EP0733097B1 - Two-part cleaning composition comprising at least one peroxide compound - Google Patents

Two-part cleaning composition comprising at least one peroxide compound Download PDF

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Publication number
EP0733097B1
EP0733097B1 EP95903289A EP95903289A EP0733097B1 EP 0733097 B1 EP0733097 B1 EP 0733097B1 EP 95903289 A EP95903289 A EP 95903289A EP 95903289 A EP95903289 A EP 95903289A EP 0733097 B1 EP0733097 B1 EP 0733097B1
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EP
European Patent Office
Prior art keywords
composition
kit according
peroxide
alkaline
component
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.)
Revoked
Application number
EP95903289A
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German (de)
English (en)
French (fr)
Other versions
EP0733097A1 (en
Inventor
Gillian Smith
Royston Reginald Smith
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.)
Unilever PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
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
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Priority claimed from GB939325046A external-priority patent/GB9325046D0/en
Priority claimed from GB9406972A external-priority patent/GB9406972D0/en
Priority claimed from GB9413098A external-priority patent/GB9413098D0/en
Priority claimed from GB9415908A external-priority patent/GB9415908D0/en
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP0733097A1 publication Critical patent/EP0733097A1/en
Application granted granted Critical
Publication of EP0733097B1 publication Critical patent/EP0733097B1/en
Anticipated expiration legal-status Critical
Revoked legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3947—Liquid compositions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B11/00—Single-unit hand-held apparatus in which flow of contents is produced by the muscular force of the operator at the moment of use
    • B05B11/01—Single-unit hand-held apparatus in which flow of contents is produced by the muscular force of the operator at the moment of use characterised by the means producing the flow
    • B05B11/10—Pump arrangements for transferring the contents from the container to a pump chamber by a sucking effect and forcing the contents out through the dispensing nozzle
    • B05B11/1081—Arrangements for pumping several liquids or other fluent materials from several containers, e.g. for mixing them at the moment of pumping
    • 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

Definitions

  • the present invention relates to cleaning compositions which comprise at least two components which are stored separately and mixed shortly before use, at least one of said components comprising a peroxide compound.
  • peroxide compound is meant a compound comprising a peroxy (HOO-) group, including hydrogen peroxide and both organic and inorganic peroxides.
  • the present invention provides compositions which are particularly well adapted for use in cleaning and sterilising household surfaces and the removal of discolouration caused by mould growth. Such discolouration is a known problem, particularly under humid conditions.
  • compositions which remove, kill or bleach mould on surfaces have previously comprised strong solutions of alkali metal hypochlorite to be sprayed onto the surface.
  • hypochlorite has an unpleasant odour and, when sprayed, hypochlorite solutions can produce droplets which cause significant respiratory irritation.
  • bleaching agents are known, particularly peroxides.
  • peroxides are often either unstable in formulations or exhibit poor bleaching performance at their most stable pH.
  • Toothpastes and peroxide-based hair bleaching compositions have been formulated as weakly acidic peroxide solutions or gels and separate weakly alkaline solutions or pastes which are mixed just before use.
  • the known advantage of this form of product being that the peroxide is more stable to decomposition under acidic conditions and yet is more effective as a bleaching agent under alkaline conditions.
  • JP-A-60/038497 relates to a foaming, two-part drain cleaning composition which comprises:
  • compositions (a) and (b), including the surfactants and terpene are sequentially or simultaneously dosed into a toilet bowl and pass into the drains where the composition produces a body of foam which acts to clean or if necessary unblock the drain.
  • US 3760986 discloses a dispensing bottle for dispensing two separate fluids to a common point.
  • a bottle is formed with an opening at the top and a divider extending through the interior of the bottle to define two compartments which provide dual reservoirs for fluids.
  • the apparatus disclosed further comprises pump means to simultaneously withdraw fluid from each compartment, via separate draw tubes, and discharge the fluid to a common point.
  • This device enables an alkaline and an acid material to be stored separately and sprayed from a single unit to a common point.
  • the pumps used in this apparatus are of a type wherein an inlet valve of a working chamber comprises a ball held against a valve seat by a spring such that as a piston compresses the working fluid the ball is forced against the seat and the working fluid cannot return down the draw tubes into the reservoirs.
  • CASTNER is an integral package and dispenser. Although it can be envisaged that the device could be disassembled and refilled, such an activity could prove hazardous due to the nature of the liquids involved. CASTNER proposes that the device be provided with closable ports for refilling, although such an activity is envisaged to be dangerous where oxidising or corrosive liquids are concerned.
  • US 4826048 discloses a dispenser for pharmaceutical or cosmetic liquids which comprises a pair of bottles each provided with a separate pump. In this case, the bottles may be removed for refilling or replacement.
  • US 5152461 discloses a dispenser with a single pump and a pair of bottles which can be detached for refilling or replacement.
  • the invention provides a kit of parts comprising:
  • the present specification means a spray of discrete droplets or a jet of foam, the operative consideration being that one or preferably both of the compositions are ejected from the unit with sufficient force that can be deposited upon a surface which is displaced horizontally from the unit.
  • the unit is adapted to produce a spray comprising a mixture of compositions (a) and (b).
  • a unit can be adapted to produce separate sprays of compositions (a) and (b) such as by means of sequential spraying through a single spray means or simultaneous spraying through separate spray means.
  • the production of a single spray which comprises a mixture of (a) and (b) is preferred.
  • a second aspect of the present invention provides a method of cleaning hard surfaces which comprises the steps of:
  • the cleaning operation comprises the step of contacting the product of step (a) with the surface to be cleaned for a period in excess of 5 minutes.
  • the preferred peroxide compound is hydrogen peroxide although it is envisaged that other peroxides could be employed, provided that they are stable in the compositions of the invention.
  • hydrogen peroxide shows better bleaching performance at an alkaline pH, particularly above pH 10. However, hydrogen peroxide shows reduced stability at this pH as compared with its stability at acid or neutral pH.
  • peroxide compounds can be employed.
  • peracids particularly peracetic acid and persulphates particularly potassium mono-persulphate.
  • suspensions of solid peroxides can be employed it is preferred that solutions of a soluble peroxide are employed.
  • Such solutions are preferably aqueous although other solvents can be employed when the practice is chemically reactive with, or in the presence of water.
  • the diacetyl ester of ethylene glycol is a suitable solvent.
  • Preferred levels of peroxide compound range from 1-50%wt of the composition containing the peroxide compound.
  • levels below 4%wt peroxide are less effective as bleaching agents, whereas solutions containing more than 50%wt peroxide can be hazardous.
  • peracetic and persulphates levels of 1-10%wt in the neat compositions are preferred.
  • an important aspect of the present invention is that two components are mixed either before or during the spraying operation. It is preferred that the mixing ratio falls into the range 2:1-1:2, with ratios around 50:50 being particularly preferred. It will be appreciated that the optimal mixing ratio will be to some degree dependent on the nature and quantities of the components present, the operative consideration being that the mixed composition should have an alkaline pH overall.
  • aqueous solutions according to the present invention can attain a nature acid pH. It is particularly preferred that the pH of the acid or neutral peroxide composition falls into the range of above 2 to less than 8, with preferred pH's being around 5. While solutions of pH below 2 can be used it is preferable to avoid such acid compositions due to hazards of spillage or contact with the skin of a user.
  • alkaline compositions a pH above 10 is preferred.
  • the most preferred pH range is 11-13.
  • the alkaline reserve of the alkaline composition should be such that the pH remains high, preferably at pH 8 or above and more preferably above pH 10, after the addition of the acidic or neutral peroxide compound containing composition.
  • the alkaline composition should preferably not have a pH so high as to be hazardous to use.
  • mineral or organic acids with optional buffer salts, can be employed provided that these acids and salts are not peroxide sensitive.
  • di-sodium hydrogen citrate and/or trisodium citrate can be used to achieve the required acid pH.
  • the presence of the trisodium citrate or other buffer salt being advantageous in that it prevent a downward drift in the pH of the acidic peroxide compound containing composition over prolonged storage.
  • Alkaline pH can be attained by the use of alkali earth or metal or ammonium hydroxides, particularly potassium and sodium hydroxides. Carbonates and/or bicarbonates can be present in the alkaline composition, as can borates, silicates, phosphates, and/or other buffers. Preferably the alkaline composition comprises 0.5-1.5 molar commercial caustic soda in aqueous solution.
  • the alkaline and the acidic or neutral compositions can be mixed in any ratio between 1:10 and 10:1.
  • the required ratio being somewhat dependent on the pH of the two compositions and the particular pH modifying agents present.
  • compositions should generally be formulated such that when mixed in a ratio of from 2:1-1:2, preferably, 1:1 the resulting solution has the desired pH, i.e. a pH at which the peroxide compound present is effective as a bleaching agent.
  • a pH at which the peroxide compound present is effective as a bleaching agent i.e. a pH at which the peroxide compound present is effective as a bleaching agent.
  • the preferred pH after mixing with alkali is pH 10-12, more preferably ph 11-11.5.
  • monopersulphate and peracetic acid the preferred pH after mixing is around pH 8.
  • Thickener is an optional component of the present invention, being essential only in certain aspects of the invention. It is believed that thickeners can function in two ways.
  • An irritant mist comprises relatively large population of fine droplets, whereas in the presence of a thickening agent a relatively small population of fine droplets is produced.
  • cellulose derivatives particularly hydroxy alkyl cellulose derivatives including hydroxy propyl methyl cellulose are particularly effective at thickening the acid peroxide composition to the extent required to achieve good spraying characteristics.
  • thickeners can be selected such that the compositions thicken significantly when the components are mixed. This has the significant advantage that the composition does not run off sloping or vertical surfaces (such as the walls of shower stalls) when applied.
  • Typical levels of thickener range from 0.05-5%wt.
  • the thickener component is a polymer
  • the most preferred thickeners are those which exhibit a marked increase in composition viscosity at above the pH of the acidic peroxide-containing composition.
  • the thickener is originally present in an acidic, peroxide compound containing composition at a pH where a low viscosity is exhibited, and, in use the solution is mixed with a more alkaline composition in a quantity such that the pH of the resulting mixture is one at which the thickener exhibits an increased viscosity.
  • Suitable polymers include those which only thicken compositions substantially at alkaline pH.
  • Such polymers include polyacrylic acids (such as those available in the market as the 'Carbopol' (TM) series and acrylate copolymers.
  • the thickener can be present in the alkaline composition, provided that the pH of this composition is sufficiently high, and that when an acidic or neutral peroxide-containing composition is added in sufficient quantity the pH falls into a region where an increased viscosity is exhibited.
  • Thickener components include clays, silicas, and mixed surfactant systems. Where significant thickening on mixing is required, the common factor between the thickeners is that when the acidic or neutral peroxide compound containing composition and the alkaline composition are mixed in the presence of the thickener components, the resulting mixture has a higher viscosity than either of the compositions taken alone.
  • the thickener components are all peroxide stable, but only required that, where used, the or each thickener component is chemically stable in either the acidic or neutral peroxide compound containing composition or the alkaline composition.
  • At least one of said peroxide containing or alkaline compositions further comprises a cationic surfactant.
  • Preferred cationic surfactants include the quaternary ammonium compounds of the formula: R1.R2.R3.R4.NX Wherein R1-R4 are alkyl and X is an anion.
  • R1 and R2 are C8-C18 alkyl and R2 and R3 are C1-C4 alkyl.
  • X is a halide.
  • Particularly preferred cationics include dialkyl dimethyl ammonium halides. We have determined that didecyl dimethyl ammonium chloride is particularly suitable.
  • surfactants in addition to the cationic surfactant, are generally present in the compositions of the present invention so as to assist in the cleaning process in which the compositions are used.
  • the presence of further surfactant is however optional.
  • surfactants are required to be peroxide-stable or not will be determine whether the surfactant is incorporated in the acid/neutral or alkaline composition.
  • peroxide-stable surfactants include anionic surfactants such as primary or secondary alkane sulphonates, primary alkyl sulphates and/or alkyl aryl sulphonates. Most preferable are nonionic surfactants, particularly those which comprise alkoxylated alcohols. Mixtures of two or more of these surfactants can be used. Alkyl sulphate surfactants and/or ethoxylated alcohols are particularly preferred.
  • the surfactant can be provided as a component of the alkaline component.
  • ethoxylated alcohols are stable in either acid/neutral hydrogen peroxide solutions or alkaline solutions.
  • Typical levels of surfactants range from 0.1-20%wt of the component containing them. Levels of surfactant around 2-10%wt on total liquid component are particularly preferred.
  • Fungicides and/or other biocides, antimicrobials etc. other than the peroxides can be present, provided that they are stable in either the acidic/neutral component or the alkaline component.
  • perfumes perfumes, solvents, which may be required to solvate certain fungicides, and bleach stabilizers.
  • Bleach stabilisers will be required in the peroxide compound is decomposed by transition metals present in the composition. Accordingly it is preferable that the composition further comprises a transition metal complexing bleach stabiliser selected from phosphates, phosphonic acids or phosphonates, stannates, and carboxylates.
  • a transition metal complexing bleach stabiliser selected from phosphates, phosphonic acids or phosphonates, stannates, and carboxylates.
  • Preferred metal ion complexing agents are selected from dipicolinic acid, ethylene diamine tetra acetic acid (EDTA) and its salts, hydroxy-ethylidene diphosphonic acid (Dequest 2010, RTM), ethylene diamine tetra (methylene phosphonic acid) (Dequest 2040, RTM), diethylene triamine penta(methylene phosphonic acid) (Dequest 2060, RTM).
  • EDTA ethylene diamine tetra acetic acid
  • the phosphonic acid derivatives are particularly preferred.
  • the level of metal ion complexing agent should fall into the range 0.01-5%wt, with levels around 0.1%wt being particularly preferred.
  • the alkaline component further comprises a transition metal or halide bleach decomposing agent which reacts with the acidic or neutral peroxide containing composition.
  • the alkaline component comprises a halide, preferably a bromide.
  • solvents can be included in the compositions of the invention so as to solvate components of the compositions.
  • solvents can function to improve the cleaning and or wetting properties of the product as sprayed onto a surface to be cleaned.
  • Suitable solvents include the glycol ethers.
  • a preferred solvent is BUTYL DIGOL (TM), which we have determined to be stable in the alkaline composition. Preferred solvent levels range from 2-12%wt with 3-8%wt being particularly preferred.
  • the apparatus aspect of the present invention provides for a two-part container which enables simultaneous or sequential spraying of compositions which comprise:
  • the containers which define the reservoirs for the compositions comprise a draw tube, valve means to prevent liquid returning along said draw tube and meaning to releasably engage said container with a pumping and spraying head.
  • the container described above is of particular utility when used in combination with a dual-reservoir pumping and spraying head of the type described with reference to the background of the invention.
  • the prior art envisages that the containers alone can be disassembled from the spraying apparatus, or that the containers be disassembled from the spraying apparatus together with an associated pump, there is no disclosure of a container with an integral draw tube and non-return valve which can be removed from the pumping and spraying apparatus.
  • valve means allows liquid to be drawn from the container when the container is engaged with the pumping and spraying head.
  • Suitable valve means include a valve seat and a check element urged against the seat by spring means. It is preferred to use a ball valve urged against an annular seat by a helical spring.
  • valve means further comprise means to prevent discharge of the contents of the container prior to attachment of the spray head. This feature is particularly useful if the contents of the container are chemically aggressive, i.e. if corrosive or oxidising contents are employed.
  • Said means to prevent discharge can comprise a membrane closing the egress from the container.
  • the arrangement being such that the membrane is pierced before or as the container is engaged with the pumping and spraying head.
  • Particularly preferred containers have a second valve means which acts to prevent discharge of the container contents when the container is not engaged with the pumping means.
  • a second valve means which acts to prevent discharge of the container contents when the container is not engaged with the pumping means.
  • Such a construction has the advantage that a partially empty contained can be disengaged from the pumping and spraying head without risk that the contents will be discharged.
  • a second check element is held against a second valve seat by spring means, unless displaced by a member projecting from the pumping and spraying head.
  • the invention extends to the containers described above filled with an aqueous solution of a peroxide compound and/or alkali. All of these species are either corrosive or otherwise harmful and gas-evolving reactions can occur when they are mixed.
  • valve means prevents the container being refilled by an unskilled or ill-informed user. If the containers could be refilled with ease, a user might be led to operate a dual reservoir pumping and spraying device of the type described above with solutions such as hypochlorite and strong acid, which produce a potentially deadly cloud of chlorine gas when these solutions are allowed to react.
  • FIG 1 and la show a container according to the present invention, in isolation as in figure la or assembled together with a similar container and a spraying and pumping head.
  • FIG 2 and 2a show alternative embodiments of the invention with particular detail of the valve means.
  • FIG 3 shows a detail of a preferred valve means in an embodiment of the present invention.
  • Unglazed ceramic tiles (simulating glazed tile grout) were treated with a fungal liquid medium (Saboraud Liquid Medium) and inoculated with spores of Penicillium chrysogenum (a green mould common in bathrooms and kitchens) by exposure of the tiles to spores released from a culture of the fungus maintained on an agar plate (Czapek Dox agar + 2% malt extract).
  • the tiles were stored in damp conditions (relative humidity around 90%) to encourage growth and the backs of the tiles were sprayed with water to maintain conditions which favoured growth of the mould.
  • the tiles were used as such to evaluate the effect of the composition of the invention on fresh mould, whereas the effect of the composition on aged mould was determined after autoclaving of the tiles.
  • Composition A 0.15% Methocell J12MS (hydroxy propyl methyl cellulose), 0.2% DEQUEST 2060 (TM ex. Monsanto), 6.0% Hydrogen Peroxide, 1.0% Disodium hydrogen citrate, 4.0% NE-208T (TM ex. Nippon Oil) primary alcohol ethoxylate, nonionic surfactant, 0.2% Perfume composition 'A' was adjusted to pH 5.0 with 20% sodium hydroxide solution.
  • Methocell solution was prepared by gradually adding the polymer to distilled water and stirring to disperse. The dispersion was heated to approximately 60 Celcius and the pH adjusted to 9.0 with NaOH. The solution was stirred for around one hour while cooling to ambient to give a clear viscous stock solution.
  • Composition B 0.1% ACUSOL 810 (TM ex. Rohm and Haas) : acrylic crosslinked copolymer, 1.9% NaOH 4.0% NE-208T (TM ex. Nippon Oil) primary alcohol ethoxylate, nonionic surfactant, 1.0% Didecyl dimethyl ammonium chloride, 4.0% BUTYL DIGOL (TM),
  • compositions were separately loaded into identical trigger spray bottles and sprayed simultaneously from a single unit onto the same region of a tile prepared as described above while the tile was maintained with a near vertical slope. A small amount of foam formed on the surface of the tile and remained. It was determined that aged (autoclaved) mould was partially bleached over a period of 20 min whereas substantial bleaching of fresh mould occurred in the same period. After overnight treatment (around 14 hours) nearly complete bleaching of both fresh and aged mould was observed.
  • Figures 1 and la shows container [1] with draw tube [2] and valve means [3] in the upper surface [4].
  • FIG 1 the container [1] is assembled together with a second container [11] and a spraying and pumping head [10].
  • the spraying and pumping head When the spraying and pumping head is operated, liquid is drawn by pump means within the head from each of the containers [1] and [11], mixed, and ejected in the form of a spray via nozzle [12].
  • FIGs 2 and 2a show detail of the valve means [3] in the upper surface [4] with the pumping and spraying head [10] removed.
  • the valve means [3] comprise a cylindrical body with openings at opposed ends.
  • the body houses a spring means such as helical spring [7] and a check element such as ball [6]. Unless disturbed, the spring means [7] urges the check element [6] against a valve seat [7a] to prevent flow of liquid from within the cylindrical body into the draw tube [2].
  • the pumping means within the pumping and spraying head [10] are connected to the valve means [3].
  • Latching means, such as fittings [5] are provided to assist and maintain engagement of the valve means [3] with the spraying and pumping head [10].
  • means are provided to prevent egress of liquid from within container [1] before the container[1] is attached to the spraying and pumping head.
  • said means comprise a membrane [9] which closes the upper opening of the cylindrical body until pierced by an element within the spraying and pumping head: in this embodiment the seat of the spring [7] is provided by stop [9a] upon which defines an aperture closed by the membrane.
  • said means comprise a second ball valve which comprises a valve seat [8a] against which ball [8] is urged by spring 7.
  • a second ball valve which comprises a valve seat [8a] against which ball [8] is urged by spring 7.
  • an element within the spraying and pumping head pushes the ball [8] off the seat [8a] when the valve means [3] are engaged with the spraying and pumping head.
  • the second ball valve closes when the container [1] is detached from the spraying and pumping head [10].
  • FIG 3 shows further detail of the valve means [3] in the upper surface [4] with the pumping and spraying head [10] removed.
  • the valve means [3] comprise a cylindrical body with openings at opposed ends.
  • the body again houses a spring means such as helical spring [7] and a check element such as ball [6].
  • Latching means, such as fittings [5] are provided to assist and maintain engagement of the container with the spraying and pumping head [10].
  • Figure 3 also shows a venting aperture [13] and a porous plug [14] located between the body and the outer shroud [15].
  • the venting aperture [13] allows gas generated within the container [1] to escape.
  • the aperture [13] also allows air to flow into the container so as to equalise the pressure within the container with the ambient when the liquid contents of the container are removed by the spraying and pumping head via the draw tube [2].
  • pumping means within the spraying and pumping head [10] generates a partial vacuum in the cylindrical body: excess pressure within the container [1] forces liquid up the draw tube [2] and urges ball [6] off the seat [6a] against the resistance of the spring [7]. Liquid can then flow from the container [1] to into the spraying and pumping head.
  • liquids from containers [1] and [11] are mixed prior to ejection through the nozzle [12]. When operation of the spraying and pumping head ceases, flow of the mixed liquids back into container [1] is prevented by ball [6].

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
EP95903289A 1993-12-07 1994-11-25 Two-part cleaning composition comprising at least one peroxide compound Revoked EP0733097B1 (en)

Applications Claiming Priority (9)

Application Number Priority Date Filing Date Title
GB9325046 1993-12-07
GB939325046A GB9325046D0 (en) 1993-12-07 1993-12-07 Two part cleaning composition comprising peroxide
GB9406972A GB9406972D0 (en) 1994-04-08 1994-04-08 Two part cleaning composition comprising peroxide and container suitable therefor
GB9406972 1994-04-08
GB9413098A GB9413098D0 (en) 1994-06-29 1994-06-29 Two part cleaning composition comprising peroxide
GB9413098 1994-06-29
GB9415908 1994-08-05
GB9415908A GB9415908D0 (en) 1994-08-05 1994-08-05 Package for liquids and package containing liquids
PCT/EP1994/003924 WO1995016023A1 (en) 1993-12-07 1994-11-25 Two-part cleaning composition comprising at least one peroxide compound

Publications (2)

Publication Number Publication Date
EP0733097A1 EP0733097A1 (en) 1996-09-25
EP0733097B1 true EP0733097B1 (en) 1998-10-21

Family

ID=27451090

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95903289A Revoked EP0733097B1 (en) 1993-12-07 1994-11-25 Two-part cleaning composition comprising at least one peroxide compound

Country Status (12)

Country Link
EP (1) EP0733097B1 (ja)
JP (1) JPH09506130A (ja)
CN (1) CN1141647A (ja)
AU (1) AU701927B2 (ja)
BR (1) BR9408256A (ja)
CA (1) CA2176224A1 (ja)
DE (1) DE69414131T2 (ja)
ES (1) ES2122520T3 (ja)
HU (1) HU219545B (ja)
MY (1) MY112266A (ja)
TW (1) TW288997B (ja)
WO (1) WO1995016023A1 (ja)

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DE10358536B4 (de) * 2003-12-13 2006-05-18 Henkel Kgaa Mehrkomponenten-Thin-To-Thick-System
US9789216B2 (en) 2012-12-14 2017-10-17 Saban Ventures Pty Limited Synergistic disinfection enhancement
US10206404B2 (en) 2012-12-14 2019-02-19 Saban Ventures Pty Limited Disinfectant

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US5767055A (en) * 1996-02-23 1998-06-16 The Clorox Company Apparatus for surface cleaning
AU1962997A (en) * 1996-02-23 1997-09-10 Clorox Company, The Composition and apparatus for surface cleaning
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DE19644653A1 (de) * 1996-10-26 1998-04-30 Diversey Gmbh Verfahren und Vorrichtung zur Reinigung von mit Fett-, Stärke- und/oder Eiweißschmutz hochbelasteten Flächen, insbesondere in der Lebensmittelindustrie
AU6256098A (en) * 1997-02-05 1998-08-25 S.C. Johnson & Son, Inc. Bleaching cleaner that foams
EP0916334A1 (en) * 1997-11-07 1999-05-19 Unilever Plc Detergent composition
EP0997525A1 (en) 1998-10-30 2000-05-03 The Procter & Gamble Company Process of cleaning carpets with a composition comprising a poly (vinyl methyl ether/maleic acid) copolymer
US6548470B1 (en) 1998-12-14 2003-04-15 The Procter & Gamble Company Bleaching compositions
EP1010751B1 (en) * 1998-12-14 2005-04-20 The Procter & Gamble Company Bleaching compositions
EP1010750A1 (en) * 1998-12-14 2000-06-21 The Procter & Gamble Company Bleaching compositions
GB2373511B (en) * 1999-03-18 2003-10-15 Mark Gary Mullane Cleaning formulation
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JPH09506130A (ja) 1997-06-17
TW288997B (ja) 1996-10-21
AU701927B2 (en) 1999-02-11
DE69414131D1 (de) 1998-11-26
BR9408256A (pt) 1996-12-10
HUT76860A (en) 1997-12-29
CN1141647A (zh) 1997-01-29
CA2176224A1 (en) 1995-06-15
MY112266A (en) 2001-05-31
AU1240695A (en) 1995-06-27
ES2122520T3 (es) 1998-12-16
WO1995016023A1 (en) 1995-06-15
HU9601562D0 (en) 1996-08-28
DE69414131T2 (de) 1999-03-11
EP0733097A1 (en) 1996-09-25
HU219545B (hu) 2001-05-28

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