publication number
EP1497404A2
EP1497404A2 EP03746071A EP03746071A EP1497404A2 EP 1497404 A2 EP1497404 A2 EP 1497404A2 EP 03746071 A EP03746071 A EP 03746071A EP 03746071 A EP03746071 A EP 03746071A EP 1497404 A2 EP1497404 A2 EP 1497404A2
Authority
EP
European Patent Office
Prior art keywords
solution
hypochlorite
foam
cleaning composition
range
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP03746071A
Other languages
German (de)
English (en)
Other versions
EP1497404A4 (fr
Inventor
Munzer Makansi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
KLING 'N KLEEN PRODUCTS Inc
Original Assignee
Fiber Engineering Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fiber Engineering Inc filed Critical Fiber Engineering Inc
Priority claimed from PCT/US2003/009641 external-priority patent/WO2003085073A2/fr
Publication of EP1497404A2 publication Critical patent/EP1497404A2/fr
Publication of EP1497404A4 publication Critical patent/EP1497404A4/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/75—Amino oxides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0094—Process for making liquid detergent compositions, e.g. slurries, pastes or gels
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/044—Hydroxides or bases
    • 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
    • C11D3/395—Bleaching agents
    • C11D3/3956—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
    • C11D9/00—Compositions of detergents based essentially on soap
    • C11D9/04—Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/06—Inorganic compounds
    • C11D9/08—Water-soluble 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
    • C11D9/00—Compositions of detergents based essentially on soap
    • C11D9/04—Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
    • C11D9/42—Per-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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/40—Specific cleaning or washing processes
    • C11D2111/42—Application of foam or a temporary coating on the surface to be cleaned

Definitions

  • This invention relates to a cleaning composition for removing stubborn mildew and other mycological stains from surfaces, the cleaning composition comprising m aqueous solution of an alkali metal hypochlorite, an alkaline builder, and a hypochJorite-compatible surfactant. More particularly, the invention concerns such a cleaning composition which is Stud foam having a particular combination of characteristics and a process for preparing the cleaning composition fluid foam.
  • aqueous miidew-re oving products are available commercially for home use.
  • the aqueous products contain a metal hypochlorite, an alkaline builder for maintaining the aqueous product at a pH of at least 11 , and a surfactant.
  • Such products typically are dispensed from plastic bottles equipped with hand-activated pumps for spraying the cleaner on a surf ⁇ ce.
  • the sprayed cleaning compositions usually are dispensed as liquids, short-lived foams, thickened liquids or gels.
  • thickening agents to increase viscosity and change flow characteristics of aqueous hypochiorite-containing cleaning compositions in order to improve their cleaning ability is disclosed in various patents, as for example in United States Patents 5,549,842 (Chang), 4,900,467 (Smith), 4,800,036 (Rose et al), and 4,337,163 (Schi ⁇ p).
  • the thickened liquids usually are disclosed for use as detergents in dish washers, sink drains and laundry washers, and some are also suggested for removing mildew.
  • Additives for stabilizing aqueous hypochlorite solutions against decomposition caused by temperature and oilier aging effects during storage are known.
  • United States Patent 4,071,463 (Steinhauer) discloses for use as an alkali metal hypochlorite stabilizer, certain synthetic detergents (e.g., alkali metal alkyl sulfates and alkyl aryl sulfonates) and United States Patent 4,898,681 (Burton), discloses calcium chelate of disodium ethylenediaminetetraacetic acid for such stabilizing use.
  • certain synthetic detergents e.g., alkali metal alkyl sulfates and alkyl aryl sulfonates
  • United States Patent 4,898,681 (Burton) discloses calcium chelate of disodium ethylenediaminetetraacetic acid for such stabilizing use.
  • aqueous alkali metal hypochlorite cleaning compositions are useful for removing some mildew stains from surfaces, improvements are desired to greatly increase the cleaning efficiency of mildew stain removal so that scrubbing and/or high-pressure water-hosing normally is not required after the cleaning composition is used on a stained surface.
  • the present invention provides a cleaning composition for removing stubborn mildew from a surface normally without scrubbing.
  • the cleaning composition is of the type that comprises an aqueous solution of an alkali metal hypochlorite, an alkaline builder that maintains the solution at a pH of at least 11, and a hypochlorite-compatible surfactant.
  • the cleaning composition is a fluid foam that has, in combination, as measured by methods described hereinafter, (a) a precursor-solution relative viscosity of no greater than three, preferably in the range of 0.8 to 1.5, (b) a syneresis value in the range of 2 to 40%, preferably in the range of 10 to 30%, (c) a foam horizontal thickness half-life of at least 12 minutes, preferably at least 15 minutes, and (d) a vertical-surface clingability of at least 7 minutes, preferably at least 10 minutes.
  • a preferred alkali metal hypochlorite is sodium hypochlorite which is present in a concentration in the range of 1 to 15 percent, preferably 3 to 10%, by total weight of the aqueous cleaning composition.
  • a preferred alkaline builder is sodium hydroxide or potassium hydroxide.
  • the aqueous solution of alkali metal hypochlorite is free of undesired metal ions.
  • Preferred compatible surfactants are a c ⁇ camine oxide, a sodium alkyl alkanoate and sodium dodecyl diphenyl disulfonate, present in a concentration range of 0.1 to 10%,
  • the invention also provides a method for forming the above-described cleaning composition fluid foam.
  • the method comprises (a) preparing an aqueous solution of an alkali metal hypochlorite, preferably purified of unwanted metal ions, an alkaline builder that maintains the solution at a pH of at least 11, and a hypochlorite-compatible surfactant in a container and (b) vigorously agitating the solution in the presence of a gas with mechanical stirrers Or by fiuidic/pneumatic action of a fluid jet, preferably produced by a mechanical breakup actuator of an aerosol dispenser in the presence of propellant,
  • the foam is produced with a low- boiling hydrocarbon propellant in an aerosol dispenser made of materials compatible with the aqueous solution.
  • Preferred propellants include propane, butane, isobutane and mixtures thereof in a concentration of 1 to 15%, preferably 3 to 10%, by weight of the aqueous cleaning composition.
  • all parts and surfaces that contact the aqueous cleaning composition are of hypochlorite-compatible metal, rubber or plastic.
  • Preferred plastic materials are polyethylene, polypropylene, nylon and polyester.
  • FIG. 1 is a side view of a graduated glass cylinder 10 in which the heights of foam 11 and separated liquid 12 are measured during a "syneresis value" test and wherein h 0 is the original height of the foam in the filled cylinder at the start of the test, and hi and h 2 are respectively the thickness of the separated liquid layer and the thickness of the foam layer at a given time during the test; and
  • FIG. 2 is a schematic representation of an aerosol dispenser suitable for dispensing an aqueous foam of the invention, wherein 20 is a cylindrical container, 21 is a hypochlorite- compatible inner liner of the container, 22 is a similarly lined cover in which is mounted a valve assembly comprising housing 23, gasket 24, spring 25, hollow valve stem 26, button actuator 27, exit nozzle 28, and dip tube 29, and wherein 30 is a mixture of aqueous hypochlorite solution and propellant liquid, 40 is a space filled with propellant vapor, and 50 is a layer of liquid propellant, normally present before the dispenser is shaken prior to use.
  • 20 is a cylindrical container
  • 21 is a hypochlorite- compatible inner liner of the container
  • 22 is a similarly lined cover in which is mounted a valve assembly comprising housing 23, gasket 24, spring 25, hollow valve stem 26, button actuator 27, exit nozzle 28, and dip tube 29, and wherein 30 is a mixture of aqueous hypochlorite solution and propellant liquid
  • 40 is a space filled with propel
  • Mildew refers to any one or combination of mycological stains including household mildew, algae, fungus, spores etc.
  • “Stubborn mildew stain” refers to gray or black mildew which grew on a surface over a long period of time during which the mildew color typically changed from yellow to pink to green and finally to gray and black.
  • “Alkaline builder”, also referred to in the art as an “override substance” is a chemical buffer that maintains an aqueous alkali metal hypochlorite solution at a pH of at least 11 , and helps prevent decomposition of the solution, thereby increasing the shelf life of the solution.
  • “Compatible” means that a particular material or substance being referred to does not substantially adversely affect cleaning efficiency of a fluid foam of the invention or the performance of its dispenser device,
  • Crossability refers to the ability of a foam to cling or adhere to a vertical surface, measured as described herein below.
  • Olemer refers to an electric mixer, usually used in food preparation, but employed herein to prepare fluid foams of various compositions, as reported in the Examples.
  • 'Touched dispenser or “barrier dispenser” refers to a pressurized dispenser in which the aqueous hypochlorite solution is contained inside a pouch made of materials compatible with the solution, the pouch itself being suspended from and sealed to the dispenser valve and not in intimate contact with the inner walls of the dispenser.
  • "Stabilized hypochlorite” or “purified hypochlorite” refers to alkali metal hypochlorite solution from which detrimental impurities, including meal ions such as aluminum, copper and iron, were removed by filtration or by chelation or by other techniques.
  • “Cleanability” refers to a numerical ranking of the degree of whiteness or color shade change that occurs as a result of the application of a cleaning composition to a stained panel, measured as described herein below.
  • Precursor solution refers to the cleaning composition of aqueous solution of alkali metal hypochlorite, alkaline builder, surfactant and optional additives, prior to conversion of the cleaning composition into a fluid foam.
  • “Syneresis value” is a measure of the amount of liquid that separates from a fluid foam, measured as described herein below,
  • “Horizontal thickness half life” is the time interval required for an aqueous foam to lose 50% of its thickness, as measured in the syneresis value test.
  • Actuator with mechanical breakup refers to a known actuator which incorporates a feature to reduce spray particle size (e.g., a circular or near circular swirl chamber, or a channel with several tangential entries).
  • the cleaning effectiveness of different products is tested on a landscaping timber that has stubborn mildew stains distributed over its surface
  • the stained landscaping timber typically measures 240 cm. (8 feet) in length and about 7.2cm. (3-in) by 10.2 cm. (4 inch) in rectangular cross section with rounded edges.
  • Landscaping timbers of this type frequently are found in yard or garden areas around residential homes. When exposed to the environment of a humid climate for a long time (e.g., a few years), the timbers become covered with a layer of a high intensity grey or black, stubborn mycological stains.
  • Such stained timbers are ideal for running a large number of tests to evaluate and compare, side by side, the effectiveness of different mildew removers.
  • a landscaping timber is placed horizontally on the ground with the longer side of its cross section perpendicular to the ground.
  • the timber is then marked with vertical lines to divide the timber into test panels of about 5-cm width.
  • the panels are numbered for identification. Every other panel is used as a test panel on which a sample of the cleaning composition being tested is placed for a predetermined period of time. At the end of the time period, the test panel is rinsed with water.
  • the non-treated stained alternate panels on each side of the test panel serve as controls.
  • the test panels are allowed to dry without scrubbing. Then, the cleanliness of each test panel is measured relative to its adjacent controls by a metliod known as "Gray Scale for Evaluating Changes in Color", referred to as ISO International Standard R105/ ⁇ , Part 2.
  • the difference between the color of the test item and its adjacent controls is matched with the closest contrast between gray color pairs printed on a standard template.
  • the scale on the gray scale template extends from 1 for the largest difference in color contrast to 5 for no visible contrast difference, with fractions in between making a total of 10 gray scale panel pahs .
  • the relative viscosity of an aqueous precursor solution i.e., the aqueous solution of alkali metal hypochlorite, alkaline builder, surfactant and optional additives, prior to conversion into a fluid foam cleaner
  • a simple laboratory apparatus having a vertical arrangement of a right conical plastic funnel with an outlet tube attached and sealed to a plastic capillary tube.
  • the internal diameter of the circular upper end of the funnel is 5.1 cm.
  • the diameter of the circular lower end of the funnel is 0.64 cm.
  • the distance between the upper and lower ends of the conical portion of the funnel is of 4.5 cm.
  • An exit stem extends 2.5 cm from the lower end of the funnel, A 17,8-cm long capillary tube of 0.1-cm internal diameter is inserted 2.0 cm into the end of the funnel stem and sealed thereto.
  • the total capacity of the apparatus from the upper end of the funnel to the outlet end of the capillary tube is 35 cm 3 . All flows through the apparatus are measured at 21°C.
  • To determine the relative viscosity of an aqueous liquid (a) the apparatus is first completely filled with the liquid, (b) the time required for the liquid to flow through the apparatus is measured and (c) the time required for the same volume water to flow through the apparatus is measured.
  • the relative viscosity, RV, of the aqueous liquid is defined as the ratio of t test to t water , where t tes t is the measured time for the test liquid to flow through the apparatus and er is the measured time for water to flow through the apparatus.
  • Relative viscosities at different shear rates are obtained by repeating the procedure with capillaries of different dimensions. The relative viscosities reported herein were measured on precursor solution at a shear rate of 7 sec' 1 .
  • Syneresis Value and Foam Horizontal Thickness Half-life The syneresis value and the horizontal thickness half-life of a fluid foam are measured with a graduated plastic or glass cylinder, as depicted in FIG.l.
  • the cylinder is initially filled completely to its full internal height h» with a cleaning composition foam and the cylinder is placed upright on a horizontal surface.
  • the thickness h 2 of foam layer 11 and the thickness hi of separated liquid layer 12 are measured as functions of time during the test.
  • a graph is prepared of the thickness h 2 of the foam, expressed as a % of the initial foam thickness h 0 , versus time and the horizontal thickness half-life of a cleaning composition fluid foam is determined as the time (measured from the start of the test) at which 100(h 2 / o) equals 50%.
  • a typical cleaning composition is a fluid foam that contains (a) an aqueous solution of an alkali metal hypochlorite, preferably sodium hypochlorite or potassium hypochlorite in a concentration range of 1% to 15% by total weight of the solution; (b) an alkaline builder, preferably sodium hydroxide or potassium hydroxide in a concentration range of 0.01%to 1.0% in excess of amount needed to maintain the aqueous solution at apH of at least 11, (c) a hypochlorite compatible surfactant, in a concentration range of 0.1 to 10%, such as a cocamine oxide, and (d) other optional enhancing agents, such a compatible fragrance, a soap- scum remover, such as tri-sodium phosphate, in a concentration range of l%to 10%, and a hypochlorite stabilizer, such as a chelating agent in a concentration range of 0.005% to 0.25%.
  • an alkaline builder preferably sodium hydroxide or potassium hydro
  • the cleaning composition fluid foam of the invention has a combination of characteristics that provides greatly improved mildew-removing efficiency to the cleaner.
  • the characteristics of the cleaning composition foam are (a) a relative viscosity of the aqueous precursor solution of no greater than 3, preferably 0.8 to 1.5, (b) a foam syneresis value in the range of 2 to 40%, preferably 10 to 30%, (c) a foam horizontal thickness half life of at least 12 minutes, preferably at least 15 minutes, and (d) a foam vertical-surface clingability of at least 7 minutes, preferably at least 10 minutes.
  • the cleaning composition fluid foam of the invention brings into contact with a stained surface substantially larger amounts of stain-removing alkali metal hypochlorite for longer times than is provided by known aqueous cleaning compositions of equal hypochlorite concentration apphed to a stained surface in the form of a sprayed liquid, a short-lived foam, a thickened liquid or a gel.
  • the superior cleaning efficiency of the fluid foams of the invention compared to known cleaners of similar composition is believed to be a result of the liquid-rich cells of the fluid foam of the invention clinging strongly to the surface being cleaned and the cells breaking up slowly so that a continuous source of the alkali metal hypochlorite is efficiently delivered to the stained surface.
  • a fluid foam of the invention has a longer contact time with the stained surface and provides a greater amount stain-removing agents to react with the stain.
  • the present inventor found that the fluid foams of the invention provide better cleaning without scrubbing than any of the known hypochiorite- containing cleaners he tested. Substantially the same superior cleaning results, as were obtained in the cleaning of the mildew covered surfaces of the landscaping timbers, are obtained when the fluid foam cleaning compositions of the invention are apphed to stained surfaces of painted wood, plastic film, cement, plaster, fabric or the hke.
  • the cleaning composition fluid foam of the invention even without the inclusion of a fragrance, was found to mask to a substantial degree, the smell of the alkali metal hypochlorite. Also, during application of the fluid foam cleaning composition of the invention to a stained surface, the typically opaque white color of the fluid foam provided an easily seen indicator of whether the cleaner had missed any particular area of the surface. The present inventor further found that fluid foam cleaner of the invention also removed soap scum, dirt and oily stains.
  • Fluid foams having characteristics outside the combination of characteristics set forth above for the fluid foam of this invention are deficient in their ability to remove stubborn mycological and mildew stains without brushing or scrubbing.
  • a thick liquid having high relative viscosity is not readily formed into a fluid foam cleaning composition of the invention and is not readily removable from a surface by rinsing.
  • scrubbing is required to remove a layer of the cleaner that remains on the surface even after rinsing.
  • a fluid foam having very low syneresis value does not clean well because it does not carry and release an adequate amount of the active cleaning agent to the stained surface, even if the vertical clingability of the foam is high.
  • a foam that has an excessively large syneresis value often is too thin and slippery, which prevents the foam from adhering to the stained surface long enough to accomplish the cleaning.
  • a foam having very short horizontal thickness half-life or a very low vertical surface clingability also leaves the stained surface too quickly to allow for adequate cleaning.
  • the process for producing a cleaning composition fluid foam of the invention typically comprises two-steps. First an aqueous solution is prepared containing an alkali metal hypochlorite, an alkaline builder that maintains the solution at a pH of at least 11, and a hypochlorite-compatible surfactant, each in the desired concentrations recited herein before. Then the solution is vigorously agitated in the presence of a gas. The vigorous agitation can be achieved with mechanical stirrers, but preferably is provided by the fluidic/pneumatic action of a fluid jet, such as is produced by a mechanical breakup actuator of an aerosol dispenser in the presence of propellant.
  • the foam is produced with a low-boiling hydrocarbon propellant in an aerosol dispenser made of materials compatible with the aqueous solution.
  • propellants include propane, n-butane, isobutane and mixtures thereof in a concentration of 1 to 15% by the weight of the aqueous solution.
  • Parts and surfaces of the aerosol dispenser that contact the aqueous solution are of hypochlorite-compatible metal, rubber or plastic.
  • aqueous solution of alkali metal hypochlorite, alkaline builder and surfactant in accordance with the concentrations required for the fluid foam cleaner of the present invention, is mixed and placed in the container of the aerosol dispenser.
  • the outer wall of the dispenser container typically is of a metal, plastic or glass of sufficient strength to withstand the internal pressures expected during use.
  • the container has an inner liner made of hypochlorite-compatible glass or plastic. Polyethylene and polypropylene are preferred liner materials.
  • a container particularly suited for use with the aqueous solutions is commercially available from ALCAON PACKAGING of ALgroup Wheaton of Netherlands.
  • the aerosol dispenser as depicted in FIG. 2, comprises a cylindrical container 20 having a cover (also called a "mounting cup") 22 attached to the top of the container.
  • the container has an inner liner insert 21 of hypochlorite compatible material.
  • Cover 22 has a hypochlorite- compatible material laminated to its inner surface.
  • Valve components of the aerosol dispenser are pre-assembled to form a valve assembly unit, which includes housing 23, valve stem gasket 24, spring 25, valve stem 26, actuator button 27 containing nozzle 28, and dip tube 29.
  • the valve assembly unit is inserted thrqugh an opening in the center of cover 22 and is attached to the cover to form a valve/cover assembly.
  • An aqueous precursor solution is prepared, mixed and loaded into container 20.
  • the pre-assembled valve/cover assembly is installed in the container.
  • the hypochlorite-compatible material laminated to the circumferential edge of cover 22 is brought into contact with the upper rim of hypochlorite-compatible inner liner 21 of container 20 and men the circumferential edge of cover 22 and the top edge of container 20 are mechanically crimped together, so that the hypochlorite-comopatible materials of the cover laminate and the container inner liner form a seal.
  • a cover-sealing gasket not shown in Fig.2, can be installed. All parts of the aerosol dispenser are made of materials compatible with aqueous hypochlorite solution.
  • the housing and valve stem can be made of nylon, the dip tube and actuator button of polyethylene or polypropylene, the valve stem gasket of butyl rubber U ⁇ 33, of an ethylene/propylene copolymer or of Viton ® synthetic rubber (from Dupont Dow Elastomers LLC of Wilmington, Delaware) and the coil spring of passivated stainless steel, tantalum or titanium.
  • the cylindrical container and cover can be made of aluminum, steel or tin plate, the cover being laminated with a film of polyethylene or polypropylene on its inner surfaces and die cylinder having an inner liner insert of polyethylene or polypropylene.
  • propellant usually as liquid
  • aqueous solution aqueous solution
  • Preferred propellants include propane, butane, isobutane and mixtures thereof in quantities amounting to 1 to 15% of the weight of the aqueous solution.
  • the dispenser is shaken to mix the propellant with the aqueous liquid in the container.
  • Nozzle 28 has a mechanical break-up actuator insert located just upstream of the nozzle exit.
  • the mixture emerging from the actuator nozzle is like a mist that when dispensed onto a surface, converts almost immediately to fluid foam of the invention.
  • certain design features can improve sprayed foam formation. Such features include, upstream of the exit nozzle, mechanical breakup mechanisms to reduce spray particle size. Typical break-up mechanisms include a circular or near circular swirl chamber, one or more tangential entries to a chamber, orifices, screens, and/or special exit nozzles.
  • the aerosol dispenser can also include an extension tube, not shown in Fig.2, which extends from the exit of button 27 and has a mechanical break-up orifice located at the exit end of the extension tube.
  • fluid foam of the invention was produced by vigorously agitating aqueous alkali metal hypochlorite solution, while in contact with a gas, such as air, or a low boiling liquid hydrocarbon propellant. Vigorous agitation was produced by mechanical or fluidic/pneumatic means. Test foams of the invention prepared by vigorous mechanical agitation of liquid solution in the presence of air were produced in an 800-watt AC "Osterizer" manufactured by Oster Corporation of Miluakee, Wisconsin, having a 1.2-liter-capacity glass container. The foam produced by the Osterizer was dispensed to a test panel surface by pouring, by brushing or with a spatula. When vigorous agitation was provided by an aerosol dispenser, a dispenser of the general type illustrated in FIG.
  • Example 2 This example quantitatively demonstrates the greater mildew-removing effectiveness of aqueous hypochiorite-containing cleaning compositions apphed as fluid foams of the invention over the same hypochiorite-containing compositions apphed as liquids. Side by side comparisons were made of the cleaning effectiveness on the same mildew stained landscaping timber.
  • aqueous solutions Five different aqueous solutions were prepared. The solutions had spdium hypochlorite concentrations of 1, 2, 3, 4 and 5 %. Each solution also contained a 0.5 % concentration sodium hydroxide alkaline builder to maintain the aqueous solution at a pH of at least 11 and a 1.5 % concentration of non-ionic surfactant "Barlox 12"cocamine oxide (available from Lonza Speciality Chemical Company of New Jersey).
  • the surfactant has an average molecular weight of 249 and is a mixture of N,N- ⁇ me yl-l-dodecylamine-N-oxide, N,N-dimethyl-l-tetradecyl- amine-N-oxide, and N,N-dimethyl-l-hexadecyIamine-N-oxide.
  • a 200-cm 3 portion of each liquid solution was converted to a fluid foam of the invention by vigorous mechanical agitation of the solution in an Osterizer set at a high (i.e., "whip" setting) for 20 seconds. Then each liquid solution and its corresponding same composition fluid foam were applied to side-by-side cleanability test panels of a landscaping timber stained with stubborn mildew.
  • Clorox Uquid bleach the product designated "f ' in the table, with a 5.25% NaOCl concentration was the best performing commercial product, but its cleanability rating was only 4,0, in contrast to a rating of 14,0 for a foam of the invention having an NaOCl concentration of 5% (see Table I).
  • a thickened aqueous composition which was substantially the same as the composition disclosed in Example 2 of U.S. Patent 4,800,036 (Rose), was prepared as follows. To 544.2 grams of a 5.25% active NaOCl aqueous bleach (sold by Clorox Corporation), 441.5 grams of distilled water were added. Then, 7.14 grams of hexadecyltrimethlammonium bromide and 7.14 grams of sodium p-toluene sulfonate were added to the aqueous bleach.
  • the last two solid ingredients were dissolved in the liquid by stirring with a spatula for about 30 minutes,
  • the resulting solution which was transferred to a plastic bottle, had calculated concentrations of 2.86% NaOCl; 0.71%hexadecyltrimethylammonium bromide, 0,71% sodium p-toluene sulfonate and 95.72% water.
  • the solution was yellowish, very thick (viscous) compared to water and tended to form clumps or streaks of even thicker Uquid dispersed in the solution when the container was shaken.
  • Cleanability tests were performed by applying this aqueous formulation to the test panels in three different ways, namely (1) as liquid solution poured onto the test panel, (2) as a spray, dispensed from the same hand-pumped spray foaming device as was used for commercial sample "a” of Example 2, and (3) as a foam prepared by whipping a 200-cm 3 portion of the solution for 30 seconds in the Osterizer immediately before being applied to a test panel.
  • These three test samples were designated Tl, T2 and T3.
  • a thickened foam such as T3, which was prepared in the Osterizer, is not disclosed or suggested in U.S. Patent 4,800,036.
  • the aqueous cleaning composition fluid foams of the invention with which the above- described thickened formulations were compared were designated as Samples 6 and 7.
  • the samples contained 0.5 and 0.3% NaOH alkaline builder respectively and 1.5% Barlox cocamine oxide surfactant. NaOCl concentrations in Samples 6 and 7 were 5.0 and 3,0 % respectively.
  • Precursor solutions of Samples 6 and 7 had relative viscosities in the range of 1.1 to 1.5. Samples 6 and 7 were then vigorously agitated in the Osterizer to produce fluid foam of the invention.
  • the fluid foams of Samples 6 and 7 had vertical surface clingabilities in the range of 7 to 12 minutes and horizontal half-lifes of greater than 15.
  • each of the thickened samples had a precursor solution of vastly higher relative viscosity (e.g., at least 500% the viscosity of water) and a very short vertical clingability of less than 20 seconds.
  • Table HI shows that the apphcations of the thickened liquid and spray (Tl and T2 respectively) performed poorly in the cleanability tests compared to the fluid foams of the invention. Even when the thickened formulation was vigorously agitated in the Osterizer to form a foam, the cleanability ratings of the thickened foam was much inferior to the foams of the invention. It was also noted that the thickened Uquid and spray samples had a consistency resembling that of an uncooked beaten egg and had a tendency to run down and slip off the vertical panels. Further, after the tests panels were rinsed with water, some amounts of sticky film remained on the panels and could not be rinsed away without scrubbing or brushing. By contrast the surfaces treated with the foam of this invention were completely cleaned by simple rinsing with room temperature water with no residues left behind.
  • FIG.2 This example illustrates the use of an aerosol dispenser of the general design depicted in 'Fig.2 to produce fluid foam cleaning composition of the invention.
  • An aqueous solution was prepared to contain.5% sodium hypochlorite, 0.5% sodium hydroxide alkaline builder, and 1.5% Barlox-12 surfactant which contains 30% cocamine oxide in water.
  • a 320-cm 3 volume of the aqueous solution was loaded into each of several aerosol dispenser containers. Each dispense measured 15 cm high by 6,3 cm in diameter. The internal surfaces of the containers were epoxy- coated.
  • the dispensers were equipped with valves and actuators of the mechanical break-up type having an orifice diameter of 0.045 cm (0,018 inch).
  • AERON ® NP-31 consisting of 81,3 %n-butane, 16.6 %propane and 2.1 % isobutane, and having a nominal vapor pressure of 225 KPa (33 psig;)
  • AERON ® NP-46 consisting of 68.5 %n-butane, 31.5 % propane, and having a nominal vapor pressure of 317 KPa (46 psig);
  • AERON ® NP-70 consisting of 42.5 % n-butane and 57.5 % propane and having a: vapor pressure of 483 KPa (70 psig).
  • the AERON ® propellants were obtained from Diversified Propellant Company International, Inc., USA. All percentages for the propellant compositions are in mole %.
  • the containers were loaded to provide propellant concentrations of 5, 3, 2 and 1.25 % by total weight of the aqueous solution.
  • the foam properties and cleanability ratings of the aerosol-dispenser- produced fluid foams were then measured. The measurements showed the following:
  • This example illustrates the use of a pouched or barrier dispenser as an aerosol dispenser system for producing fluid foam of this invention
  • an aqueous hypochlorite solution and propellant are injected inside a flexible pouch suspended from the valve inside the dispenser container and the space between the pouch and the wall of the container is filled with nitrogen or air.
  • Two pouches of different material were tested. In each test, the pouch was attached to an aerosol valve assembly similar to the type depicted in the dispenser of Fig.2. hi the first test, the pouch was made of a plastic film that was lined with a layer of nylon polymer. The pouch was filled with the same composition aqueous hypochlorite solution as was used in Example 4.
  • the solution contained 5% sodium hypochlorite, 0.5% sodium hydroxide alkaline builder, and 1.5% Barlox-12 surfactant. Pressurized air filled the space between the pouch and the inner wall of the container. This pouched dispenser system initially produced good quality foam having satisfactory cleanability ratings, but after several days of storage, the system developed leaks.
  • the pouch was constructed from two layers of plastic film between which was a layer of aluminum foil. This pouch had a capacity of 215 cm 3 .
  • the internal volume of the container was 329 cm 3 .
  • the pouch was filled with 202 grams of solution of the same composition as was used in the test described in the preceding paragraph.
  • the space between the pouch and the walls of the dispenser container was filled with nitrogen at a pressure of 172 KPa absolute (25 psia).
  • a charge of 6 grams of pressurized propellant AERON ® NP-46 (consisting of 68.5 mole % n-butane and 31.5 mole % propane) was injected into the solution to provide a propellant concentration of 2.96% in the solution.
  • test aqueous solution was formulated to contain a 5% concentration of NaOCl, sufficient NaOH to maintain the solution at an initial pH of at least 11, and a 1.5% concentration of Barlox-12 surfactant.
  • the test solutions were then converted by Osterizer agitation to fluid foam cleaners which were then subjected to the cleanability rating test.
  • the 10-minute cleanability ratings of the foams are recorded in the following table. Table IV, Stability of foam cleaners

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne une mousse fluide de composition aqueuse de nettoyage contenant un hypochlorite de métal alcalin possédant une combinaison particulière de viscosité relative de solution de précurseur, de valeur de synérèse de la mousse, de demi-vie d'épaisseur horizontale de la mousse et de propriété d'adhérence de la mousse sur une paroi verticale, et qui, comparée à de compositions connues de nettoyage contenant un hypochlorite, permet d'obtenir un nettoyage supérieur de moisissure tenace sans lavage. Cette mousse fluide de composition de nettoyage est produite par agitation vigoureuse d'une solution aqueuse d'hypochlorite contenant un adjuvant alcalin et un tensioactif en présence d'un gaz, ou par injection d'un gaz propulseur sous pression dans un diffuseur d'aérosol contenant une telle solution, puis par passage du mélange solution/gaz propulseur dans un dispositif de scission mécanique disposé dans l'assemblage de valve du diffuseur d'aérosol.
EP03746071A 2002-04-01 2003-03-28 Elimination de coloration tenace de moisissure Withdrawn EP1497404A4 (fr)

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US36936602P 2002-04-01 2002-04-01
US369366P 2002-04-01
PCT/US2003/009641 WO2003085073A2 (fr) 2002-04-01 2003-03-28 Elimination de coloration tenace de moisissure

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Citations (14)

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GB1367067A (en) * 1970-10-06 1974-09-18 Wilkinson Sword Ltd Compositions containing a source of hypochlorite ions
EP0095045A1 (fr) * 1982-05-26 1983-11-30 Alfred Kärcher GmbH & Co. Liquide décontaminant
EP0595590A2 (fr) * 1992-10-30 1994-05-04 Diversey Corporation Agents de nettoyage non-chlorés à basse alkalinité et à haute rétention
EP0606707A1 (fr) * 1993-01-11 1994-07-20 The Clorox Company Solutions d'hypochlorite épaissies à odeur produit de blanchiment réduite, procédé de fabrication et utilisation
WO1994024259A1 (fr) * 1993-04-15 1994-10-27 Unilever Plc Composition de nettoyage hygienique et appareil destine a pulveriser ladite composition
JPH0841497A (ja) * 1994-08-03 1996-02-13 Kao Corp 硬質表面用漂白剤組成物
US5597793A (en) * 1993-06-01 1997-01-28 Ecolab Inc. Adherent foam cleaning compositions
DE19626906C1 (de) * 1996-07-04 1998-03-12 Henkel Kgaa Mittel für die Reinigung harter Oberflächen
US5728665A (en) * 1995-09-13 1998-03-17 The Clorox Company Composition and method for developing extensional viscosity in cleaning compositions
US5804545A (en) * 1993-11-24 1998-09-08 West Argo, Inc. Stable alkaline chlorine compositions
US5916859A (en) * 1992-10-19 1999-06-29 The Clorox Company Hexadecyl amine oxide/counterion composition and method for developing extensional viscosity in cleaning compositions
DE19915839A1 (de) * 1999-04-08 2000-10-19 Cognis Deutschland Gmbh Wäßrige Bleich- und Desinfektionsmittel
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JP2001316697A (ja) * 2000-04-28 2001-11-16 Lion Corp 漂白剤組成物

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JPH0649880B2 (ja) * 1986-06-04 1994-06-29 ユニ・チヤ−ム株式会社 起泡性液体洗浄剤組成物

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Publication number Priority date Publication date Assignee Title
GB1367067A (en) * 1970-10-06 1974-09-18 Wilkinson Sword Ltd Compositions containing a source of hypochlorite ions
EP0095045A1 (fr) * 1982-05-26 1983-11-30 Alfred Kärcher GmbH & Co. Liquide décontaminant
US5916859A (en) * 1992-10-19 1999-06-29 The Clorox Company Hexadecyl amine oxide/counterion composition and method for developing extensional viscosity in cleaning compositions
EP0595590A2 (fr) * 1992-10-30 1994-05-04 Diversey Corporation Agents de nettoyage non-chlorés à basse alkalinité et à haute rétention
US6180583B1 (en) * 1992-11-03 2001-01-30 The Procter & Gamble Company Cleaning compositions containing short-chain surfactants
EP0606707A1 (fr) * 1993-01-11 1994-07-20 The Clorox Company Solutions d'hypochlorite épaissies à odeur produit de blanchiment réduite, procédé de fabrication et utilisation
WO1994024259A1 (fr) * 1993-04-15 1994-10-27 Unilever Plc Composition de nettoyage hygienique et appareil destine a pulveriser ladite composition
US5597793A (en) * 1993-06-01 1997-01-28 Ecolab Inc. Adherent foam cleaning compositions
US5804545A (en) * 1993-11-24 1998-09-08 West Argo, Inc. Stable alkaline chlorine compositions
JPH0841497A (ja) * 1994-08-03 1996-02-13 Kao Corp 硬質表面用漂白剤組成物
US5728665A (en) * 1995-09-13 1998-03-17 The Clorox Company Composition and method for developing extensional viscosity in cleaning compositions
DE19626906C1 (de) * 1996-07-04 1998-03-12 Henkel Kgaa Mittel für die Reinigung harter Oberflächen
DE19915839A1 (de) * 1999-04-08 2000-10-19 Cognis Deutschland Gmbh Wäßrige Bleich- und Desinfektionsmittel
JP2001316697A (ja) * 2000-04-28 2001-11-16 Lion Corp 漂白剤組成物

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DATABASE WPI Section Ch, Week 198804 Derwent Publications Ltd., London, GB; Class A97, AN 1998-025265 XP002318480 & JP 62 286000 A (UNI CHARM KK) 11 December 1987 (1987-12-11) *
PATENT ABSTRACTS OF JAPAN vol. 1996, no. 06, 28 June 1996 (1996-06-28) & JP 08 041497 A (KAO CORP), 13 February 1996 (1996-02-13) *
PATENT ABSTRACTS OF JAPAN vol. 2002, no. 03, 3 April 2002 (2002-04-03) & JP 2001 316697 A (LION CORP; LION AKZO KK), 16 November 2001 (2001-11-16) *
See also references of WO03085073A2 *

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