TWO-PART DISINFECTANT SYSTEM COMPRISING A COLOUR INDICATOR

Abstract

A disinfectant system comprises a first part comprising a first reagent in a carrier medium; and a second part which is miscible with the first part and which comprises a second reagent in a carrier medium. The first reagent and the second reagent will react when mixed to provide a chlorine dioxide disinfecting composition. The first part or the second part further comprises an anthocyanin, anthocyanidin or betanin dyestuff, which oxidises in the presence of chlorine dioxide to produce a visible colour change upon mixing of the first reagent with the second reagent, and the colour change does not occur upon exposure of the dyestuff-containing part to a disinfecting composition comprising hydrogen peroxide and/or peracetic acid.

Claims

1. A disinfectant system comprising: (a) a first part comprising a first reagent in a carrier medium; and (b) a second part which is miscible with the first part and which comprises a second reagent in a carrier medium; wherein the first reagent and the second reagent will react when the first and second parts are mixed to provide a chlorine dioxide disinfecting composition; the first part or the second part further comprising a dyestuff that oxidises in the presence of chlorine dioxide to produce a visible colour change upon mixing of the first part with the second part; wherein said colour change does not occur upon exposure of the dyestuff-containing part to a hydrogen peroxide disinfectant and/or a peracetic acid disinfectant; wherein the dyestuff is an anthocyanin dyestuff, an anthocyanidin dyestuff, or a betanin dyestuff.

2. A disinfectant system according to claim 1, wherein the dyestuff comprises an anthocyanin dyestuff selected from the group consisting of black carrot extract, purple carrot extract, haskapa berry extract, and blackcurrant extract.

3. A disinfectant system according to claim 1, wherein the dyestuff comprises an anthocyanidin dyestuff selected from the group consisting of bilberry extract and blue pea extract.

4. A disinfectant system according to claim 1, wherein the dyestuff comprises a betanin dyestuff selected from the group consisting of red beetroot powder and beetroot juice concentrate.

5. A disinfectant system according to claim 1, wherein the dyestuff changes from coloured to colourless in the presence of chlorine dioxide.

6. A disinfectant system according to claim 1, wherein the first reagent comprises a metal chlorite and the second reagent comprises an acid.

7. A disinfectant system according to claim 1, wherein the first part is contained in a dispenser whereby it may be dispensed as a fluid.

8. A disinfectant system according to claim 1, wherein the second part is absorbed or impregnated in at least one wipe.

9. A disinfectant system according to claim 1, wherein the first part and the second part each comprise liquids.

10. A disinfectant system according to claim 1, wherein the first part and the second part each comprise foams.

11. A disinfectant system according to claim 6, wherein the second part comprises the dyestuff.

12. A disinfectant system according to claim 1, wherein the first part or the second part comprises between about 0.1 wt% and about 2 wt% of the dyestuff.

13. A disinfectant system according to claim 1, wherein, after mixing of the first reagent with the second reagent, substantially all of the dyestuff is oxidised by the resulting chlorine dioxide.

14. A disinfectant system according to claim 1, wherein said colour change does not occur upon exposure of the dyestuff-containing part to a quaternary ammonium compound-based disinfecting composition.

15. A disinfectant system according to claim 1, wherein said colour change does not occur upon exposure of the dyestuff-containing part to a triamine-based disinfecting composition.

16. A method of verifying the production of a chlorine dioxide disinfecting composition using the disinfectant system of claim 1, the method comprising: mixing the first part and the second part; during mixing of the first part and the second part, observing said colour change; and determining that the chlorine dioxide disinfecting composition has been produced when said colour change is complete and spatially uniform.

17-21. (canceled)

22. A disinfectant system comprising: (a) a first part comprising a first reagent in a carrier medium; and (b) a second part which is miscible with the first part and which comprises a second reagent in a carrier medium; wherein the first reagent and the second reagent will react when the first and second parts are mixed to provide a chlorine dioxide disinfecting composition; the first part or the second part further comprising a dyestuff selected from the group consisting of black carrot extract, purple carrot extract, haskapa berry extract, blackcurrant extract, bilberry extract, blue pea extract, red beetroot powder and beetroot juice concentrate.

23. A disinfectant system according to claim 22, wherein the dyestuff is black carrot extract.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0027] The invention will now be further described, by way of example only, with reference to the following drawings, in which:

[0028] FIGS. 1 and 2 show prior art disinfectant systems;

[0029] FIG. 3 shows a disinfectant system in accordance with an embodiment of the present invention;

[0030] FIG. 4 shows absorbance measurements as a function of wavelength for an anthocyanin dyestuff in one part of a two-part disinfectant system before and after activation with the other part of the disinfectant system;

[0031] FIG. 5 shows chlorine dioxide generation as a function of time for a disinfectant system including an anthocyanin dyestuff and for a disinfectant system not including a dyestuff;

[0032] FIG. 6 shows comparative examples of fabric wipes treated with different disinfecting compositions;

[0033] FIG. 7 and shows absorbance measurements as a function of wavelength for an anthocyanin dyestuff solution upon exposure to different disinfecting compositions; and

[0034] FIG. 8 is a schematic view of apparatus in accordance with another aspect of the invention.

DETAILED DESCRIPTION

[0035] The prior art systems illustrated in FIGS. 1 and 2 are suitable for use in the present invention, but with the difference that, in a first embodiment, the second part further comprises an anthocyanin dyestuff.

[0036] In the present example, the first part comprises less than 1% sodium chlorite, and less than 2.5% amphoteric surfactant. The remainder is deionised water. In this specification, all parts are by weight unless otherwise indicated. Operation of the pump trigger dispenses the first part as a foam.

[0037] The wipes 16 are impregnated with an aqueous acid solution (second part). In this example, the acid solution comprises 1-5% citric acid and 1% Antho Black Carrot Extract as the anthocyanin dyestuff. The remainder is deionised water.

[0038] The anthocyanin dyestuff provides the fabric wipe 16 (FIG. 3) with a characteristic colour. In this embodiment, the wipe 16 has a pinkish-red colour before the first part is added. We have found that, in the presence of chlorine dioxide, the anthocyanin dyestuff is readily oxidised to a non-coloured substance. This results in the wipe 16 losing its characteristic colour. The system provides a positive indication when chlorine dioxide has been generated and the action of generating the chlorine dioxide can be verified by the end user.

[0039] Use of a stable, selective dyestuff allows for the verification of not only the presence of chlorine dioxide but additionally the correct level of chlorine dioxide to ensure efficacy. The dyestuff also provides an environmental risk mitigator in the event of using the product outside of its recommended use temperature. The rationale is that the rate of chlorine dioxide generation is slower at colder temperatures and faster at higher temperatures. The rate of dye oxidation will be proportional to the level of chlorine dioxide generated.

[0040] Various dyestuffs were investigated for the ability to provide selectivity towards chlorine dioxide. In addition, the safety profile of each dye required assessment to ensure that during the oxidation process no harmful byproducts were formed which would have the potential to be detrimental to patient safety.

[0041] Potassium iodide, for example, exhibits a detectable colour change upon oxidation in the presence of chlorine dioxide, but also exhibits the same behaviour with other common oxidising disinfectants, such as hydrogen peroxide. Potassium iodide is therefore non-selective for chlorine dioxide and is not suitable for use in the present invention. Metal-based pigments are generally not suitable, as they are not readily oxidised by chlorine dioxide.

[0042] Research led to the finding that anthocyanin-based dyes, anthocyanidin-based dyes and betanin-based dyes are suitable for use in chlorine dioxide disinfectant systems because of ease of oxidation, selectivity and safety.

[0043] Anthocyanins, such as Antho Black Carrot Extract (AnthoCarrot), are a family of naturally derived pigments which are often responsible for the red-blue colours observed in fruits and vegetables. These compounds are readily found in food, being present in much of our produce as well as being used as natural dyes and food additives. Anthocyanins for food use are referred to by the E-number E163 and include E163(ii) Grape skin extract (Enociania, Eno), E163(iii) Blackcurrant extract, E163(iv) Purple corn colour, E163(v) Red cabbage colour, E163 (vi) Black carrot extract, E163 (vii) Purple sweet potato colour, E163 (viii) Red radish colour, E163(ix) Elderberry colour and E163(x) Hibiscus colour.

[0044] Anthocyanins have no reported toxicological information or warnings and are generally considered safe for use.

[0045] Anthocyanin (AnthoCarrot) is red when incorporated into a phase two liquid solution (i.e. the aqueous acid second part of the disinfectant system) and is oxidised to colourless when activated with a phase one foam (i.e. a foam containing the sodium chlorite-containing first part). In order to assess the degree of oxidation of anthocyanin, post activation, spectrophotometric analysis of activated (mixed) and non-activated (before mixing) phase two liquid solution with 0.5% anthocyanin (AnthoCarrot) was conducted.

[0046] Samples were activated with a 1:3 addition of phase one foam solution to phase two liquid solution and allowed to reach peak chlorine dioxide generation before testing (2 minutes). FIG. 4 shows the spectroscopic results, which shows that all anthocyanin is broken down by the generated chlorine dioxide. This can be best observed by the absence of the peak at 350 nm in the activated sample versus the non-activated sample, when maintaining equal anthocyanin starting concentrations.

[0047] Several chlorine dioxide generation tests were conducted to ensure that, although oxidation of the dyestuff consumes some chlorine dioxide, overall chlorine dioxide generation is still reaching expected levels. FIG. 5 shows chloride dioxide generation profiles for multiple samples of the foam-liquid system described above with and without the dyestuff. The graph of FIG. 5 shows that, during the initial reaction of the dyestuff with chlorine dioxide, slight interference is observed, however after about 30 seconds curve profiles and peak levels, within experimental error, are substantially identical.

[0048] Confirmatory microbiological testing was also conducted which shows efficacy is maintained on inclusion of the selective dyestuff.

[0049] Dye selectivity testing was conducted to test whether the anthocyanin dye would react or degrade in the presence of other common use high level disinfectants and oxidisers, including hydrogen peroxide, peracetic acid, and chlorine. Tests were conducted on wipes impregnated with 9 ml of 1% AnthoCarrot base, with 3 ml of each product (equivalent to a single dose of the first part from the pump 2). The wipes were then scrunched by hand for 15 s with pictures taken at time points 0, 30 and 60 s. The wipes are shown in FIG. 6, in which light contrast areas correspond to the characteristic pink-red colour of the AnthoCarrot dye and dark contrast areas correspond to wet regions of the wipes contacting the work surface. The results are summarised in Table 1.

TABLE-US-00001 Test product Description Colour change after 60 s Incidin Oxyfoam hydrogen peroxide-based disinfectant none Amity Virusolve + bis (3-aminopropyl) dodecylamine with didecyldimethyl ammonium chloride none H.sub.2O.sub.2 hydrogen peroxide 3% none Peracetic acid 10,000 ppm stabilised with hydrogen peroxide none Per-acid 10,000 ppm stabilised with hydrogen peroxide none Chlorine 1000 ppm incomplete colour loss

[0050] As can be seen, only chlorine (1000 ppm) influenced the dye. No other high level disinfectant or strong oxidiser fully degraded the colour in the wipes. Chlorine successfully removed much of the dye colouration, however it was not able to fully degrade it, with some spotting remaining even at 60 s. Furthermore, the wipe itself was affected by chlorine, with it turning to an off-white colour rather than its original colour, as the wipes do when exposed to chlorine dioxide. Based on this it can be safely said that the anthocyanin dye has a high specific selectivity for chlorine dioxide and can be used as a measure of wipe activation.

[0051] In a further selectivity test, 0.5% anthocyanin (AnthoCarrot) was added to common oxidisers in liquid form and the resulting mixture spectroscopically analysed. The results are shown in FIG. 7, and show that peracetic acid and hydrogen peroxide were unable to fully oxidise the dye with colour still observed. Chlorine mostly decomposed the dye, but a precipitate formed.

[0052] Various other dyes have been tested to assess suitability for use in the present invention. The primary requirements for a suitable dyestuff are that it is stable in at least one of the two parts of the disinfectant system, was readily oxidised in the presence of chlorine dioxide and was unstable or not oxidised in other leading oxidising compounds.

[0053] Samples of dyes where tested on liquid and wipe variants of the second part of the system for stability and chlorine dioxide generated from the combination of the second part with samples of liquid and foam versions of the first part, and in addition tested against the below oxidisers/disinfectants which are commonly used: [0054] Hydrogen peroxide (30,000 ppm) [0055] Hydrogen peroxide spray – with surfactant (commercial product – Ecolab Oxifoam) [0056] Peracetic acid 10,000 ppm [0057] Peracetic acid/hydrogen peroxide combination (10,000 ppm) [0058] Chlorine 1,000 ppm [0059] Triamine/quaternary ammonium disinfectant (Amity Virosol +)

[0060] The following types of dyestuffs were tested and identified as suitable for selective oxidation by chlorine dioxide and stability prior to use. None of the dyes produced an identical outcome result when used with the above disinfectants: [0061] Anthocyanins, including black carrot extract (e.g. AnthoCarrot L-WS E163); purple carrot powder, haskapa berry extract, E163 food colouring additives; blackcurrant extract; [0062] Anthocyanidins, including bilberry extract and clitoria ternatea (blue pea extract); [0063] Betanins, including red beetroot powder, E162 beetroot powder and beetroot juice concentrate.

[0064] Several other dyestuffs were found to be less suitable for use, compared to anthocyanin, anthocyanidin and betanin dyestuffs. For example: [0065] Carmosine (E122) and allura red (E129) are readily oxidised by chlorine dioxide but have the potential to form harmful by-products if subjected to extremes of heat; [0066] Tartrazine (E102, Cl 19140 FD&C Yellow) was found to oxidise in the presence of oxidising disinfectants other than chlorine dioxide; [0067] Chromium oxide did not fully oxidise in the presence of chlorine dioxide and produced a precipitate on reaction; [0068] Ponceau (E124) did not oxidise when exposed to chlorine dioxide at levels up to 2000 ppm; [0069] Indigo carmine has the potential to form harmful by-products; [0070] Xanthene dyes have the potential to form harmful degradation products; and [0071] Brilliant Blue FCF (E133, Food Blue 2 Cl 42090) was found to oxidise in the presence of oxidising disinfectants other than chlorine dioxide.

[0072] A further benefit of the disinfectant system of the present invention is that the use of a chlorine dioxide-selective dyestuff allows for confirmation not just that chlorine dioxide has been produced, but that the correct level of chlorine dioxide has been generated. The rate at which the chosen dyestuff is oxidised is directly proportional to the rate of inclusion. It is therefore possible to tailor the inclusion rate (i.e. the amount of dyestuff added) to ensure that total removal of colour occurs once a certain chlorine dioxide level has been reached.

[0073] It is known that chlorine dioxide rate of generation is directly proportional to temperature (see, for example, Mo et at., “Kinetics of the Preparation of Chlorine dioxide by Sodium Chlorite and Hydrochloric Acid at Low Concentration”, Chemical Engineering Transactions (46) 49-54 2015). Higher temperatures result in faster rates of generation. As the rate of dye oxidation is directly proportional to the rate of generation, the inclusion of a selective chlorine dioxide dye indicator allows for the mitigation of temperature on the rate of generation in use. Accordingly, regardless of the temperature at which the system is being used, it can be relied upon that until all dye colour has visibly disappeared the desired chlorine dioxide level has not been reached.

[0074] Testing was conducted to show that the inclusion of an anthocyanin dyestuff provided positive confirmation of the correct level of chlorine dioxide. Testing was conducted using the AnthoCarrot dye and two other comparative examples with solutions reacted at various temperatures, as set out in Table 2. When all dyestuff was oxidised, spectrophotometry analysis confirmed that intended levels of chlorine dioxide had been generated. Analysing chlorine dioxide levels before all dye had oxidised showed sub optimal levels of chlorine dioxide. Each dye tested was used in a different chlorine dioxide formulation with a different intended final concentration to show that the verification effect was observed across multiple dye stuffs and products.

TABLE-US-00002 time to total dye oxidation and desired chlorine dioxide generation (average of three replicates) Temperature Dyestuff 4° C. 20° C. 60° C. Anthocyanin 180 seconds 83 seconds 34 seconds Food Blue 2 Cl 42090 / CI 19140 FDC yellow dye 92 seconds 31 seconds 3 seconds Xanthene dye (red) 80 seconds 38 seconds 5 seconds

[0075] These results show that various dyestuffs, including anthocyanin dyestuffs suitable for use in the present invention, can effectively confirm the presence of a desired level of chlorine dioxide by exhibiting total oxidation, regardless of temperature. By increasing or decreasing the dye inclusion rate, the concentration of chlorine dioxide at which the dye is fully oxidised can be suitably selected.

[0076] Using a camera and appropriate software, or other suitable apparatus, it is possible to accurately determine the presence or absence of the dye pigment. This allows robust verification that active chlorine dioxide has been generated.

[0077] Referring now to FIG. 8, a schematic apparatus 18 for determining whether a wipe 16 contains sufficient chlorine dioxide is illustrated. The apparatus 18 includes a lamp 20 for illuminating at least one surface region of the fabric wipe 16 with at least one wavelength of light corresponding to a wavelength absorbed by the selective dyestuff. In the present example, Antho Black Carrot Extract absorbs light in the range about 450 to about 560 nm, with a peak at about 530 nm (green). The apparatus 18 includes a device 22 for measuring the intensity of the at least one wavelength of light, and a comparator device 24 for comparing the intensity value with a preset threshold value. A signalling device 26 signals that the wipe contains sufficient chlorine dioxide if the intensity value is at or above the threshold value (indicating that the dyestuff is not absorbing the light). If the intensity value is below the threshold value, the signalling device 26 signals that the wipe 16 contains insufficient chlorine dioxide (the dyestuff is absorbing the light). In this example, the signalling device includes a display 28 that provides a visual indicator. It will be understood that other signals may be used, including sounds or coloured lights, and that signals may additionally or alternatively be logged digitally on a PC or other suitable device.

[0078] The step of determining the intensity value may comprise measuring the intensity of at least one wavelength of light reflected from a plurality of surface regions of the fabric wipe and calculating the intensity value as the mean average of each measurement. To facilitate this, the apparatus 18 may further comprise a component for calculating the intensity value as the mean average of a plurality of intensity measurements.

[0079] The apparatus may be arranged to measure the intensity of multiple wavelengths of light and/or a range of wavelengths of light. The wavelength or wavelengths selected should preferably correspond to a wavelength that is strongly absorbed by the dye before activation and that is not absorbed after activation, and preferably should avoid any interference from chlorine dioxide, which exhibits absorption at around 360 nm and around 445 nm. For Antho Black Carrot Extract, the selected wavelength may be in the range of between around 500 nm and around 560 nm, and is preferably around 530 nm.

[0080] As an alternative to spectroscopic analysis, it is also possible to use a machine vision system in which image analysis techniques are used to discern the pre- and post-reaction colours to determine when sufficient chlorine dioxide has been produced.

[0081] The term “fluid” is used herein to include liquids, foams, sprays, pastes, aerosols, powders, sols and gels. It is particularly preferred that the first part is dispensed as a foam or a spray to facilitate its coverage of a desired area of the wipe. The term “chlorine dioxide disinfecting composition” is used to refer to disinfecting compositions in which the active agent is chlorine dioxide.

[0082] While the above-described examples relate to a disinfectant system comprising a foam activator (providing the first part) and a fabric wipe (providing the second part), with the dyestuff included in the second part, this is merely one example. Table 3 describes examples of possible delivery forms for the first part, including sodium chlorite, and Table 4 describes examples of possible delivery forms for the second part, including an acid.

TABLE-US-00003 First part examples Form Description Powder A product containing powdered sodium chlorite as the chlorine dioxide releasing agent with a strength of 5-15% (nominal 10%), and a flow agent to assist with maintaining powder properties and reducing clumping. Liquid A product containing liquid sodium chlorite as the chlorine dioxide releasing agent with a strength of 0.25% to 10% (0.5-4.0% nominal) and a diluent (preferably water, alternatively glycols, ethers, surfactants or any combination of these). Foam A product utilising a liquid formulation containing liquid sodium chlorite as the chlorine dioxide releasing agent with a strength of 0.25% to 10% (0.5-4.0% nominal), a surfactant (cationic, anionic, non-ionic, amphoteric or any ratio or combination thereof) with an inclusion rate of 0.5 – 25%, and a diluent (preferably water, alternatively glycols, ethers, surfactants or any combination of these) which is deployed via a foam pump apparatus. Wipe A substrate (synthetic, naturally derived, or any combination, with or without production-included dyes), impregnated with a solution of the above liquid formulation.

TABLE-US-00004 Second part examples Form Description Powder A product containing powdered acid (preferably citric acid anhydrous, however can be substituted for comparable acids such, but not limited to, malic or tartaric acid) with an inclusion rate of 40-90% (nominal 60%), a dyestuff selective for chlorine dioxide, with an inclusion rate of 0.01%-5.00% (nominal 1.00%), and a free flow agent to maintain powder mobility and reduce clumping (preferably fumed silica). Liquid A product containing a soluble/dissolved acid (preferably citric acid monohydrate, however can be substituted for comparable acids, or combination of, such as, but not limited to, malic, tartaric, citric acid anhydrous, phosphoric, hydrochloric or sulphuric acid) with an inclusion rate of 1-30% (nominal 1-10%), a dyestuff selective for chlorine dioxide, with an inclusion rate of 0.01%-5.00% (nominal 1.00%), and a diluent (preferably water, alternatively glycols, ethers, surfactants or any combination of these). Foam A product containing a soluble/dissolved acid (preferably citric acid monohydrate, however can be substituted for comparable acids, or combination of, such as, but not limited to, malic, tartaric, citric acid anhydrous, phosphoric, hydrochloric or sulphuric acid) with an inclusion rate of 1-30% (nominal 1-10%), a dyestuff selective for chlorine dioxide, with an inclusion rate of 0.01%-5.00% (nominal 1.00%), a surfactant (cationic, anionic, non-ionic, amphoteric or any ratio or combination thereof) with an inclusion rate of 0.5 –25%, and a diluent (preferably water, alternatively glycols, ethers, surfactants or any combination of these) which is deployed via a foam pump apparatus. Wipe A substrate (synthetic, naturally derived, or any combination of these) impregnated with a solution of the above liquid formulation. The dyestuff selective for chlorine dioxide can be incorporated, if desired, into the manufacturing process of the substrate material, so that it is in-situ prior to impregnation with liquid.

[0083] In either or both parts, additional components may be added to enhance performance or provide desired effects or behaviour. These include, for example, powdered/liquid surfactants (preferably non-ionic, but may include cationic, amphoteric and/or anionic); chelating agents with high affinity for sodium sequestration (to increase rate of sodium chlorite decomposition) and foam building; dyes; fragrances; fragrance suppressants (such as zeolites); secondary oxidisers such as sodium percarbonate; absorbent materials (including superabsorbent polymers, naturally derived clays and pumice blends etc.); and thickening agents.

[0084] Table 5 presents some possible combinations of these delivery forms. In some cases, mixing of the parts results in a concentrated disinfecting composition, which may be diluted before use. In other cases, mixing of the parts creates a ready-to-use disinfecting product. The ratio of the parts for mixing can be selected according to the composition and application, and may be between 1:3 and 3:1 or greater. In some examples, the ratio is 1:1.

TABLE-US-00005 Possible delivery combinations First part Second part Further dilution Liquid Liquid Dependant on application Liquid Powder Dependant on application Liquid Wipe No Liquid Foam Dependant on application Powder Powder Dependant on application Powder Liquid Dependant on application Powder Wipe No Powder Foam Dependant on application Wipe Liquid Dependant on application Wipe Foam No Foam Liquid Dependant on application Foam Powder Dependant on application Foam Wipe No Foam Foam Dependant on application

[0085] A delivery combination in which both the first and second parts are delivered as foams is described in WO 2006/079822 A1. In such a system, the foams can be mixed together after delivery from a dispenser, or may be mixed within the dispenser immediately before delivery. In the context of the present invention, the selective dyestuff is added to either or both of the first and second parts, so that the mixture of foams first exhibits the pre-change colour of the dyestuff, and then the colour changes to the post-oxidation colour once sufficient chlorine dioxide has been generated in the mixture. The mixed foams can be applied directly to a surface or item, to a wipe for subsequent application to the surface, or in any other suitable way.

[0086] Further modifications and variations not explicitly described above may also be contemplated without departing from the scope of the invention as defined in the appended claims.