WO 2005/039377 PCT/IB2004/052178 TABLEWARE-WASHING PROCESS INCLUDING A BIOCIDE Field of the Invention 5 This invention relates to a ware washing process. More particularly, but not exclusively, this invention relates to a ware washing process that is conducted in the presence of a biocide. Background to the Invention 10 In this specification, the use of the word "ware" means items which are used in the preparation and consumption of food and drink, including, but not limited to items such as cutlery, crockery, pots, pans and tableware. 15 The success of conventional ware washing processes and the associated use of conventional detergents tends to be found in their removal of common food soils under alkaline conditions, using inorganic alkalis. While these processes remove a large number of fats, proteins and sugars, due to the solubility of such soils in water, it is well documented that these soils lend themselves, 20 primarily, to removal under warm or even hot conditions. Industrial and household auto ware washing is presently, conventionally a warm water multi stage process, including a prewash stage (typically conducted at temperatures of 350C - 400C and wherein bulk soils are removed from the ware), a detergent wash stage (typically conducted at temperatures of 550C 25 650C and wherein the ware is washed with a detergent) and a rinse stage (typically conducted at temperatures of approximately 850C and wherein the ware are rinsed so as to remove any residual detergent thereon). The current practice requires operation of washing machines at these relatively high temperatures in order to ensure, first, the breaking of chemical and/or physical 30 bonds between the soils and the item to be washed and, second, the precipitating out of solution of those soils via a chelation or sequestration process.
WO 2005/039377 PCT/IB2004/052178 2 A disadvantage of conventional warm water washing is the increased energy consumption associated with generating hot water, as well as the increased down-time and maintenance of washing machine components, including boilers and elements, that is required, relative to cold-wash machines. 5 In this specification, the term "warm water washing" means washing at temperatures above 350C, typically in the range 350C - 850C, while the analogous term "cold water washing" means washing at temperatures below 350C, typically in the range 10*C - 250C. 10 Another disadvantage associated with warm water washing processes is the fact that they tend to generate relatively hot to humid conditions in the machine, which conditions are conducive to the sustainability of various forms of bio organisms such as bacteria, algae, fungi and moulds. These same 15 conditions also create a habitable environment that is favoured by pests such as cockroaches. Accordingly, warm water warewashing processes tend to lend themselves to at least some objectionable, unhygienic consequences. The use of biocides, such as ozone,. in a warm water washing process is 20 known in order to overcome the above problems. The ozone is typically bubbled through water held in the re-circulating or wash tank of a ware washing machine. One of the disadvantages is that an insufficient amount of ozone is infused into the water so as to completely destroy all the bacteria on the ware in the ware washer. 25 Object of the Invention It is an object of the invention to provide an alternative ware washing process, that, it is believed, will overcome or at least minimize the disadvantages and 30 difficulties with the prior art as set out above.
Summary of the Invention According to the present invention there is provided a ware washing process including the steps of: 5 (i) washing ware in a washing cavity of a ware washer with water and a ware washing detergent; (ii) rinsing the ware in the ware washer with water; and (iii) introducing a biocide at a pH of between 4 and 6 prior to the washing or 10 rinsing of the ware into the washing cavity of the ware washer at a rate of 500 to 900 mg/hour in order to provide a gaseous atmosphere thereof in the washing cavity, the biocide being introduced into the washing cavity by means of a separate biocide nozzle situated above a bottom spray arm independently of the introduction water. 15 The water may be at a temperature below 35'C, preferably between 15*C to 25*C. Preferably, the biocide is ozone. 20 In one embodiment of the invention, the ozone is dosed into the washing cavity in the gaseous phase at a rate of 780 mg/hour. The ozone is preferably generated by means of an ozone generator having an ozone outlet in fluid flow communication with the washing cavity. 25 In one embodiment of the invention, the biocide may be introduced into the washing cavity at a temperature in the range of 15'C to 25"C. Furthermore, the biocide may be introduced into the cavity at a pH of between 2 and 12. 3 2020114_1 (GHMaters) WO 2005/039377 PCT/IB2004/052178 4 In one embodiment of the invention, a pre-rinse stage may be introduced prior to washing the ware, the pre-rinse stage being used to remove bulk soil from the ware using water only. During the step of pre-rinsing, the biocide may be introduced into the washing cavity at a pH of between 4 and 6. 5 In another embodiment of the invention, water used in the process and exposed to the biocide may be recycled. It will be appreciated that where the biocide is ozone the water exposed thereto may be ozone infused water. 10 The ware washing detergent may include an inorganic alkali, a complexing agent and at least one surfactant. In a preferred embodiment of the invention, a caustic alkali is used. Preferably the caustic alkali is selected from the class of compounds selected from the 15 group consisting of alkali metal hydroxides. More preferably the inorganic caustic alkali may be sodium hydroxide or potassium hydroxide. The complexing agent may be a compound selected from the group consisting of a phosphate, an amino carboxylic acid, nitrolo triacetic acid 20 (NTA), ethylenediamine tetra-acetic acid (EDTA), a phosphonic acid, a phosphonobutone, an acrylate and any combination thereof. In a preferred embodiment of the invention, two complexing agents are used, namely EDTA and NTA. 25 In an embodiment of the invention, the at least one surfactant may be selected from the group consisting of anionic or non-ionic surfactants. Preferably the ware washing detergent composition comprises a mixture of surfactants, preferably a mixture including alkyl polyglucoside (for example 30 Triton BG-10 ) and alkylamino polyethoxy prolypropoxy propanol (for example Triton CF-32).
WO 2005/039377 PCT/IB2004/052178 5 The ware washing detergent may include between 0.1% - 55% (m/m) of the inorganic alkali, between 0.1% - 45% (m/m) of the complexing agent, and between 0.05 - 20% (m/m) of surfactant. 5 Additives may also be included in the ware washing detergent, for example anti scaling agents and/or coupling agents. In one embodiment of the invention the anti scaling agent used is BayhibitTM AM or Belclene@ 650 which are trade names for products in which the active ingredient is 2 phosphono butane 1,2,4 tricarboxylic acid. The coupling agent is preferably caustic soda 10 lye. In a preferred embodiment of the invention, the ware washing detergent comprises: Component % composition (by mass) EDTA 4.00 NTA 7.00 Caustic soda lye 40.05 Water (softened) 46.70886 Triton BG-10 0.06615 Triton CF-32 0.08976 Bayhibit T M AM or Belclene@ 650 0.01963 Water (softened) 2.0656 15 In a further embodiment of the invention, the step of rinsing the wares, that is step (ii) above, may include the use of a rinse aid composition which may comprise one or more alkoxylated alcohols; and an acid. 20 The rinse aid composition may include between 0.1% to 90% (m/m) of alkoxylated alcohol, and between 0.1% to 25% (m/m) of acid. The chain length of the alkoxylated alcohol may be varied between C4 to C22.
WO 2005/039377 PCT/IB2004/052178 6 In one embodiment of the invention the alkoxylated alcohol may comprise an ethoxylated alcohol and the degree of ethoxylation of the ethoxylated alcohol may be varied between 1 mole to 30 mole ethylene oxide. 5 In a preferred embodiment of the invention a mixture of alkoxylated alcohols is used, the mixture comprising alkoxylated alcohols known in the trade as Synperonic T M LF/RA30 and SynperonicTM LF/RA260. 10 Preferably, the mixture of the alkoxylated alcohols is 100% active with the cloud point of a 1% solution of the alkoxylated alcohol in water, at a temperature of less than 22*C. The acid may be an organic acid and may be selected from the group 15 consisting of citric acid, acetic acid, sulfamic acid, phosphoric acid and any combination thereof. Preferably the acid is citric acid. In a preferred embodiment of the invention, the rinse aid composition comprises: 20 Component % composition (by mass) Propyl alcohol 40.00 Citric Acid 0.10 Water (softened) 49.40 Synperonic T M LF/RA30 5.50 Synperonic T M LF/RA260 5.00 In a preferred embodiment of the invention, the rinse aid composition may further include a dye. 25 According to a second aspect of the invention there is provided the use of a biocide in a ware washing process, the biocide being introduced into a washing cavity of a ware washer so as to provide a gaseous atmosphere therein. Preferably the biocide is introduced independently from the water used to 5 wash ware located in the washing cavity. Preferably the biocide and its introduction into the washing cavity is as described above. According to a third aspect of the invention, there is provided a ware washer connectable to a source of water, the ware washer including a washing cavity, 10 wherein ware in the form of items which are used in the preparation and consumption of food and drink may be loaded therein, a water inlet for introducing water into the washing cavity and at least one inlet for introducing detergent or rinse aid into the washing cavity, the ware washer being characterized in that it includes introduction means for introducing biocide into 15 the washing cavity in gaseous phase and independently of water, prior to or contemporaneously with or subsequently to washing or rinsing, so as to provide a gaseous atmosphere thereof in the washing cavity, wherein the biocide is ozone and the introduction means includes an ozone generator having a separate ozone nozzle in fluid flow communication with the washing 20 cavity for introducing ozone into the ware washer. The biocide introduction means may be separate from the means for introducing water into the washing cavity. The washing cavity may be accessed by means of a door and may be configured to receive ware therein. 25 It will be appreciated that the ware washer will be in fluid flow communication with a source of water and will have a water inlet, wherein water is introduced into the washing cavity, and a water outlet, wherein dirty water is disposed of. In an embodiment of the invention, biocide infused water may be recycled by 30 means of a recycling system. 7 97'tROM 1 fICHMnfInI WO 2005/039377 PCT/IB2004/052178 8 Detailed Description of the Invention Without limiting the scope of the invention and by means of example only, an embodiment of the invention will now be described and exemplified with 5 reference to the accompanying figure. Figure 1: is a cross sectional side view of the ware washer used in the ware washing process according to the invention. Example 1: Experimental Procedure for the Determination of the Efficacy of Ozone as a Biocide in Ware Washinq 10 Each Formulation was evaluated using a Hobart F25 ware washer. More particularly, the Hobart F25 ware washer (10) used had been modified (not shown) by disconnecting the heating elements so that the ware washing 15 process could only be carried out at ambient temperatures within the cold water washing range. The particular results discussed below were conducted and recorded at an ambient temperature of 17.4 0 C. The ware washer (10) was further modified by including an ozone generator 20 (15) having an ozone outlet (20) in fluid flow communication with a washing cavity (25) of the ware washer (10), so that ozone in gaseous phase could be introduced into the washing cavity (25) thereby to create an atmosphere of ozone therein. The washing cavity (25) can be accessed by means of a door (30) through which ware (32) may be loaded into the ware washer (10). 25 It will be appreciated that the ware washer (10) is connected to a source of water (not shown) and has an inlet (35) for water and an outlet (40) for soiled water. The ware washer (10) also includes inlets (45) for introducing detergents and / or rinse aids into the washing cavity (25). 30 WO 2005/039377 PCT/IB2004/052178 9 The Hobart F25 ware washer was operated on a 6 minute ware washing process that included a pre-rinse cycle, a wash cycle and a rinse cycle. The detergent and rinse aid were both dosed automatically into the washing machine. 5 The solutions used were made up to the following concentrations: * detergent: 50 ml in 50 1 of water; and * rinse aid: 5 ml in 20 1 of water. 10 Uniform standard white dinner plates were used for the experiment. The rate of addition of ozone in gaseous phase was 780 mg/hour giving less than 1 ppm concentration and the process of addition of the ozone in gaseous phase into the washing machine during the 6 minute wash cycle was conducted at a rate of 780 mg per hour. 15 Bacteria counts were conducted before and after washing, and with and without ozone, the results of which are tabulated below in Tables 1, 2 and 3. The trial achieved a kill rate of 100% of all bacteria detected when using ozone. 20 Ozone Usage Trial in Warewashing Machines Scope of trial 25 To determine the kill efficacy of ozone on selected bacteria in warewashing machine. Bacteria used 30 * staphylococcus aureus; " escherichia coli;. " pseudomonas auruginosa;. * bacillus subtilis; WO 2005/039377 PCT/IB2004/052178 10 " salmonella typhi; and a listeria monocytogenes, the above bacteria having been sourced from the following batches obtained 5 from the South African Bureau of Standards: " S. aureus (STA 53) * E.coli (SABS TCC ESC 37) " P.Aeruginose (PSE 16) 10 9 B.subtillis (BAC 35) e Salmonella (SAL 10) e Listeria (LI 5) Testing Methodology and Tabulated Results 15 1. The surface of the plate used to conduct the testing on was swabbed prior to testing, and the plate was washed with commercially available detergent. 20 2. The surface of each plate on which testing was to be conducted was divided into two columns with 12 rows each. 3. The column on the left hand side was marked "Before Washing" and the column on the right hand side was marked "After Washing". 25 4. Loopfulls of each bacteria culture were placed and suspended into 5 ml separate aliquots of sterile milk, with each such aliquot being tested for the presence of antibiotics. Only those aliquots indicating a negative result for the presence of antibiotics were used in further 30 experimentation. 5. Each row on each plate was inoculated with solutions of the respective bacteria-types specified above.
WO 2005/039377 PCT/IB2004/052178 11 6. The plates were left to dry in an incubator for 10-15 minutes. 7. Each row in the column on the left hand side of the plate marked 5 "Before Washing" was swabbed so as to establish the presence and/or quantities of bacteria present on the ware. Table 1: Measured Bacteria Counts Before Washing with Ozone Swab Total Staph E.coli Pseudomon Bacillus Salmonell Listeria Descript Aerobic SGS SGS as spp Cereus a OXOID ion Count 1TP:01 1TP:00 OXOID 6 th SGS spp. 6 TH Ed SABS 763 2 4 EDD (1990) 1TP:011 1TO:018 (1990) Swab 1 0 Swab 2 0 Swab 3 >3000 Swab 4 214 Swab 5 Present Swab 6 Present Swab 7 Present Swab 8 0 10 8. Plates were then washed in the ware washing machine in the presence of ozone, together with a ware washing detergent comprising: Component % composition (by mass) EDTA 4.00 NTA 7.00 Caustic soda lye 40.05 Water (softened) 46.70886 Triton BG-10 0.06615 Triton CF-32 0.08976 WO 2005/039377 PCT/IB2004/052178 12 Bayhibit T M AM or Belclene@ 650 0.01963 Water (softened) 2.0656 and a rinse aid composition comprising: Component % composition (by mass) Propyl alcohol 40.00 Citric Acid 0.10 Water (softened) 49.40 Synperonic T M LF/RA30 5.50 Synperonic T M LF/RA260 5.00 5 9. After the wash cycle was completed, the plates was removed from the ware washer and the right hand side of each row in the "After Washing" column was swabbed so as to determine whether any bacteria was present thereon. 10 Table 2: Measured Bacteria Counts After Washing with Ozone Swab Total Staph E.coli Pseudomo Bacillus Salmon Listeria Descript Aerobic SGS SGS n as spp Cereus ella OXOID ion Count 1TP:012 1TP:004 OXOID 6 th SGS spp. 6 TH Ed SABS EDD 1TP:011 1TO:01 (1990) 763 (1990) 8 Swab 9 None Detected Swab None 10 Detected Swab None 11 Detected Swab None 12 Detected Swab Absent WO 2005/039377 PCT/IB2004/052178 13 13 Swab 0 14 It will be seen from the above table that no bacteria was found on the ware and thus a 100% kill rate was achieved when using ozone. 5 The above testing methodology was repeated without using Ozone. The results are shown in Table 3, where it can be seen that without using ozone, not all the bacteria was removed. Table 3: Measured Bacteria Counts Before and After Washing Without 10 Ozone. Staph E.coli Pseudomon Bacillus Salmonell Listeria SGS SGS as spp Cereus a OXOID 1TP:012 1TP:004 OXOID 6 th SGS spp. 6 TH Ed EDD (1990) 1TP:011 1TO:018 (1990) Measured counts 2x6 3 19 x 10 10n 41 500 Before wash Measured counts 1200 4600 12200 1370 2040 20 After wash Example 2: Description of the Cycles in a Preferred Cold Warewashing Process 15 The ware washing process used in the evaluation of the efficacy of ozone as a biocide in ware washers was a 6 minute cycle which included a pre-rinse cycle, wash cycle and rinse cycle. Both the detergent as well as the rinse aid (as described above) were automatically dosed into the ware washer at a rate of 50 mi per 20 e water for the detergent and 25 mt per 20 water for rinse 20 aid. The ozone was dosed into the ware washer in a gaseous phase at a rate of 780 mg per hour. The ozone generating unit was designed to commence dispensing ozone into the ware washer on activation of the ware washer, and to cease operation when the washing cycle had been completed. Example 3: Relative Performance Evaluation: Variable Rates of Introduction 5 of Ozone into the Washing Machine The experimental procedure as described in Example 1 were repeated, varying only the rate of addition of ozone into the ware washer from 500 mg per hour to 900 mg per hour. Consideration and comparison of the results 10 obtained revealed that the optimum was found at 780 mg per hour. It is worth noting that the bacterial load used in the experimental tests conducted were exceedingly high and such loads would not normally be found in practice and therefore the ozone value could be reduced significantly. 15 The optimum dosages for the detergent and rinse aid were found, similarly, to be 50 me per 20e water and 25 me per 251 water respectively, although this could vary substantially depending on the degree of soiling and also bacterial load. 20 It will be appreciated that numerous embodiments of the invention may be performed without departing from the scope and spirit of the invention as claimed. 25 In the claims which follow and in the preceding description of the invention, except where the context requires otherwise due to express language or necessary implication, the word "comprise" or variations such as "comprises" or "comprising" is used in an inclusive sense, i.e. to specify the presence of the stated features but not to preclude the presence or addition of further 30 features in various embodiments of the invention. It is to be understood that, if any prior art publication is referred to herein, such reference does not constitute an admission that the publication forms a part of the common general knowledge in the art, in Australia or any other country. 14 97TRM1 I HMattnrI