WO1995016023A1 - 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
WO1995016023A1
WO1995016023A1 PCT/EP1994/003924 EP9403924W WO9516023A1 WO 1995016023 A1 WO1995016023 A1 WO 1995016023A1 EP 9403924 W EP9403924 W EP 9403924W WO 9516023 A1 WO9516023 A1 WO 9516023A1
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WO
WIPO (PCT)
Prior art keywords
composition
kit according
peroxide
compositions
alkaline
Prior art date
Application number
PCT/EP1994/003924
Other languages
French (fr)
Inventor
Gillian Smith
Royston Reginald Smith
Original Assignee
Unilever Plc
Unilever N.V.
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
Priority to GB9325046.2 priority Critical
Priority to GB939325046A priority patent/GB9325046D0/en
Priority to GB9406972A priority patent/GB9406972D0/en
Priority to GB9406972.1 priority
Priority to GB9413098A priority patent/GB9413098D0/en
Priority to GB9413098.6 priority
Priority to GB9415908.4 priority
Priority to GB9415908A priority patent/GB9415908D0/en
Application filed by Unilever Plc, Unilever N.V. filed Critical Unilever Plc
Publication of WO1995016023A1 publication Critical patent/WO1995016023A1/en
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=27451090&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO1995016023(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING LIQUIDS OR OTHER FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05BSPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B11/00Single-unit, i.e. unitary, hand-held apparatus comprising a container and a discharge nozzle attached thereto, in which flow of liquid or other fluent material is produced by the muscular energy of the operator at the moment of use or by an equivalent manipulator independent from the apparatus
    • B05B11/30Single-unit, i.e. unitary, hand-held apparatus comprising a container and a discharge nozzle attached thereto, in which flow of liquid or other fluent material is produced by the muscular energy of the operator at the moment of use or by an equivalent manipulator independent from the apparatus the flow being effected by a pump
    • B05B11/3081Arrangements for pumping several liquids or other fluent materials from several containers, e.g. for mixing them at the moment of pumping
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials characterised by their shape or physical properties
    • C11D17/04Detergent materials characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3947Liquid compositions

Abstract

Improved cleaning performance, especially as regards the removal of moulds, can be achieved by the use of two separate liquid compositions, a first of which contains an acid or neutral composition which comprises a peroxide and a second of which contains an alkaline composition, said first and second compositions being stored separately and sprayed from a single unit to a common point. By ensuring that these compositions are sprayed, either sequentially or simultaneously onto a surface where they react together to produce an alkaline peroxide solution, it is possible to overcome the problems of instability on storage and ensure that the mixed compositions are delivered at a pH at which the peroxide compound is active as a bleaching agent.

Description

TWO PART CLEANING COMPOSITION COMPRISING AT LEAST ONE PEROXIDE COMPOUND

FIELD OF THE INVENTION

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. By peroxide compound is meant a compound comprising a peroxy (HOO-) group, including hydrogen peroxide and both organic and inorganic peroxides.

BACKGROUND TO THE INVENTION

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. One problem with said compositions is that the hypochlorite has an unpleasant odour and, when sprayed, hypochlorite solutions can produce droplets which cause significant respiratory irritation.

Other bleaching agents are known, particularly peroxides. However, 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.

Other two-part peroxide based compositions are disclosed in JP-A-60/038497 (LION BRANDS), which relates to a foaming, two-part drain cleaning composition which comprises:

a) 0.5-50%wt hydrogen peroxide,

b) alkali, having an alkalinity 0.1-50% based on sodium hydroxide,

c) surface active agent in (a) or (b) , and,

d) terpene alcohol/cyclic terpene alcohol in (a) or (b) .

The 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.

Other forms of simultaneous delivery of two components are known. US 3760986 (CASTNER et al: 1973), discloses a dispensing bottle for dispensing two separate fluids to a common point. Such 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.

The device disclosed in 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.

Some attention has been given to the provision of replaceable and/or refillable bottles in the general type of dual reservoir packaging mentioned above: e.g. EP

427609 (S.T.E.P.: 1991) and in WO/90/01959 (CORUS MEDICAL CORP: 1990) disclose spray means for attachment to a pair of bottles. In the first of these separate pumps are provided in each of the bottles. In the latter, the pumps are provided within the spraying heads and the bottles are connected to the spraying head by being impaled on needles which act as draw tubes.

US 4826048 (Pfeiffer: 1989) 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 (Proctor: 1992) discloses a dispenser with a single pump and a pair of bottles which can be detached for refilling or replacement.

BRIEF DESCRIPTION OF THE INVENTION

We have now determined that improved cleaning performance, especially as regards the removal of moulds, can be achieved by the use of two separate liquid compositions, a first of which contains an acid or neutral composition which comprises a peroxide and a second of which contains an alkaline composition, said first and second compositions being stored separately and sprayed from a single unit to a common point.

By ensuring that these compositions are sprayed, either sequentially or simultaneously onto a surface, whereby they react together to produce an alkaline peroxide composition, it is possible to overcome the problems of instability on storage and ensure that the mixed compositions are delivered at a pH at which the peroxide compound is active as a bleaching agent.

DETAILED DESCRIPTION OF THE INVENTION

As described above, the invention provides a kit of parts comprising: a) a liquid, acidic or neutral composition comprising a peroxide compound stable at the pH of the acidic or neutral composition, and,

b) a liquid, alkaline composition,

said compositions being contained in separate reservoirs of a single unit adapted to produce a spray of at least one of (a) and (b) .

By 'spray' 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.

It is preferred that the unit is adapted to produce a spray comprising a mixture of compositions (a) and (b) . In the alternative 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:

a) mixing a first, liquid, acidic or neutral composition comprising a peroxide compound with a second, liquid, alkaline composition so as to form an alkaline peroxide composition,

b) spraying the product of step (a) onto a surface to be cleaned. It is particularly preferred that 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.

Peroxides

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.

As mentioned above, 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.

In the alternative, it is envisaged that other peroxide compounds can be employed. Among the preferred alternatives are peracids, particularly peracetic acid and persulphates particularly potassium mono-persulphate. While 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. Thus, in the presence of peracetic acid the diacetyl ester of ethylene glycol is a suitable solvent.

Preferred levels of peroxide compound range from l-50%wt of the composition containing the peroxide compound. For hydrogen peroxide, levels below 4%wt peroxide are less effective as bleaching agents, whereas solutions containing more than 50%wt peroxide can be hazardous. For peracetic and persulphates levels of l-10%wt in the neat compositions are preferred.

Mixing Ratio

As will be understood from the above an important aspect of the present invention is that two components are mixed either before or during the mixing 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.

pH modifying agents

In order to attain the correct pH in the compositions which embody the present invention it can be necessary to add pH modifying agents.

In the case of acid solutions containing peroxides, further acidification may not be necessary. As is illustrated by the examples given hereafter, aqueous solutions according to the present invention can attain a natural 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. In the case of 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. However, the alkaline composition should preferably not have a pH so high as to be hazardous to use.

Where further acidification is required mineral or organic acids, with optional buffer salts, can be employed provided that these acids and salts are not peroxide sensitive. We have determined that 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.

In the method aspects of the present invention 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. As mentioned above, 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. For hydrogen peroxide the preferred pH after mixing with alkali is pH 10-12, more preferably ph 11-11.5. For monopersulphate and peracetic acid the preferred pH after mixing is around pH 8.

Thickeners

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.

We have determined that the presence of small amounts of thickener in at least one of said first and second compositions modifies the spraying behaviour of the composition to prevent the formation of an irritant mist. 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.

We have determined that certain 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.

Second, 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. Either or both of these characteristics of thickeners may be exploited in embodiments of the invention.

Typical levels of thickener range from 0.05-5%wt.

Typically, the thickener component is a polymer.

Where it is required that the compositions thicken on mixing, the most preferred thickeners are those which exhibit a marked increase in composition viscosity at above the pH of the acidic peroxide-containing composition.

Thus, in certain embodiments of the invention, 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.

We have found that a 2%wt solution of Acusol 820 (RTM ex. Rohm and Haas) an acrylate copolymer, forms a viscous gel at pH 6, whereas very little thickening is exhibited at pH 3.0. Lower levels of this polymer are employed when slight thickening so as to modify spraying behaviour are required. We have determined that acceptable spraying behaviour can be obtained when levels of this thickener of 0.05-0.5%wt are employed in the alkaline component. Alternative thickeners are those which exhibit poor thickening at very high pH. In embodiments of the invention where thickening on mixing is required, 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.

From the above it can be seen that it is not essential for all embodiments of the invention that 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.

Cationic Surfactant

It is preferred that 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.

Preferably Rl and R2 are C8-C18 alkyl and R2 and R3 are C1-C4 alkyl. Preferably X is a halide.

Particularly preferred cationics include dialkyl dimethyl ammonium halides. We have determined that didecyl dimethyl ammonium chloride is particularly suitable.

We have determined that the abovementioned cationics are stable both in the alkaline solution and the acid peroxide solution and that no significant loss of peroxide occurs when the cationic is present in the peroxide compound containing composition, when the peroxide compound is hydrogen peroxide.

Other Surfactants

Other 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.

Whether the surfactants are required to be peroxide-stable or not will be determine whether the surfactant is incorporated in the acid/neutral or alkaline composition.

Preferred, 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.

Where the surfactants are unstable in acidic, peroxide containing compositions the surfactant can be provided as a component of the alkaline component. We have determined that 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 Minors

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.

Other minor components which are optional are 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.

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 ( ethylene phosphonic acid) (Dequest 2040, RTM), diethylene triamine penta(methylene phosphonic acid) (Dequest 2060, RTM). The phosphonic acid derivatives are particularly preferred.

It is preferred that 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.

While the reactions of peroxides with the transition metals have previously been though detrimental, the reaction can be used to advantage in the compositions of the present invention. In an embodiment of the invention the alkaline component further comprises a transition metal or halide bleach decomposing agent which reacts with the acidic or neutral peroxide containing composition.

According to an embodiment of the invention in which the acidic or neutral component comprises monopersulphate as the peroxy compound, the alkaline component comprises a halide, preferably a bromide. We have determined that when acidic monopersulphate solution and alkaline bromide solution are sprayed together onto a surface, so as to give a final pH of around 8, a reaction occurs which produces hypobromite, an effective bleaching agent at pH 6 and above.

As mentioned above, solvents can be included in the compositions of the invention so as to solvate components of the compositions. In addition, 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.

Apparatus

The apparatus aspect of the present invention provides for a two-part container which enables simultaneous or sequential spraying of compositions which comprise:

a) a liquid, acidic or neutral, composition comprising a peroxide compound stable at the pH of the composition, and,

b) a liquid, alkaline composition.

Such containers are known from the art and are described in US 3760986 (CASTNER et al: 1973), which discloses a dispensing bottle for dispensing two separate fluids to a common point.

It is particularly advantageous that 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. Whereas 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.

In such an embodiment as is described above it is essential that the 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.

In preferred embodiments of the invention said 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. 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. In one such embodiment 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.

A further advantage of containers according to the preferred embodiment of the present invention is that the 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.

In order that the present invention can be further understood it will be described hereinafter by reference to non-limiting examples and with reference to the accompanying figures wherein:

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. EXAMPLES

EXAMPLE 1: compositions

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.

Two separate solutions, 'Composition A' and 'Composition B' were made up as follows, the components being added to distilled water to reach the given final concentration. Additions were in the order listed, with a five minute stirring period between each addition.

C Coommppoossiittiioonn A A::

0, .15% Methocell J12MS (hydroxy propyl methyl cellulose) ,

0, .2% DEQUEST 2060 (TM ex. Monsanto), 6 6., .00%% 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.

2% 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

44.. .00%% NE-208T (TM ex. Nippon Oil) primary alcohol ethoxylate, nonionic surfactant,

1. .0% Didecyl dimethyl ammonium chloride,

4. .0% BUTYL DIGOL (TM) ,

These 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.

It was determined that optimum bleaching was achieved with a 1:1 mixing ratio. Storage tests for up to 32 days showed that the was comparatively little loss of peroxide and/or cationic in the separately stored solutions.

EXAMPLE II: apparatus

Figures 1 and la shows container [1] with draw tube [2] and valve means [3] in the upper surface [4] .

In figure 1 the container [1] is assembled together with a second container [11] and a spraying and pumping head [10] . 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] .

Figures 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] . When assembled as in figure 1 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] .

In the embodiments shown in figures 2 and 2a means are provided to prevent egress of liquid from within container [1] before the container[1] is attached to the spraying and pumping head. In figure 2a 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. A particular advantage of this embodiment is that it is tamper-evident.

In figure 2 said means comprise a second ball valve which comprises a valve seat [8a] against which ball [8] is urged by spring 7. In the embodiment shown in figure 2 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. A particular advantage of this embodiment is that the second ball valve closes when the container [1] is detached from the spraying and pumping head [10] .

Figure 3 shows further detail of the valve means [3] in the upper surface [4] with the pumping and spraying head

[10] removed. As in figures 2 and 2a 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]. In use, 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. Within the spraying and pumping head [10] 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] .

Claims

1. A kit of parts comprising:
a) an liquid, acidic or neutral composition comprising a peroxide compound stable at the pH of the composition, and,
b) an liquid, alkaline composition,
said compositions being contained in separate reservoirs of a single unit adapted to produce a spray of at least one of (a) and (b) .
2. Kit according to claim 1 wherein at least one of composition (a) or composition (b) further comprises a cationic surfactant.
3. Kit according to claim 2 wherein the cationic surfactant is a quaternary ammonium compounds of the formula:
Rl.R2.R3.R4.NX
wherein R1-R4 are alkyl and X is an anion.
Kit according to claim 3 wherein Rl and R2 are C8-C18 alkyl and R2 and R3 are C1-C4 alkyl.
Kit according to claim 1 wherein component (a) comprises hydrogen peroxide, a monopersulphate salt, peracetic acid or a mixture thereof. 6. Kit according to claim 1 wherein at least one of components (a) and (b) further comprises a thickener component .
7. Kit according to claim 6 wherein component (a) comprises a thickening modified cellulose.
8. Kit according to claim 6 wherein component (a) comprises an acrylic crosslinked polymer.
9. Kit according to claim 1 wherein at least one of components (a) and (b) further comprises an ethoxylated alcohol anionic surfactant.
10. Kit according to claim 1 wherein at least component
(a) further comprises a metal ion complexing agent.
11. Kit according to claim 1 wherein at least component
(b) further comprises a glycol ether solvent.
12. A method of cleaning hard surfaces which comprises the steps of:
a) mixing a first, liquid, acidic or neutral composition comprising a peroxide compound with a second, liquid, alkaline composition so as to form an alkaline peroxide composition,
b) spraying the product of step (a) onto a surface to be cleaned.
PCT/EP1994/003924 1993-12-07 1994-11-25 Two-part cleaning composition comprising at least one peroxide compound WO1995016023A1 (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
GB9325046.2 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
GB9406972.1 1994-04-08
GB9413098.6 1994-06-29
GB9413098A GB9413098D0 (en) 1994-06-29 1994-06-29 Two part cleaning composition comprising peroxide
GB9415908.4 1994-08-05
GB9415908A GB9415908D0 (en) 1994-08-05 1994-08-05 Package for liquids and package containing liquids

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
EP19950903289 EP0733097B1 (en) 1993-12-07 1994-11-25 Two-part cleaning composition comprising at least one peroxide compound
CA 2176224 CA2176224A1 (en) 1993-12-07 1994-11-25 Two-part cleaning composition comprising at least one peroxide compound
DE1994614131 DE69414131T2 (en) 1993-12-07 1994-11-25 Two-part cleaning composition which contains at least one peroxide compound
HU9601562A HU219545B (en) 1993-12-07 1994-11-25 Two part cleaning composition at least one peroxide compound and method for cleaning solid surfaces
BR9408256A BR9408256A (en) 1993-12-07 1994-11-25 parts kit and process for cleaning hard surfaces
JP51592495A JPH09506130A (en) 1993-12-07 1994-11-25 Two-part cleaning composition comprising at least one peroxide compound
AU12406/95A AU701927B2 (en) 1993-12-07 1994-11-25 Two part cleaning composition comprising at least one peroxide compound
DE1994614131 DE69414131D1 (en) 1993-12-07 1994-11-25 Two-part cleaning composition which contains at least one peroxide compound

Publications (1)

Publication Number Publication Date
WO1995016023A1 true WO1995016023A1 (en) 1995-06-15

Family

ID=27451090

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1994/003924 WO1995016023A1 (en) 1993-12-07 1994-11-25 Two-part cleaning composition comprising at least one peroxide compound

Country Status (10)

Country Link
EP (1) EP0733097B1 (en)
JP (1) JPH09506130A (en)
AU (1) AU701927B2 (en)
BR (1) BR9408256A (en)
CA (1) CA2176224A1 (en)
DE (2) DE69414131T2 (en)
ES (1) ES2122520T3 (en)
HU (1) HU219545B (en)
TW (1) TW288997B (en)
WO (1) WO1995016023A1 (en)

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WO1997031087A1 (en) * 1996-02-23 1997-08-28 The Clorox Company Composition and apparatus for surface cleaning
WO1997045519A2 (en) * 1996-05-28 1997-12-04 Warwick International Group Ltd. Alkaline peroxide liquid detergent composition
EP0826027A1 (en) * 1996-02-23 1998-03-04 The Clorox Company Composition and apparatus for surface cleaning
WO1998018898A1 (en) * 1996-10-26 1998-05-07 Unilever N.V. Process and device for cleaning surfaces which are heavily soiled with grease, starch and/or proteins, especially in the food processing industry
WO1998033880A1 (en) * 1997-02-05 1998-08-06 S. C. Johnson & Son, Inc. Bleaching cleaner that foams
EP0916334A1 (en) * 1997-11-07 1999-05-19 Unilever N.V. 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
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EP1010750A1 (en) * 1998-12-14 2000-06-21 THE PROCTER & GAMBLE COMPANY Bleaching compositions
WO2000061713A1 (en) * 1999-04-12 2000-10-19 Unilever N.V. Multiple component bleaching compositions
WO2000061712A1 (en) * 1999-04-12 2000-10-19 Unilever N.V. Multiple component hard surface cleaning compositions
WO2001065939A1 (en) * 2000-03-09 2001-09-13 Unilever N.V. Bactericidal compositions comprising a quaternary ammonium salt
GB2347937B (en) * 1999-03-18 2002-09-11 Mark Gary Mullane Cleaning formulation
GB2373511A (en) * 1999-03-18 2002-09-25 Mark Gary Mullane Cleaning formulation
US6472360B1 (en) 1999-04-12 2002-10-29 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Multiple component hard surface cleaning compositions
US6479444B1 (en) 1999-07-08 2002-11-12 The Clorox Company Foaming drain cleaner
EP1275708A1 (en) * 2001-07-10 2003-01-15 Kao Corporation Two-agent type liquid bleaching compositions
US6548470B1 (en) 1998-12-14 2003-04-15 The Procter & Gamble Company Bleaching compositions
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US6660702B2 (en) 2000-12-08 2003-12-09 The Clorox Company Binary foaming drain cleaner
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GB2392917A (en) * 2002-09-10 2004-03-17 Reckitt Benckiser Inc Two-part composition containing hydrogen peroxide
GB2395526A (en) * 2002-09-13 2004-05-26 Bissell Homecare Inc Manual spray cleaner
WO2004053042A1 (en) 2002-12-06 2004-06-24 Henkel Kommanditgesellschaft Auf Aktien Multicomponent liquid detergent
GB2400379A (en) * 2003-04-10 2004-10-13 Reckitt Benckiser Nv Two-component stain treating composition
WO2005035707A1 (en) * 2003-10-06 2005-04-21 The Procter & Gamble Company Dual-compartment laundry composition containing peroxyacids
WO2005066323A1 (en) * 2004-01-06 2005-07-21 Reckitt Benckiser N.V. Carpet treating composition
WO2006007371A1 (en) * 2004-06-16 2006-01-19 S. C. Johnson & Son, Inc. Two part cleaning composition
EP1623725A2 (en) * 2003-12-19 2006-02-08 Ethicon Inc. Kit and apparatus for preparing germicidal compositions comprising phthalaldehyde
US7109155B2 (en) 2002-12-07 2006-09-19 Clariant Gmbh Liquid bleaching composition components comprising amphiphilic polymers
DE102006006153A1 (en) * 2006-02-10 2007-08-23 Rational Ag Cleaning agent for cleaning interior of equipment, has two cleaning components, where both the cleaning components have a common cleaning effect
WO2007093315A1 (en) * 2006-02-14 2007-08-23 Henkel Ag & Co. Kgaa Multicomponent thin-to-thick system
US7291649B2 (en) 2005-06-29 2007-11-06 Ethicon, Inc. Forming germicidal aromatic dialdehydes with acetals
US7390837B2 (en) 2004-01-30 2008-06-24 Ethicon, Inc. Germicidal compositions containing phenylmalonaldehyde-type compounds, or mixtures of phenylmalonaldehyde-type compounds and phthalaldehydes, and methods of using such compositions for disinfection or sterilization
US7476767B2 (en) 2004-01-30 2009-01-13 Ethicon, Inc. Alpha-hydroxy sulfonate aldehydes, germicidal compositions containing the alpha-hydroxy sulfonate aldehydes, or mixtures of alpha-hydroxy sulfonate aldehydes and phthalaldehydes, and methods of using the compounds or compositions for disinfection or sterilization
WO2010012969A1 (en) * 2008-08-01 2010-02-04 Reckitt Benckiser (Uk) Limited Composition
US7737103B2 (en) * 2003-12-13 2010-06-15 Henkel Ag & Co. Kgaa Multicomponent thin-to-thick system
EP2204092A1 (en) 2008-12-30 2010-07-07 Bissell Homecare, Inc. Manual sprayer with dual bag-on-valve assembly
US7857913B2 (en) * 2003-06-26 2010-12-28 Spindler William E Cleaning compound for cleaning surfaces in a food processing environment
US8349022B2 (en) 2009-03-11 2013-01-08 Kao Corporation Two-part hair dye
WO2015145399A1 (en) * 2014-03-28 2015-10-01 Fater S.P.A. Cleaning system comprising a sprayer bottle and a cleaning composition
US9476014B2 (en) 2013-02-14 2016-10-25 II Joseph M. Galimi Method for cleaning surfaces
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
US10226649B2 (en) 2007-04-27 2019-03-12 Kao Corporation Hair dyeing or bleaching method

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EP1541666B1 (en) 2002-07-29 2010-06-02 Kao Corporation Foamy composition for bleaching clothing
US6583103B1 (en) 2002-08-09 2003-06-24 S.C. Johnson & Son, Inc. Two part cleaning formula resulting in an effervescent liquid
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BRPI0809487B1 (en) 2007-04-27 2016-08-09 Kao Corp bleaching composition or hair dyeing in two parts
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EP0776966A1 (en) 1995-12-02 1997-06-04 THE PROCTER & GAMBLE COMPANY Liquid bleaching compositions packaged in spray-type dispenser and a process for pretreating fabrics therewith
WO1997031087A1 (en) * 1996-02-23 1997-08-28 The Clorox Company Composition and apparatus for surface cleaning
EP0826027A1 (en) * 1996-02-23 1998-03-04 The Clorox Company Composition and apparatus for surface cleaning
EP0826027A4 (en) * 1996-02-23 1999-12-08 Clorox Co Composition and apparatus for surface cleaning
US5767055A (en) * 1996-02-23 1998-06-16 The Clorox Company Apparatus for surface cleaning
WO1997045519A2 (en) * 1996-05-28 1997-12-04 Warwick International Group Ltd. Alkaline peroxide liquid detergent composition
WO1997045519A3 (en) * 1996-05-28 1998-02-19 Warwick Int Group Alkaline peroxide liquid detergent composition
AU723654B2 (en) * 1996-10-26 2000-08-31 Johnsondiversey, Inc. Process and device for cleaning surfaces which are heavily soiled with grease, starch and/or proteins, especially in the food processing industry
US5855217A (en) * 1996-10-26 1999-01-05 Diversey Lever, Inc. Process and device for cleaning surfaces which are heavily soiled with grease, starch and/or proteins, especially in the food processing industry
WO1998018898A1 (en) * 1996-10-26 1998-05-07 Unilever N.V. Process and device for cleaning surfaces which are heavily soiled with grease, starch and/or proteins, especially in the food processing industry
WO1998033880A1 (en) * 1997-02-05 1998-08-06 S. C. Johnson & Son, Inc. Bleaching cleaner that foams
EP0916334A1 (en) * 1997-11-07 1999-05-19 Unilever N.V. Detergent composition
US6114290A (en) * 1997-11-07 2000-09-05 Lever Brothers Company, Division Of Conopco, Inc. 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
WO2000036072A1 (en) * 1998-12-14 2000-06-22 The Procter & Gamble Company Bleaching compositions
EP1010751A3 (en) * 1998-12-14 2000-08-09 THE PROCTER & GAMBLE COMPANY Bleaching compositions
EP1010750A1 (en) * 1998-12-14 2000-06-21 THE PROCTER & GAMBLE COMPANY Bleaching compositions
EP1010751A2 (en) * 1998-12-14 2000-06-21 THE PROCTER & GAMBLE COMPANY Bleaching compositions
US6548470B1 (en) 1998-12-14 2003-04-15 The Procter & Gamble Company Bleaching compositions
US6869922B1 (en) 1999-03-18 2005-03-22 Mark Gary Mullane Cleaning formulation
GB2373511B (en) * 1999-03-18 2003-10-15 Mark Gary Mullane Cleaning formulation
GB2347937B (en) * 1999-03-18 2002-09-11 Mark Gary Mullane Cleaning formulation
GB2373511A (en) * 1999-03-18 2002-09-25 Mark Gary Mullane Cleaning formulation
US6391840B1 (en) * 1999-04-12 2002-05-21 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Multiple component bleaching compositions
AU752959B2 (en) * 1999-04-12 2002-10-03 Unilever Plc Multiple component hard surface cleaning compositions
US6472360B1 (en) 1999-04-12 2002-10-29 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Multiple component hard surface cleaning compositions
WO2000061713A1 (en) * 1999-04-12 2000-10-19 Unilever N.V. Multiple component bleaching compositions
WO2000061712A1 (en) * 1999-04-12 2000-10-19 Unilever N.V. Multiple component hard surface cleaning compositions
US6479444B1 (en) 1999-07-08 2002-11-12 The Clorox Company Foaming drain cleaner
WO2001065939A1 (en) * 2000-03-09 2001-09-13 Unilever N.V. Bactericidal compositions comprising a quaternary ammonium salt
US6916771B2 (en) 2000-12-08 2005-07-12 The Clorox Company Binary foaming drain cleaner
US6660702B2 (en) 2000-12-08 2003-12-09 The Clorox Company Binary foaming drain cleaner
EP1363709A1 (en) * 2001-02-01 2003-11-26 Becton, Dickinson and Company Surfactant/oxidizing agent solution and methods of use
EP1363709A4 (en) * 2001-02-01 2004-06-16 Becton Dickinson Co Surfactant/oxidizing agent solution and methods of use
EP1275708A1 (en) * 2001-07-10 2003-01-15 Kao Corporation Two-agent type liquid bleaching compositions
US6838424B2 (en) 2001-07-10 2005-01-04 Kao Corporation Two-agent type liquid bleaching compositions
AU2003246945B2 (en) * 2002-07-20 2009-03-26 Reckitt Benckiser Vanish B.V. Stain treating composition
WO2004009753A1 (en) * 2002-07-20 2004-01-29 Reckitt Benckiser N.V. Stain treating composition
AU2003246947B2 (en) * 2002-07-20 2008-10-23 Reckitt Benckiser Vanish B.V. Stain treating composition
GB2391479A (en) * 2002-08-09 2004-02-11 Reckitt Benckiser A two-part liquid hard surface cleaner
GB2392917A (en) * 2002-09-10 2004-03-17 Reckitt Benckiser Inc Two-part composition containing hydrogen peroxide
US8784504B2 (en) 2002-09-13 2014-07-22 Bissell Homecare, Inc. Carpet cleaning method
GB2432194A (en) * 2002-09-13 2007-05-16 Bissell Homecare Inc Manual spray cleaner
GB2395526B (en) * 2002-09-13 2007-05-16 Bissell Homecare Inc Manual spray cleaner
US20110139180A1 (en) * 2002-09-13 2011-06-16 Bissell Homecare, Inc. Manual spray cleaner and protectants
GB2432194B (en) * 2002-09-13 2007-09-12 Bissell Homecare Inc Manual spray cleaner
GB2395526A (en) * 2002-09-13 2004-05-26 Bissell Homecare Inc Manual spray cleaner
US8338354B2 (en) * 2002-09-13 2012-12-25 Bissell Homecare, Inc. Manual spray cleaner and protectants
WO2004053042A1 (en) 2002-12-06 2004-06-24 Henkel Kommanditgesellschaft Auf Aktien Multicomponent liquid detergent
US7109155B2 (en) 2002-12-07 2006-09-19 Clariant Gmbh Liquid bleaching composition components comprising amphiphilic polymers
GB2400379A (en) * 2003-04-10 2004-10-13 Reckitt Benckiser Nv Two-component stain treating composition
US7857913B2 (en) * 2003-06-26 2010-12-28 Spindler William E Cleaning compound for cleaning surfaces in a food processing environment
WO2005035707A1 (en) * 2003-10-06 2005-04-21 The Procter & Gamble Company Dual-compartment laundry composition containing peroxyacids
US7737103B2 (en) * 2003-12-13 2010-06-15 Henkel Ag & Co. Kgaa Multicomponent thin-to-thick system
EP1623725A2 (en) * 2003-12-19 2006-02-08 Ethicon Inc. Kit and apparatus for preparing germicidal compositions comprising phthalaldehyde
EP1623725A3 (en) * 2003-12-19 2007-05-30 Ethicon Inc. Kit and apparatus for preparing germicidal compositions comprising phthalaldehyde
AU2004312194B2 (en) * 2004-01-06 2010-05-13 Reckitt Benckiser Vanish B.V. Carpet treating composition
WO2005066323A1 (en) * 2004-01-06 2005-07-21 Reckitt Benckiser N.V. Carpet treating composition
US7476767B2 (en) 2004-01-30 2009-01-13 Ethicon, Inc. Alpha-hydroxy sulfonate aldehydes, germicidal compositions containing the alpha-hydroxy sulfonate aldehydes, or mixtures of alpha-hydroxy sulfonate aldehydes and phthalaldehydes, and methods of using the compounds or compositions for disinfection or sterilization
US7390837B2 (en) 2004-01-30 2008-06-24 Ethicon, Inc. Germicidal compositions containing phenylmalonaldehyde-type compounds, or mixtures of phenylmalonaldehyde-type compounds and phthalaldehydes, and methods of using such compositions for disinfection or sterilization
WO2006007371A1 (en) * 2004-06-16 2006-01-19 S. C. Johnson & Son, Inc. Two part cleaning composition
US7291649B2 (en) 2005-06-29 2007-11-06 Ethicon, Inc. Forming germicidal aromatic dialdehydes with acetals
DE102006006153A1 (en) * 2006-02-10 2007-08-23 Rational Ag Cleaning agent for cleaning interior of equipment, has two cleaning components, where both the cleaning components have a common cleaning effect
WO2007093315A1 (en) * 2006-02-14 2007-08-23 Henkel Ag & Co. Kgaa Multicomponent thin-to-thick system
US10226649B2 (en) 2007-04-27 2019-03-12 Kao Corporation Hair dyeing or bleaching method
WO2010012969A1 (en) * 2008-08-01 2010-02-04 Reckitt Benckiser (Uk) Limited Composition
US8791057B2 (en) 2008-08-01 2014-07-29 Reckitt & Colman (Overseas) Limited Composition
EP2204092A1 (en) 2008-12-30 2010-07-07 Bissell Homecare, Inc. Manual sprayer with dual bag-on-valve assembly
US8349022B2 (en) 2009-03-11 2013-01-08 Kao Corporation Two-part hair dye
US9789216B2 (en) 2012-12-14 2017-10-17 Saban Ventures Pty Limited Synergistic disinfection enhancement
US9872930B2 (en) 2012-12-14 2018-01-23 Saban Ventures Pty Limited Synergistic disinfection enhancement
US10206404B2 (en) 2012-12-14 2019-02-19 Saban Ventures Pty Limited Disinfectant
US9476014B2 (en) 2013-02-14 2016-10-25 II Joseph M. Galimi Method for cleaning surfaces
WO2015145399A1 (en) * 2014-03-28 2015-10-01 Fater S.P.A. Cleaning system comprising a sprayer bottle and a cleaning composition

Also Published As

Publication number Publication date
TW288997B (en) 1996-10-21
AU701927B2 (en) 1999-02-11
JPH09506130A (en) 1997-06-17
ES2122520T3 (en) 1998-12-16
HU219545B (en) 2001-05-28
EP0733097B1 (en) 1998-10-21
DE69414131D1 (en) 1998-11-26
AU1240695A (en) 1995-06-27
BR9408256A (en) 1996-12-10
HU9601562D0 (en) 1996-08-28
DE69414131T2 (en) 1999-03-11
EP0733097A1 (en) 1996-09-25
CA2176224A1 (en) 1995-06-15
HUT76860A (en) 1997-12-29

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