EP3775136A1 - Improved bleaching compositions - Google Patents

Improved bleaching compositions

Info

Publication number
EP3775136A1
EP3775136A1 EP19721669.0A EP19721669A EP3775136A1 EP 3775136 A1 EP3775136 A1 EP 3775136A1 EP 19721669 A EP19721669 A EP 19721669A EP 3775136 A1 EP3775136 A1 EP 3775136A1
Authority
EP
European Patent Office
Prior art keywords
bleaching composition
bleaching
catalyst
composition
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP19721669.0A
Other languages
German (de)
French (fr)
Inventor
Peter Woodhead
Ouardia AKDIM
Jennifer BURGUM
Claire White
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Selden Research Ltd
Original Assignee
Selden Research Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Selden Research Ltd filed Critical Selden Research Ltd
Publication of EP3775136A1 publication Critical patent/EP3775136A1/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/395—Bleaching agents
    • C11D3/3951—Bleaching agents combined with specific additives
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/391—Oxygen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3932—Inorganic compounds or complexes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/395—Bleaching agents
    • C11D3/3956—Liquid compositions

Definitions

  • the present invention relates to the provision of an improved and novel bleaching composition, more specifically variations of the bleaching composition are described that provide further improvements to the destaining and/or disinfection capabilities of the bleaching composition disclosed herein.
  • Bleaching systems for use in laundry detergents comprise the components of a bleaching composition, but certain components of the composition are provided in separate containers (for storage and transport purposes); the components of the composition only being mixed together immediately prior to use.
  • Bleaching compositions for use in laundry are also known, i.e. wherein all the components of composition that can be used for bleaching purposes are provided as a single mixture.
  • Such bleaching systems and compositions have been a common part of laundry detergents for many years. Many stains such as carrot, wine and tomato contain chromophores which are susceptible to oxidation and in the process of being oxidised lose their colour intensity.
  • Bleaching systems/compositions also have bactericidal properties which can control specific pathogens, such as MRSA, or simply reduce odours formed by bacterial contamination of the wash water.
  • bleaching compounds are chlorine based. Predominantly Sodium hypochlorite, although other chlorine based compounds, such as Calcium hypochlorite and Chlorine dioxide are also available.
  • This class of bleaching compounds also includes those compounds wherein the chlorine is generated in-situ, either from a parent molecule, such as Sodium dichloroisocyanurate which releases the bleaching agent Hypochlorous acid on dissolution in water, or from the generation of chlorine based compounds using electricity such as the electrolysis of Sodium chloride to also form Hypochlorous acid.
  • chlorinated compounds whilst cheap and effective, suffer drawbacks.
  • the compounds themselves can be relatively hazardous to the user and they often contain more hazardous impurities, such as Sodium chlorate which is present in Sodium hypochorite. They can also react with the target soil to lead to more hazardous components, such as Chloramines that are formed from the reaction of Sodium hypochlorite and Urine.
  • Chloramines that are formed from the reaction of Sodium hypochlorite and Urine.
  • the process of reacting active chlorine with the target soil often leads to that soil, or the fabric the soil sits on, developing an undesirable green colour. This is one reason why chlorine based bleaching agents are not used in hair care products - they can easily turn hair green.
  • Oxygen based bleaching agents The next most common class of bleaching agent/composition is Oxygen based bleaching agents.
  • the simplest form of Oxygen based bleaching agent, Hydrogen peroxide does not suffer the above disadvantages of Chlorine based bleaching agents. However it has far inferior bleaching performance, particularly in the field of disinfection where microorganisms often release the enzyme Catalase to deactivate the approaching Hydrogen peroxide. Therefore Hydrogen peroxide is rarely sold without other chemical components to activate it.
  • the most commonly‘activated’ Oxygen based bleaching system is Peracetic acid, formed in-situ from a source of Hydrogen peroxide and an activator such as Tetraacetylethylenediamine (TAED).
  • TAED Tetraacetylethylenediamine
  • peroxide and bleach activator system/composition A problem with the peroxide and bleach activator system/composition is that these peracid precursors tend to naturally react together during storage in aqueous media to produce the unstable peracid. To prevent such reactions from occurring during storage the components are normally supplied in powdered form. Hydrogen peroxide is usually formulated in the form of Sodium percarbonate or Sodium perborate. The bleach activator only reacts with the peroxide source once they have both dissolved into the wash solution.
  • bleach activators are available which also take a peroxide and increase its reactivity using either a catalyst or reacting it with another molecule such as a Nitrile quat. In each case the same problem is encountered: each component must be supplied separate to each other, or in anhydrous form, to prevent the activation reaction from occurring prior to use.
  • this bleaching agent should preferably be less hazardous than the Chlorine based agents.
  • Ascorbic acid is a natural molecule, commonly known as Vitamin C. It is renowned as an anti oxidant, but it has also been shown to present pro-oxidative properties under some conditions. It has been the subject of a number of patents claiming antibacterial efficacy.
  • EP 2022331 Al discloses a formulation containing a peroxide compound, a surfactant and a food preservative, which may be Ascorbic acid.
  • a peroxide compound a surfactant and a food preservative, which may be Ascorbic acid.
  • a food preservative which may be Ascorbic acid.
  • the test method disclosed in the application only demonstrates preservative properties rather than that the formulation has disinfection properties.
  • EP 2286666 Al discloses a formulation containing a metal ion having antimicrobial action, Ascorbic acid and a surfactant. Again, the data only demonstrates preservative action.
  • US 4401582A discloses a solution of Ascorbic acid. Again, there is no demonstration that it is an effective disinfectant.
  • US 3065139 discloses an anti-infectant topical preparation comprising an oxidising agent, an ene-diol and a metal catalyst.
  • a bleaching composition comprising: an enediol; an oxidising agent; and a a catalyst.
  • the bleaching composition disclosed herein has advantages over other similar known compositions in that there is no delay in the activation of the bleaching system (in many known systems there can be a 10 minute wait before the system is active following the mixing of the components, that make up such systems, in cold tap water (cold tap water as referred to herein is at a temperature in the range of 5 to 10 °C); this particularly beneficial when bleaching compositions according to the present invention are to be used to disinfect surfaces, wherein said bleaching composition are active in a matter of seconds of being made up as a solution for use as a spray for application on work surfaces, toilets, etc (or for application of the solution using a cloth).
  • the bleaching composition disclosed herein is less hazardous than corresponding systems that comprise chlorine as part of the bleaching compositions.
  • the oxidising agent is present at lower levels than those normally required in bleaching compositions.
  • the oxidising agent may be present as an impurity in an accelerator provided with the bleaching system, see below.
  • the active bleaching composition disclosed herein may comprise an aqueous solution, a water free powder, or a substantially water free slurry wherein the water content of the slurry is less than 25 wt% and preferably less than 1 wt%. It is particularly noteworthy that the bleaching composition disclosed herein, in accordance with the present invention, is particularly effective in its ability to remove stains, i.e. to act as a bleaching agent.
  • the bleaching composition is most preferably an aqueous solution.
  • the bleaching composition further comprises an accelerator.
  • the accelerator further improves the bleaching performance of the bleaching composition disclosed herein, when an accelerator is combined with the Enediol, a catalyst and oxidising agent it dramatically increases the ability of the formulation to kill bacteria or decolourise dye.
  • Great flexibility in the present formulation may be derived from the choice of accelerator as discussed below and the final product format may influence the chosen accelerator.
  • the bleaching composition further comprises an electrolyte.
  • an electrolyte to the bleaching composition provides even greater bleaching power to the bleaching composition disclosed herein.
  • the enediol is chosen from the group comprising one or more of: ascorbic acid; derivatives of ascorbic; an enediol formed from a reducing sugar; and an enediol formed from a derivative of a reducing sugar.
  • a reducing sugar is a chemical term for a sugar that acts as a reducing agent and can donate electrons to another molecule.
  • a reducing sugar is a type of carbohydrate or natural sugar that contains a free aldehyde or ketone group.
  • the enediol is chosen from the group of ascorbic acid derivatives comprising one or more of: 5,6-isopropylidene-L-ascorbic acid; and 6-O-palmitoyl-L- ascorbic acid.
  • the enediol is ascorbic acid.
  • Ascorbic acid is a particularly preferred enediol for use in the bleaching composition disclosed herein as it may be purchased as a food grade product at low cost, as well as providing compositions with excellent bleaching and disinfecting properties when used in the bleaching compositions in accordance with the present invention.
  • the enediol is present at a level in the range of 0.01 to 10 %wt when the bleaching composition is in the form of an aqueous solution.
  • References herein to the preferred ratios of components for an aqueous solution relate to an aqueous solution that is ready for use as a bleaching composition/solution.
  • the enediol is present in the bleaching composition at a level in the range of 0.1 to 3 %wt when the bleaching composition is in the form of an aqueous solution.
  • the enediol is present at a level in the range of 0.3 to 1 %wt when the bleaching composition is in the form of an aqueous solution.
  • the oxidising agent is chosen from the group comprising one or more of: a chlorine based oxidising agent; and an oxygen based oxidising agent.
  • Preferred oxygen based oxidising agents are hydrogen peroxide and agents that release hydrogen peroxide.
  • the oxygen based oxidising agent is chosen from the group comprising one or more of; Peracetic acid; tertiary butyl hydroperoxide, hydrogen peroxide; and an agent that releases hydrogen peroxide.
  • the oxidising agent is most preferably an oxygen based oxidising agent.
  • the oxidising agent that releases hydrogen peroxide is chosen from the group comprising one or more of: sodium percarbonate; and, sodium perborate.
  • the oxidising agent is hydrogen peroxide.
  • the oxidising agent is present in the range of 0.001 to 5 %wt when the bleaching composition is in the form of an aqueous solution.
  • the oxidising agent is present in the range of 0.005 to 1 %wt when the bleaching composition is in the form of an aqueous solution.
  • the oxidising agent is present in the range of 0.005 %wt to 0.3 %wt when the bleaching composition is in the form of an aqueous solution.
  • the catalyst is chosen from the group comprising one or more of: a transition metal; an oxide of a transition metal; and a salt of a transition metal. More preferably in the bleaching composition the transition metal(s) is/are chosen from the group comprising one or more of: Cobalt; Copper; Iron; Manganese; Silver; Titanium; Vanadium; and Zinc.
  • transition metal used in the bleaching system as the catalyst is copper.
  • Copper has been found to be particularly suited for use in the bleaching systems in accordance with the present invention due to it high catalytic activity in the bleaching systems disclosed herein.
  • the transition metal used in the bleaching system as the catalyst is iron.
  • Iron is particularly suited for use in the bleaching systems disclosed in accordance with the present invention because iron and its associated compounds are low cost catalysts that have a low toxicity, whilst iron (and its associated compounds as discussed herein) still have good efficacy as a catalyst.
  • the salt of the transition metal is chosen from the group comprising one or more of: a metal halide; and, a metal sulphate.
  • the catalyst is chosen from the group comprising one or more of: metallic copper; an oxide of copper; a salt of copper; metallic manganese; an oxide of manganese; a salt of manganese; metallic iron; an oxide of iron; and, a salt of iron.
  • the oxide of copper is chosen from the group comprising one or more of: copper (I) oxide; and, copper (II) oxide.
  • the metal salt is chosen from the group comprising one or more of: a copper salt; a manganese salt; and, an iron salt.
  • the copper salt is chosen from the group comprising one or more of: copper sulphate; and, copper chloride.
  • the manganese salt is manganese sulphate.
  • the iron salt is chosen from the group comprising one or more of; iron chloride; and, iron sulphate.
  • the iron may be in the +2 or +3 oxidation state.
  • the catalyst is present in the range of 0.00001 to 1 %wt when the bleaching composition is in the form of an aqueous solution.
  • the activity of the catalyst will be governed by the surface area of the catalyst; so for instance a catalyst placed in a pressure washer nozzle, for example, may last years and activate a huge amount of solution.
  • the catalyst is present in the range of 0.0001 to 0.1 %wt when the bleaching composition is in the form of an aqueous solution.
  • the catalyst is present in the range of 0.0008 to 0.01 %wt when the bleaching composition is in the form of an aqueous solution.
  • the accelerator is chosen from the group of organic compounds comprising one or more of: one or more alcohol groups; one or more ether groups; and one or more cyano groups.
  • the accelerator greatly enhances the bacterial and/or bleaching efficacy of the bleaching composition disclosed herein.
  • the oxidiser in the bleaching composition may comprise an impurity in the accelerator.
  • the accelerator comprises at least one alcohol and at least one ether group.
  • the accelerator is a glycol ether.
  • the accelerator is chosen from the group comprising one or more of the following: ethylene glycol butyl ether; diethylene glycol butyl ether; glucose; acetonitrile; hexylene glycol; PPG-2 methyl ether; dipropylene glycol; 1 -propanol; ethylene glycol; butyronitrile; acetone; ethylene glycol propyl ether; ethanol; butoxy diglycol; dipropylene glycol mono methyl ether; diethylene glycol; fructose; a surfactant that comprises an alcohol alkoxylate; and, a surfactant that comprises an alkyl poly glucoside.
  • Surfactants that comprises an alcohol alkoxylate; and, surfactants that comprises an alkyl poly glucoside are particularly useful as accelerators.
  • the accelerator is chosen from the group comprising one or more of the following: glucose; hexylene glycol; and fructose.
  • Glucose and fructose are preferentially used in the bleaching compositions disclosed herein as they function as the enediol and as the accelerator in the bleaching composition. Reducing sugars only form the transient enediol functional group in useful quantities when in alkaline conditions. So if the pH of the solution is below 9 the reducing sugar is acting as an accelerator, and should be present within the accelerator range. Above pH 9 these reducing sugars may be considered to be only an enediol
  • the accelerator is present in the range of 0.1 to 10 %wt when the bleaching composition is in the form of an aqueous solution.
  • the accelerator is present in the range of 0.1 to 5 %wt when the bleaching composition is in the form of an aqueous solution.
  • the accelerator is present in the range of 0.25 to 2 %wt. Higher levels of the accelerator (2 %wt) are used to overcome the inhibiting effects of proteins in dirty conditions.
  • the electrolyte is chosen from the group comprising one or more of a halide salt of an alkaline metal and/or a halide salt of an alkaline earth metal.
  • the alkali metal is preferably chosen from the group comprising one or more of: lithium; sodium; potassium; rubidium; caesium; and francium.
  • the alkali earth metal is preferably chosen from the group comprising one or more of: beryllium; magnesium; calcium; strontium; barium; and radium.
  • the alkaline metal salt or alkaline earth metal salt is chosen from the group comprising: a chloride salt; and an iodide salt.
  • the electrolyte is preferably chosen from the group comprising one or more of: sodium chloride; potassium iodide; and magnesium chloride.
  • the electrolyte is present at a level of up to 10 %wt when the bleaching composition is in the form of an aqueous solution.
  • the electrolyte is present in the range of 0.1 to 10 %wt when the bleaching composition is in the form of an aqueous solution.
  • the electrolyte is present in the range of 0.1 and 5 %wt when the bleaching composition is in the form of an aqueous solution.
  • the electrolyte is present in the range of 0.25 and 2 %wt when the bleaching composition is in the form of an aqueous solution.
  • the catalyst is only added to the composition immediately prior to the composition being mixed for use.
  • a bleaching composition wherein the catalyst is only added to the composition immediately prior to the composition being mixed for use. This avoids storage problems in respect of the bleaching compositions disclosed herein.
  • the catalyst further comprises a heterogeneous solid in an aqueous bleaching composition.
  • the catalyst is in the form of a powder or granules.
  • the catalyst is provided separately to the other components of the bleaching composition.
  • a bleaching composition wherein the catalyst is provided separately to the other components of the bleaching composition, Preferably in the bleaching composition the catalyst is provided separately to the other components of the bleaching composition, and the other components of the bleaching composition are exposed to the catalyst as they are poured or sprayed from a container.
  • a bleaching composition wherein the bleaching composition, following its use, dries to form a powder.
  • the bleaching composition further comprises one or more performance enhancers chosen from the group comprising pH regulators; dyes; diluents; perfumes; surfactants; rheology modifiers; suspending agents; corrosion inhibitors; water softeners; processing aids; and, defoamers.
  • performance enhancers chosen from the group comprising pH regulators; dyes; diluents; perfumes; surfactants; rheology modifiers; suspending agents; corrosion inhibitors; water softeners; processing aids; and, defoamers.
  • multiple performance enhancers may be chosen from any particular group of enhancers that are known for use in the formulation of known bleaching formulations.
  • the bleaching composition further comprises performance enhancers in the form of one or more surfactants.
  • Particularly preferred surfactants are those surfactants that can also function as accelerators, as described below.
  • the surfactant is an alcohol alkoxylate and/or an alkyl poly glucoside.
  • a bleaching composition wherein the composition is provided as a powder, a tablet or as a water free slurry, i.e. water is present in the slurry at a level below 25 wt%.
  • the present invention provides the facility to provide a dry powder that may be added to water to provide a solution that act as a bleaching composition in accordance with the invention disclosed herein.
  • the composition is provided as an aqueous solution.
  • the bleaching composition may be provided as a generally water free composition for storage and transport purposes, one or more of the components of the composition will need to be dissolved in water to provide a useable bleaching composition; even when the catalyst is separated from the other components until its use (or immediately prior to its use) as a bleaching composition.
  • a bleaching composition as an aqueous solution, wherein the catalyst is provided as a separate component that is added immediately prior to the use of the composition.
  • the bleaching composition is provided as an aqueous solution, with the catalyst provided as a separate component that, in use, is contacted with the aqueous solution.
  • a bleaching composition wherein the heterogeneous catalyst is impregnated into a cloth, a door handle, the delivery system of a triggerspray, or a cartridge containing the catalyst.
  • a bleaching composition wherein the chlorine based oxidising agent is sodium hypochlorite.
  • a bleaching composition as described above as an anti-microbial preparation.
  • an anti-microbial preparation may be used for the treatment of infections of the skin or to prevent the infection of cuts and the like.
  • the anti microbial may be provided in the form of a solution or an ointment.
  • a bleaching composition comprising of an Enediol, a catalyst, and oxidising agent and an accelerator.
  • the catalyst is a metal or metal salt and initiates the bleaching reaction.
  • the oxidising agent is a bleaching agent present at a lower level than normally used for bleaching in presently available bleaching compositions.
  • the accelerator is chosen from a number of compounds which have been found to greatly increase the bleaching performance derived from a bleaching system in accordance with the present invention that comprises the Enediol, catalyst and oxidising agent alone. Further performance gains can be made by the addition of a suitable electrolyte.
  • the inclusion rates are specified as percent by weight (%wt) unless otherwise stated, the %wt figures used relate to aqueous systems wherein water is added to the components of the bleaching system to give a total weight to the system of lOOg.
  • Enediols are a class of chemical compounds characterised by having two alcohol (OH) groups on adjacent carbon atoms which are linked by a double bond. Enediols are inherently reactive molecules so very few exist in a stable form. However the most common Enediol, Ascorbic acid, is commercially available and its structure is shown below in Figure 1. Ascorbic acid is commercially available in the form of a number of derivatives which have also been tested for bleaching performance, some of which have indeed been shown to possess bleaching performance in a formulation relating to the present invention. In order to provide clarity on which derivatives have been tested the Carbon atoms in Figure 1 have been numbered for ease of reference.
  • Enediols can also be made in-situ as transient molecules, particularly with certain sugar molecules, known as reducing sugars, which under alkaline conditions can undergo a process known as Enediol rearrangement, as shown in Figure 2.
  • An example of a transient Enediol has also been tested and demonstrated to provide bleaching performance.
  • the bleaching composition contains an Enediol, which may be present as a transient molecule formed by the dissolution and rearrangement of another molecule, preferably a molecule derived from Ascorbic acid or a reducing sugar, such as Fructose, especially preferred is Ascorbic acid or Fructose.
  • the Enediol is present between 0.01 %wt and 10 %wt in the final bleaching solution, preferably between 0.1 %wt and 3 %wt, especially preferred is between 0.3 %wt and 1 %wt.
  • the catalyst initiates the bleaching effect of the bleaching compositions disclosed herein. Tests have demonstrated that the solutions exemplified later, in the absence of the catalyst can be stable in solution for hours without producing any commercially useful bleaching agent/effect. Once the catalyst is introduced to the solution the reaction that leads to the generation of bleaching agent occurs rapidly.
  • the catalyst is homogenous.
  • the catalyst being substantially water soluble is supplied in the form of a salt of a transition metal.
  • a metal or metal salt taken from the list of Cobalt, Copper, Iron, Manganese, Silver, Titanium, Vanadium and Zinc.
  • copper salt such copper sulphate.
  • the catalyst is present between 0.00001 %wt and 1 %wt in the final bleaching solution.
  • the catalyst is present between 0.0001 %wt and 0.1 %wt, i.e. O. lmg (0.0001 %wt) of catalyst is present in an aqueous bleaching solution that has a total weight of lOOg .
  • the catalyst is present between 0.0008 %wt and 0.01 %wt.
  • the solution contains an oxidising agent, that may be an oxygen based or chlorine based oxidising agent.
  • Oxygen based oxidising agent are especially preferred as they are generally less hazardous and more environmentally friendly agents.
  • a particularly preferred oxygen based oxidising agent is Hydrogen peroxide which may be present as a Hydrogen peroxide releasing agent such as Sodium percarbonate or Sodium perborate.
  • the oxidising agent is present between 0.001 %wt and 5 %wt in the final bleaching solution, preferably between 0.01 %wt and 1 %wt.
  • a group of compounds referred to herein as accelerators have surprisingly been found to greatly enhance the bleaching performance of the formulation.
  • an accelerator is combined with the Enediol, a catalyst and oxidising agent it dramatically increases the ability of the formulation to kill bacteria or decolourise dye.
  • the accelerator contains at least one alcohol group or at least one ether group or at least one cyano group, more preferred is an accelerator which contains both an alcohol and at least one ether group, especially preferred is an accelerator taken from the list: Ethylene glycol butyl ether, Diethylene glycol butyl ether, Glucose, Acetonitrile, Hexylene glycol, PPG-2 methyl ether, Dipropylene glycol, 1 -Propanol, Ethylene glycol, Butyronitrile, Acetone, Ethylene glycol propyl ether, Ethanol, Butoxy diglycoh Dipropylene glycol mono methyl ether, Diethylene glycol, Fructose.
  • Accelerators which contain both alcohols and ether groups are commonly known as Glycol ethers. Unexpectedly many such Glycol ethers exist and have been demonstrated to be effective in increasing the bleaching power of the formulation.
  • the final choice of accelerator may also depend on other factors, such as price, odour, flammability and solubility in the final formulation.
  • the accelerator is present in the final bleaching solution between 0.1 %wt and 10 %wt preferably between 0.3 %wt and 5 %wt, especially preferred between 0.5 %wt and 2.5 %wt.
  • a suitable electrolyte preferably a halide salt of an alkaline metal or a halide salt of an alkaline earth metal, most preferably Sodium chloride.
  • the electrolyte provides a reasonable boost to the bleaching performance of the bleaching composition made up (for use) as a solution in water, i.e. improves the ability of the composition to remove stains and to act as an anti-microbial, see table 13.
  • an electrolyte in the bleaching system is particularly beneficial, (the electrolyte provides a particular benefit/advantage) when a stubborn stain needs to be removed and when an interfering substance is present, such as the protein BSA which is commonly used to mimic soil in disinfectant test standards.
  • an electrolyte is present at a level between 0.1 to 10 %wt in the final aqueous bleaching solution, preferably between 0.1 %wt and 5 %wt, especially preferred between 0.25 %wt and 2 %wt. Higher levels are generally used to overcome the inhibiting effects of proteins in dirty conditions.
  • Glucose contains the necessary functional groups (both ether and alcohol groups) to act as an accelerator and can be supplied cheaply in a solid form, making it an ideal choice for the accelerator component if the product were (is) to be supplied as a powder or tablet. It has been shown that both Hexylene glycol and Glucose provide a boost to bleaching performance, albeit not to the extent of the more effective Glycol ethers, such as Butoxy ethanol. Those skilled in the art will also realise that compounds exist that contain the necessary functional groups to act as an accelerator and/or to additionally act as a provider of a transient Enediol molecule, such as the aforementioned Fructose illustrated in Figure 2.
  • the percentage ranges given refer to the final ready to use bleaching solution, i.e. the %wt of a component in a solution comprising the components of the bleaching composition made up to a total weight of 100 g with water. If, as anticipated, the product is supplied in substantially anhydrous form for the purpose of storage stability, then the ranges should be scaled to allow for the subsequent addition of water.
  • bleaching formulations it is common in bleaching formulations to also incorporate other non-active ingredients to improve the physical characteristics, performance or stability of the bleaching product.
  • non-active ingredients include pH regulators, dyes, diluents, perfumes, surfactants, rheology modifiers, suspending agents, corrosion inhibitors, water softeners, processing aids, defoamers.
  • the choice of surfactant can have an influence on performance. It is known that low levels of surfactant can aid the biocidal efficacy of formulations by increasing the permeability of the cell membrane to the biocidal active. Fikewise, the surfactant has the potential to improve the wetting of the heterogeneous catalyst, thereby improving the contact between the formulation and the catalyst. Surfactants reduce the surface tension of the liquid (a bleaching composition), making it easier for the bleaching composition to interact with a stain or a pathogen.
  • surfactants may inhibit the biocidal efficacy of the formulation, by preferentially locking an essential component of the formulation inside a micelle. They may also bind to the catalyst surface and reduce its activity. There may be other factors to consider when choosing the type and inclusion level of the surfactant, such as the requirement to solubilise perfume or disperse fatty stains, which may in some part be either synergistic or detrimental to the bleaching performance. Therefore the choice of surfactant, if one is used, is broad. Those skilled in the art will note that contained in the structure of some surfactants are functional groups detailed in the present application as accelerators. Such surfactants include Fatty alcohol alkoxylates and Alkyl poly glucosides.
  • a further benefit of the present invention is that many of the stability issues common with bleaching systems can be overcome by supplying the catalyst in a heterogeneous form. In this way, the catalyst can be provided as a separate part of the system and therefore does not exert an influence on the formulation during storage.
  • This benefit may be utilised to provide superior long term storage of a concentrated liquitab or powder, similar to that described in the first embodiment, or enable a diluted bleaching solution to retain its bleaching properties for a longer period of time at the point of use by delaying activation of the bleaching solution until it is applied to the surface to be disinfected.
  • a preferred application of the heterogeneous catalyst is to impregnate part of the delivery system of a triggerspray bottle (container) such that the bleaching solution passes over the catalyst on the way out of a container onto, for example, a wine stain on a carpet.
  • a similar preferred application is to pass the solution through a cartridge containing the catalyst in a low or high pressure spraying device which may be used to bleach a larger area, such as to disinfect a food production line.
  • a low or high pressure spraying device which may be used to bleach a larger area, such as to disinfect a food production line.
  • Another preferred example is to impregnate the catalyst into a cloth so that the bleaching solution is sprayed onto a surface, such as kitchen work surface, and the action of wiping the surface with the impregnated cloth activates the solution containing the remaining components of the formulation and thus creates the desired bleaching effect which disinfects the surface.
  • the catalyst could be impregnated into an object, such as washroom door handle, so that the remaining components of the formulation could be sprayed or wiped onto the object and activated by the catalyst embedded in the object.
  • a further preferred example is to supply the product in a flexible vial and squeeze the product through a small opening impregnated with catalyst onto skin or a wound.
  • the formulations are substantially similar to the first embodiment but the transition metal salt is removed and replaced by a solid heterogeneous catalyst incorporated into the delivery mechanism, as described above.
  • heterogeneous catalysts include transition metals and transition metal salts, preferably metals, metal oxides and metal phosphates taken from the list comprising of Cobalt, Copper, Iron, Manganese, Silver, Titanium, Vanadium and Zinc. Especially preferred is catalyst containing Copper or an oxide of Copper. Those skilled in the art may also dope the catalyst with further metals and/or their salts.
  • the activity of the heterogeneous catalyst will in part be related to its surface area, the surface structure, the wetting of the catalyst by the solution and the dwell time on the catalyst surface.
  • simple factors such as the weight of the catalyst are of little relevance.
  • weights are included for consistency, but those skilled in the art will be careful not to infer that one catalyst has superior chemical activation of the bleaching system as physical characteristics described above may be a greater contributor to the observed differences.
  • the heterogeneous catalyst is supplied as a powder or granules.
  • Those skilled in the art may choose to support the catalyst, or impregnate the catalyst, into any one of a wide variety of structures to increase its surface area, to prevent its leaching or facilitate the placing of to the catalyst in a commercial device.
  • Bleaching compositions have a variety of uses. Those skilled in the art could readily make variations to the bleaching compositions disclosed herein such that they are suitable for stain removal on hard or fabric surfaces, disinfection of hard or fabric surfaces, disinfection of human or animal skin, disinfection of food, removal of moss or algae.
  • the flexibility of the invention matches the multiple and varied uses of bleaching formulations.
  • the efficacy requirements for disinfection can vary significantly according to the task being undertaken. Examples of which will be illustrated below.
  • a food production line may be cleaned and disinfected at the end of each production run, with no intention of using the line again before the next day.
  • the disinfection requirements of the product therefore are not particularly onerous, killing only bacteria in clean conditions over a prolonged contact time.
  • Of greater significance are the requirements to reduce contamination of the next food produced with the disinfectant, so in such a case either weak solutions of the most effective ingredients may be favoured, or selecting the accelerator and optional surfactant may be selected from food grade ingredients (see table 12).
  • Suitable formulations for such an application are given in formula references Xld (see table 10) and XIIc (see table 12).
  • the formulations disclosed in the present invention have been tested to the disinfectant test standard EN 1276 or EN 13697, incorporated herein by reference.
  • EN 1276 test requires mixing a solution of disinfectant in standardised hard water with a suspension of bacteria in the presence of an artificial soil for a set period of time. After this set period of time a separate solution is added to inactivate the disinfectant to prevent any more bacteria being killed. The surviving bacteria are then counted to determine the reduction in bacteria caused by the disinfectant.
  • the EN 13697 test is similar, except the bacteria and artificial soil are placed on a disc and the disinfectant is placed on top, again for a set period of time before the addition of an inactivator to stop the bactericidal action of the disinfectant.
  • This EN 13697 is known as a‘surface’ test and can be significantly harder to pass than the EN 1276‘suspension’ test. Both tests require the product to be evaluated against four stipulated bacteria: Psuedomonas aeruginosa, Escherichia coli, Staphylococcus aureus, and Enterococcus hirae.
  • the requirements of the product may vary considerably.
  • the product (bleaching composition system/solution/formulation) may be applied to a particularly stubborn stain shortly before the sheet goes into a washing machine, such that the bleaching solution washed out when a laundry cycle is started.
  • it may be favourable to use a particularly fast acting version of the formulation or formulations developed for high levels of interfering substances or difficult stains. Suitable formulations are given in formula references IVb, Va, Vc. see below.
  • the product may be used to remove a wine stain on a sensitive rug.
  • a far weaker bleaching solution as the risk of damage to the fabric is of far greater concern.
  • it may also be beneficial to use a formulation which dries to a powder so that it can be vacuumed away once dried. Suitable formulations are given in formula references Id, Illb and Hid, see below.
  • formulations detailed herein illustrate the breadth of suitable formulations provided by the invention disclosed herein, the skilled addressee will appreciate that various modifications may be made to said formulations, and alternative formulations based on the disclosure herein may be perfectly suitable for use as bleaching compositions even in respect of further tougher tasks. There may also be commercial factors to take into consideration when considering formulations, e.g. it may be desirable from a marketing perspective to select naturally occurring ingredients and alter the concentrations to obtain a desired efficacy.
  • Bactericidal efficacy data was conducted to the EN 1276 disinfectant test standard against Staphylococcus aureus, which had been shown to be the limiting organism in the EN 1276 test.
  • the pass criteria is a log reduction in bacteria of greater than 5.
  • Staphylococcus aureus was also shown to be the limiting organism in the aforementioned EN 13697 test.
  • a syringe was used to pass the test solutions through a capsule containing 75mg of catalyst granules and a filter.
  • water is added to the other components of the bleaching composition to give a total final weight for the aqueous bleaching solution of lOOg (as indicated by“Water (To lOOg) - l00g”and“To lOOg”. 3
  • Example 2 Different catalysts were evaluated in the solution (bleaching composition/in accordance with the invention disclosed herein). Where heterogeneous catalysts were used, the powder or granules were placed in the jar with the dye containing solution freely able to diffuse over them. The catalysts were evaluated with differing levels of hydrogen peroxide. Although some catalysts are less effective than others their performance can be boosted with the addition of electrolyte, as exemplified in Tables 3 and 4, wherein an electrolyte is included in the form of Sodium chloride, or by using a higher temperature.
  • accelerators of choice are multifunctional, in that they will contribute significantly to the cleaning process in addition to bleaching property of the bleaching composition/solution. It may therefore be preferable to use higher levels of accelerators which have the additional advantage that lower levels of the Enediol or oxidising agent will be needed to maintain bleaching performance.
  • Example 1 as disclosed above is a relatively straightforward test of bleaching performance and demonstrates how the product can be formulated for favourable conditions.
  • there are normally interfering substances present which can make the task of bleaching stains significantly harder.
  • BSA Bovine Serum Albumin
  • the level of the accelerators and/or electrolytes may be increased to ensure that the compositions bleach the required stains in a period of time of less than 30 minutes as exemplified by the time it takes a composition.
  • Enediols were investigated. Some of the commercially available Enediols are derivatives of Ascorbic acid. In Table 8 these derivatives are identified by referring to the position of the Alcohol (OH) group modified according to the Carbon numbering system shown in Figure 1. Some of the derivatives are not water soluble and led to the solution becoming opaque. For these samples the exact L* values could not be determined by the analytical equipment so a visual indication has been given in such cases.
  • An example of a molecule which forms a transient Enediol group is exemplified in Table 8 as Fructose, and the pH of the bleaching composition disclosed below (see Vid) was modified accordingly to an alkaline pH of 10.8 using solid sodium hydroxide. Table 8
  • the oxidising agent is thought to initiate the bleaching effect. It is present at a lower level than that normally required to produce an effective bleaching effect.
  • table 9 a number of different oxidising agents were evaluated. Table 9
  • Table 9 shows that a number of different oxidising agents may be used.
  • the bactericidal efficacy of the bleaching composition as illustrated was tested and the performance of the compositions was compared with and without various accelerators in Table 10.
  • the oxidising agent is Sodium percarbonate.
  • the data in table 10 demonstrates that the accelerators greatly increase the bactericidal efficacy of the bleaching composition comprising of Ascorbic acid, Sodium percarbonate and Copper sulphate. It can also be seen that Ethylene glycol butyl ether has no efficacy as a bactericide on its own.
  • bleaching compositions Provides data demonstrating that higher amounts of accelerator enable the formulation (bleaching compositions) to pass the efficacy requirements of more challenging test tests.
  • some applications for the bleaching composition may only require the product to disinfect in clean conditions over prolonged contact times, whereas other applications may require shorter contact times or the ability to still disinfect in the presence of interfering substances.
  • electrolytes can improve the bleaching power of the formulation.
  • Table 13 see below progressively more challenging conditions are again used to demonstrate the benefits of incorporating an electrolyte.
  • the electrolyte can be an alkali metal halide or an alkali earth metal halide.
  • This table provides data relating to the evaluation of the use of water insoluble metal catalysts.
  • the data in table 16 shows that a number of transition metals and their oxides can make suitable catalysts in the bleaching compositions of the patent invention.
  • Table 17 see below, the quantity of catalyst was explored to see if greater quantities of catalyst enabled the formulation to work in more challenging conditions. Table 17 provides data in respect of varying the catalyst concentration.
  • the data provided above demonstrates the range of formulation possibilities for the bleaching composition disclosed herein) to kill bacteria in varying conditions. It is acknowledged that bacteria are one of the easier microorganisms to kill. It can be seen that the formulation (bleaching composition disclosed herein) is capable of killing more difficult microorganisms by raising the concentrations of some of the components.
  • Table 18 the performance against the yeast Candida albicans according to an EN 1650 test (included herein by reference) is compared against the bacteria Staphylococcus aureus according to the EN 1276 test.
  • EN 1650 is very similar to the aforementioned EN 1276 but is tailored to test for yeasts and fungi rather than bacteria.
  • the pass criteria for EN 1650 is a log reduction of greater than 4, rather than the log 5 required for EN 1276.
  • Table 18 provides data demonstrating bleaching efficacy (of bleaching compositions according to the invention) against yeasts.
  • the data in table 18 shows that, as expected, the yeast Candida albicans is a more challenging microorganism to disinfect than the bacteria Staphylococcus aureus.
  • formulations disclosed herein demonstrate that acceptable performance can be achieved by raising the concentration of the catalyst, Copper sulfate, that is used in the bleaching compositions.
  • the above disinfectant efficacy tests are known as Suspension tests.
  • the Surface test can also be used to demonstrate efficacy.
  • the commonly used Surface test is EN 13697 (included herein by reference), which in some cases can be significantly harder to pass than the EN 1276 test.
  • Table 19 demonstrates the higher levels of substances used to pass this test (EN 13697) in the desirable short contact time of 1 minute. Note that the pass criteria for EN 13697 is a log reduction of greater than 4.
  • the data in table 19 shows that the bleaching composition can meet the efficacy requirements of the more challenging EN 13697 test method using higher levels of the Enediol Ascorbic acid; the accelerator Ethylene glycol butyl ether, or the electrolyte, sodium chloride.
  • the components used to provide a bleaching composition were initially supplied in a substantially water free formulation to improve the shelf-life of the product (bleaching composition disclosed herein). It is not always necessary to remove every trace of water to improve stability. Indeed some common ingredients are supplied in a form known as a hydrate in which water is bound to their structures even in the solid form; in such formulations it is believed that the water content of the formulation comprises less than 25 %wt of the total weight of the formulation that is stored and subsequently added to water to provide a bleaching composition in accordance with the present invention.
  • the formulations were made up in a substantially water free form, a set weight of the formulation was then dissolved in water to the concentration indicated in the table below. To lOOg of this solution 2mg of Acid red 14 dye was added and the same technique as detailed above was used to measure the time required for half the dye to be destroyed.
  • the 1% solution of the bleaching composition comprises lg of a formulation (wherein the ratio of AA to sodium percarbonate is 83.3 to 16.7 respectively) to which 99 g of water was added to provide a solution comprising a total weight of lOOg, subsequently 0.0008g of copper sulfate and 2 mg of acid red were added to the solution and the time taken for half of the dye to be destroyed was determined (as shown in the table). This is how the test samples were made up in respect of tables 21 to 25.
  • the data shows that the heterogenous catalyst works effectively in such a system. Whilst the time to reach 50% stain removal may be longer than the time for a corresponding system comprising the homogeneous, this feature may be advantageous where a bleaching composition is to be used to treat delicate materials.
  • the data in table 22a shows that iron is a suitable catalyst for use in the bleaching compositions disclosed in accordance with the present invention.
  • the formulations disclosed above are provided as powders that can be added to water to form a solution (bleaching composition) in accordance with the invention disclosed herein.
  • the choice of accelerators for a powdered formulation is limited since many of the desirable chemicals are present in a liquid state at room temperature. However, the use of the powdered accelerator, glucose, is tested below (see Table 23).
  • the metal catalyst is preferably copper or iron. Table 23
  • the data in table 23 demonstrates that the accelerator glucose gives a mild boost to performance when compared to a formulation of Ascorbic acid and Sodium percarbonate in the same ratio (1F). Furthermore, glucose is a relatively cheap ingredient and the data shows that this improved performance can be maintained with much lower levels of Sodium percarbonate and Glucose.
  • the data in table 24 shows that optimal bleaching performance is obtained between a ratio of Fructose : Sodium percarbonate of 5: 1 and 300: 1, i.e. when the ratio of the reducing sugar, (in this case fructose) that is used as the Enediol is between 5: 1 and 300: 1 relative to the oxidising agent (sodium percarbonate - an oxygen based oxidising agent).
  • Table 25 shows that optimal bleaching performance is obtained between a ratio of Fructose : Sodium percarbonate of 5: 1 and 300: 1, i.e. when the ratio of the reducing sugar, (in this case fructose) that is used as the Enediol is between 5: 1 and 300: 1 relative to the oxidising agent (sodium percarbonate - an oxygen based oxidising agent).
  • a liquid accelerator was used to make a slurry of powdered Ascorbic acid and Sodium percarbonate dispersed in the accelerator glycerine. On this occasion the heterogenous catalyst Copper (I) oxide was used.
  • the data demonstrates that the accelerator glycerine enhances the performance of the heterogenous system in Table 22.
  • Glycerine was used to provide a slurry of a dry mixture that is water free (the water content of the slurry being less than 1 wt% of the total mass of the slurry). Such a slurry may be added to water to provide a bleaching composition and such slurries may be stored for prolonged periods prior to their use.
  • a bleaching composition containing an Enediol, an oxidiser, a catalyst and an accelerator containing an Enediol, an oxidiser, a catalyst and an accelerator.
  • the oxidiser may be present as an impurity in the accelerator.
  • a bleaching composition wherein the Enediol is a molecule derived from Ascorbic acid or more preferably Ascorbic acid.
  • a bleaching composition wherein the oxidiser is Hydrogen peroxide, or a Hydrogen peroxide adduct such as Sodium percarbonate.
  • a bleaching composition wherein the catalyst contains at least one transition metal or at least one salt formed from a transition metal or a combination of at least one transition metal and one salt formed from a transition metal.
  • a bleaching composition wherein the metal or the salt formed from the metal is taken from the group of period 4 transition metals, preferred is a metal or metal salt taken from the list of Cobalt, Copper, Iron, Manganese, Silver, Titanium, Vanadium and Zinc, especially preferred is a metal or metal salt containing Copper.
  • a bleaching composition which additionally contains an electrolyte, preferably an alkali metal halide.
  • a bleaching composition which additionally contains a surfactant, preferably an Alcohol alkoxylate or an Alkyl poly glucoside.
  • a bleaching composition which additionally contains any one of a pH regulator, dye, diluent, perfume, surfactant, rheology modifier, suspending agent, corrosion inhibitor, water softener, processing aid or defoamer.
  • the use of ascorbic acid at levels between 5 and 10 wt% may be required when the bleaching composition is to be used to kill viruses and spores.
  • the use of the catalyst at higher levels may be required when the bleaching composition is to be used to kill viruses and spores.
  • the use of the accelerator at higher levels e.g. 10 to 20 %wt
  • the use of the electrolyte at higher levels e.g. 2.5 to 10 %wt may be required when the bleaching composition is to be used to kill viruses and spores.
  • a bleaching composition wherein the catalyst is substantially water insoluble and is contained in part of the delivery mechanism such as part of a spraying device, embedded in a wiping device or impregnated into a surface onto which or through which the remaining components of the bleaching solution can be applied.
  • a bleaching composition wherein the catalyst is substantially water and mixed with the remaining components of the bleaching solution at the point of use through a dosing device, or is contained as a powder within a substantially anhydrous formulation which is dissolved in water immediately prior to use.
  • a bleaching composition wherein at least one of the essential components of the bleaching composition is present in a powdered form and suspended in a slurry of one of the other essential components or an additional substance, as referred to immediately above, to prevent premature activation of the bleaching composition.

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Abstract

A bleaching composition comprising: an enediol; an oxidising agent; and a, a catalyst.

Description

IMPROVED BLEACHING COMPOSITIONS
Technical Field of the Invention
The present invention relates to the provision of an improved and novel bleaching composition, more specifically variations of the bleaching composition are described that provide further improvements to the destaining and/or disinfection capabilities of the bleaching composition disclosed herein.
Background to the Invention
Bleaching systems for use in laundry detergents are known, these systems comprise the components of a bleaching composition, but certain components of the composition are provided in separate containers (for storage and transport purposes); the components of the composition only being mixed together immediately prior to use. Bleaching compositions for use in laundry are also known, i.e. wherein all the components of composition that can be used for bleaching purposes are provided as a single mixture. Such bleaching systems and compositions have been a common part of laundry detergents for many years. Many stains such as carrot, wine and tomato contain chromophores which are susceptible to oxidation and in the process of being oxidised lose their colour intensity.
Bleaching systems/compositions also have bactericidal properties which can control specific pathogens, such as MRSA, or simply reduce odours formed by bacterial contamination of the wash water.
Although the products that comprise a bleaching composition are often marketed separately for the purposes of destaining and disinfection it is recognised that the two properties are normally, to some degree, present in all bleaching formulations/systems/compositions.
The most common bleaching compounds are chlorine based. Predominantly Sodium hypochlorite, although other chlorine based compounds, such as Calcium hypochlorite and Chlorine dioxide are also available. This class of bleaching compounds (chlorine based compounds) also includes those compounds wherein the chlorine is generated in-situ, either from a parent molecule, such as Sodium dichloroisocyanurate which releases the bleaching agent Hypochlorous acid on dissolution in water, or from the generation of chlorine based compounds using electricity such as the electrolysis of Sodium chloride to also form Hypochlorous acid.
These chlorinated compounds, whilst cheap and effective, suffer drawbacks. The compounds themselves can be relatively hazardous to the user and they often contain more hazardous impurities, such as Sodium chlorate which is present in Sodium hypochorite. They can also react with the target soil to lead to more hazardous components, such as Chloramines that are formed from the reaction of Sodium hypochlorite and Urine. In the field of destaining, the process of reacting active chlorine with the target soil (stain) often leads to that soil, or the fabric the soil sits on, developing an undesirable green colour. This is one reason why chlorine based bleaching agents are not used in hair care products - they can easily turn hair green.
The next most common class of bleaching agent/composition is Oxygen based bleaching agents. The simplest form of Oxygen based bleaching agent, Hydrogen peroxide, does not suffer the above disadvantages of Chlorine based bleaching agents. However it has far inferior bleaching performance, particularly in the field of disinfection where microorganisms often release the enzyme Catalase to deactivate the approaching Hydrogen peroxide. Therefore Hydrogen peroxide is rarely sold without other chemical components to activate it. The most commonly‘activated’ Oxygen based bleaching system is Peracetic acid, formed in-situ from a source of Hydrogen peroxide and an activator such as Tetraacetylethylenediamine (TAED).
A problem with the peroxide and bleach activator system/composition is that these peracid precursors tend to naturally react together during storage in aqueous media to produce the unstable peracid. To prevent such reactions from occurring during storage the components are normally supplied in powdered form. Hydrogen peroxide is usually formulated in the form of Sodium percarbonate or Sodium perborate. The bleach activator only reacts with the peroxide source once they have both dissolved into the wash solution.
Other bleach activators are available which also take a peroxide and increase its reactivity using either a catalyst or reacting it with another molecule such as a Nitrile quat. In each case the same problem is encountered: each component must be supplied separate to each other, or in anhydrous form, to prevent the activation reaction from occurring prior to use.
The major issue with these activated Oxygen based bleaching systems is that a certain amount of time and certain temperature are required for the two pre-cursors to react to together and form the effective bleaching agent an amount of time and temperature is needed. Typically, over 10 minutes is required in cold tap water, which is normally between 5 and 10 °C in the UK, to form the bleaching component, which then requires further time to conduct the bleaching process. Whilst this is only a limited drawback in a laundry machine or an automatic dishwasher machine, whereby a portion of the machine cycle can be effectively used to form the bleaching system in-situ. It is normally impractical to provide the necessary time and temperature for a surface disinfectant to generate such efficacious bleaching systems.
A review of the commonly used bleach activators can be found in the Handbook of Detergents: Part: Applications, Chapter 16, Applications of Bleaching Detergent Formulations; Gerd Reinhardt and Georg Borchers.
Efforts have been made to produce an effective Oxygen based bleaching system which is not generated in-situ. These efforts have focussed on taking the aforementioned Peracetic acid and supplying it in a way to overcome its numerous disadvantages. WO 93/10088 in particular tries to address the storage stability issues of Peracetic acid but it cannot be supplied as anything other than a very dilute solution without creating odour issues.
There remains a need for an effective bleaching agent which can act quickly and effectively against stains and microorganisms. Furthermore, this bleaching agent should preferably be less hazardous than the Chlorine based agents.
Ascorbic acid is a natural molecule, commonly known as Vitamin C. It is renowned as an anti oxidant, but it has also been shown to present pro-oxidative properties under some conditions. It has been the subject of a number of patents claiming antibacterial efficacy.
EP 2022331 Al discloses a formulation containing a peroxide compound, a surfactant and a food preservative, which may be Ascorbic acid. In the patent claims are made regarding the disinfection properties of Ascorbic acid, but the test method disclosed in the application only demonstrates preservative properties rather than that the formulation has disinfection properties.
EP 2286666 Al discloses a formulation containing a metal ion having antimicrobial action, Ascorbic acid and a surfactant. Again, the data only demonstrates preservative action.
US 4401582A discloses a solution of Ascorbic acid. Again, there is no demonstration that it is an effective disinfectant.
US 3065139 discloses an anti-infectant topical preparation comprising an oxidising agent, an ene-diol and a metal catalyst.
None of the patents identified above disclose effective decolourising (bleaching) agents.
Summary of the Invention
According to a first aspect of the invention there is provided a bleaching composition comprising: an enediol; an oxidising agent; and a a catalyst.
The bleaching composition disclosed herein has advantages over other similar known compositions in that there is no delay in the activation of the bleaching system (in many known systems there can be a 10 minute wait before the system is active following the mixing of the components, that make up such systems, in cold tap water (cold tap water as referred to herein is at a temperature in the range of 5 to 10 °C); this particularly beneficial when bleaching compositions according to the present invention are to be used to disinfect surfaces, wherein said bleaching composition are active in a matter of seconds of being made up as a solution for use as a spray for application on work surfaces, toilets, etc (or for application of the solution using a cloth). The bleaching composition disclosed herein is less hazardous than corresponding systems that comprise chlorine as part of the bleaching compositions. The oxidising agent is present at lower levels than those normally required in bleaching compositions. Advantageously, the oxidising agent may be present as an impurity in an accelerator provided with the bleaching system, see below. The active bleaching composition disclosed herein may comprise an aqueous solution, a water free powder, or a substantially water free slurry wherein the water content of the slurry is less than 25 wt% and preferably less than 1 wt%. It is particularly noteworthy that the bleaching composition disclosed herein, in accordance with the present invention, is particularly effective in its ability to remove stains, i.e. to act as a bleaching agent.
The bleaching composition is most preferably an aqueous solution.
Preferably the bleaching composition further comprises an accelerator. The accelerator further improves the bleaching performance of the bleaching composition disclosed herein, when an accelerator is combined with the Enediol, a catalyst and oxidising agent it dramatically increases the ability of the formulation to kill bacteria or decolourise dye. Great flexibility in the present formulation may be derived from the choice of accelerator as discussed below and the final product format may influence the chosen accelerator.
Preferably the bleaching composition further comprises an electrolyte. The addition of an electrolyte to the bleaching composition provides even greater bleaching power to the bleaching composition disclosed herein.
Preferably in the bleaching composition the enediol is chosen from the group comprising one or more of: ascorbic acid; derivatives of ascorbic; an enediol formed from a reducing sugar; and an enediol formed from a derivative of a reducing sugar. A reducing sugar is a chemical term for a sugar that acts as a reducing agent and can donate electrons to another molecule. Specifically, a reducing sugar is a type of carbohydrate or natural sugar that contains a free aldehyde or ketone group.
Preferably in the bleaching composition the enediol is chosen from the group of ascorbic acid derivatives comprising one or more of: 5,6-isopropylidene-L-ascorbic acid; and 6-O-palmitoyl-L- ascorbic acid.
More preferably in the bleaching composition the enediol is ascorbic acid. Ascorbic acid is a particularly preferred enediol for use in the bleaching composition disclosed herein as it may be purchased as a food grade product at low cost, as well as providing compositions with excellent bleaching and disinfecting properties when used in the bleaching compositions in accordance with the present invention.
More preferably in the bleaching composition the enediol is present at a level in the range of 0.01 to 10 %wt when the bleaching composition is in the form of an aqueous solution. References herein to the preferred ratios of components for an aqueous solution relate to an aqueous solution that is ready for use as a bleaching composition/solution.
More preferably in the bleaching composition the enediol is present in the bleaching composition at a level in the range of 0.1 to 3 %wt when the bleaching composition is in the form of an aqueous solution.
More preferably in the bleaching composition the enediol is present at a level in the range of 0.3 to 1 %wt when the bleaching composition is in the form of an aqueous solution.
More preferably in the bleaching composition the oxidising agent is chosen from the group comprising one or more of: a chlorine based oxidising agent; and an oxygen based oxidising agent.
Preferred oxygen based oxidising agents are hydrogen peroxide and agents that release hydrogen peroxide.
Preferably the oxygen based oxidising agent is chosen from the group comprising one or more of; Peracetic acid; tertiary butyl hydroperoxide, hydrogen peroxide; and an agent that releases hydrogen peroxide.
The oxidising agent is most preferably an oxygen based oxidising agent.
More preferably in the bleaching composition the oxidising agent that releases hydrogen peroxide is chosen from the group comprising one or more of: sodium percarbonate; and, sodium perborate.
More preferably in the bleaching composition the oxidising agent is hydrogen peroxide.
Preferably in the bleaching composition the oxidising agent is present in the range of 0.001 to 5 %wt when the bleaching composition is in the form of an aqueous solution.
Preferably in the bleaching composition the oxidising agent is present in the range of 0.005 to 1 %wt when the bleaching composition is in the form of an aqueous solution.
Preferably in the bleaching composition the oxidising agent is present in the range of 0.005 %wt to 0.3 %wt when the bleaching composition is in the form of an aqueous solution.
Preferably in the bleaching composition the catalyst is chosen from the group comprising one or more of: a transition metal; an oxide of a transition metal; and a salt of a transition metal. More preferably in the bleaching composition the transition metal(s) is/are chosen from the group comprising one or more of: Cobalt; Copper; Iron; Manganese; Silver; Titanium; Vanadium; and Zinc.
More preferably the transition metal used in the bleaching system as the catalyst is copper.
Copper has been found to be particularly suited for use in the bleaching systems in accordance with the present invention due to it high catalytic activity in the bleaching systems disclosed herein.
More preferably the transition metal used in the bleaching system as the catalyst is iron. Iron is particularly suited for use in the bleaching systems disclosed in accordance with the present invention because iron and its associated compounds are low cost catalysts that have a low toxicity, whilst iron (and its associated compounds as discussed herein) still have good efficacy as a catalyst.
More preferably in the bleaching composition the salt of the transition metal is chosen from the group comprising one or more of: a metal halide; and, a metal sulphate.
More preferably in the bleaching composition the catalyst is chosen from the group comprising one or more of: metallic copper; an oxide of copper; a salt of copper; metallic manganese; an oxide of manganese; a salt of manganese; metallic iron; an oxide of iron; and, a salt of iron.
More preferably in the bleaching composition the oxide of copper is chosen from the group comprising one or more of: copper (I) oxide; and, copper (II) oxide.
More preferably in the bleaching composition the metal salt is chosen from the group comprising one or more of: a copper salt; a manganese salt; and, an iron salt.
More preferably in the bleaching composition the copper salt is chosen from the group comprising one or more of: copper sulphate; and, copper chloride.
More preferably in the bleaching composition the manganese salt is manganese sulphate.
More preferably in the bleaching composition the iron salt is chosen from the group comprising one or more of; iron chloride; and, iron sulphate. In respect of the iron chloride salt, the iron may be in the +2 or +3 oxidation state.
Preferably in the bleaching composition the catalyst is present in the range of 0.00001 to 1 %wt when the bleaching composition is in the form of an aqueous solution. The skilled addressee will appreciate that when a heterogeneous catalyst is used the activity of the catalyst will be governed by the surface area of the catalyst; so for instance a catalyst placed in a pressure washer nozzle, for example, may last years and activate a huge amount of solution.
Preferably in the bleaching composition the catalyst is present in the range of 0.0001 to 0.1 %wt when the bleaching composition is in the form of an aqueous solution. Preferably in the bleaching composition the catalyst is present in the range of 0.0008 to 0.01 %wt when the bleaching composition is in the form of an aqueous solution.
Preferably in the bleaching composition the accelerator is chosen from the group of organic compounds comprising one or more of: one or more alcohol groups; one or more ether groups; and one or more cyano groups. The accelerator greatly enhances the bacterial and/or bleaching efficacy of the bleaching composition disclosed herein. The oxidiser in the bleaching composition may comprise an impurity in the accelerator.
Preferably in the bleaching composition the accelerator comprises at least one alcohol and at least one ether group.
Preferably in the bleaching composition the accelerator is a glycol ether.
Preferably in the bleaching composition the accelerator is chosen from the group comprising one or more of the following: ethylene glycol butyl ether; diethylene glycol butyl ether; glucose; acetonitrile; hexylene glycol; PPG-2 methyl ether; dipropylene glycol; 1 -propanol; ethylene glycol; butyronitrile; acetone; ethylene glycol propyl ether; ethanol; butoxy diglycol; dipropylene glycol mono methyl ether; diethylene glycol; fructose; a surfactant that comprises an alcohol alkoxylate; and, a surfactant that comprises an alkyl poly glucoside. Surfactants that comprises an alcohol alkoxylate; and, surfactants that comprises an alkyl poly glucoside are particularly useful as accelerators.
Preferably in the bleaching composition the accelerator is chosen from the group comprising one or more of the following: glucose; hexylene glycol; and fructose.
Glucose and fructose are preferentially used in the bleaching compositions disclosed herein as they function as the enediol and as the accelerator in the bleaching composition. Reducing sugars only form the transient enediol functional group in useful quantities when in alkaline conditions. So if the pH of the solution is below 9 the reducing sugar is acting as an accelerator, and should be present within the accelerator range. Above pH 9 these reducing sugars may be considered to be only an enediol
Preferably in the bleaching composition the accelerator is present in the range of 0.1 to 10 %wt when the bleaching composition is in the form of an aqueous solution.
Preferably in the bleaching composition the accelerator is present in the range of 0.1 to 5 %wt when the bleaching composition is in the form of an aqueous solution.
Preferably in the bleaching composition the accelerator is present in the range of 0.25 to 2 %wt. Higher levels of the accelerator (2 %wt) are used to overcome the inhibiting effects of proteins in dirty conditions. Preferably in the bleaching composition the electrolyte is chosen from the group comprising one or more of a halide salt of an alkaline metal and/or a halide salt of an alkaline earth metal.
The alkali metal is preferably chosen from the group comprising one or more of: lithium; sodium; potassium; rubidium; caesium; and francium.
The alkali earth metal is preferably chosen from the group comprising one or more of: beryllium; magnesium; calcium; strontium; barium; and radium.
More preferably in the bleaching composition the alkaline metal salt or alkaline earth metal salt is chosen from the group comprising: a chloride salt; and an iodide salt.
More preferably in the bleaching composition the electrolyte is preferably chosen from the group comprising one or more of: sodium chloride; potassium iodide; and magnesium chloride.
Preferably in the bleaching composition the electrolyte is present at a level of up to 10 %wt when the bleaching composition is in the form of an aqueous solution.
Preferably in the bleaching composition the electrolyte is present in the range of 0.1 to 10 %wt when the bleaching composition is in the form of an aqueous solution.
More preferably in the bleaching composition the electrolyte is present in the range of 0.1 and 5 %wt when the bleaching composition is in the form of an aqueous solution.
More preferably in the bleaching composition the electrolyte is present in the range of 0.25 and 2 %wt when the bleaching composition is in the form of an aqueous solution.
Preferably in the bleaching composition the catalyst is only added to the composition immediately prior to the composition being mixed for use.
In accordance with a further aspect of the invention there is provided a bleaching composition wherein the catalyst is only added to the composition immediately prior to the composition being mixed for use. This avoids storage problems in respect of the bleaching compositions disclosed herein.
More preferably in the bleaching composition the catalyst further comprises a heterogeneous solid in an aqueous bleaching composition.
More preferably in the bleaching composition the catalyst is in the form of a powder or granules.
Preferably in the bleaching composition the catalyst is provided separately to the other components of the bleaching composition.
According to another aspect of the invention there is provided a bleaching composition wherein the catalyst is provided separately to the other components of the bleaching composition, Preferably in the bleaching composition the catalyst is provided separately to the other components of the bleaching composition, and the other components of the bleaching composition are exposed to the catalyst as they are poured or sprayed from a container.
According to another aspect of the invention there is provided a bleaching composition wherein the bleaching composition, following its use, dries to form a powder.
Preferably the bleaching composition further comprises one or more performance enhancers chosen from the group comprising pH regulators; dyes; diluents; perfumes; surfactants; rheology modifiers; suspending agents; corrosion inhibitors; water softeners; processing aids; and, defoamers.
It will be appreciated that multiple performance enhancers may be chosen from any particular group of enhancers that are known for use in the formulation of known bleaching formulations.
Preferably the bleaching composition further comprises performance enhancers in the form of one or more surfactants.
Particularly preferred surfactants are those surfactants that can also function as accelerators, as described below.
Preferably in the bleaching composition the surfactant is an alcohol alkoxylate and/or an alkyl poly glucoside.
Surfactants are particularly preferred performance enhancers for the reasons discussed below
According to another aspect of the invention there is provided a bleaching composition wherein the composition is provided as a powder, a tablet or as a water free slurry, i.e. water is present in the slurry at a level below 25 wt%. The present invention provides the facility to provide a dry powder that may be added to water to provide a solution that act as a bleaching composition in accordance with the invention disclosed herein.
Preferably in the bleaching composition the composition is provided as an aqueous solution. The skilled addressee will appreciate that whilst the bleaching composition may be provided as a generally water free composition for storage and transport purposes, one or more of the components of the composition will need to be dissolved in water to provide a useable bleaching composition; even when the catalyst is separated from the other components until its use (or immediately prior to its use) as a bleaching composition.
According to a further aspect of the invention there is provided a bleaching composition as an aqueous solution, wherein the catalyst is provided as a separate component that is added immediately prior to the use of the composition. Preferably the bleaching composition is provided as an aqueous solution, with the catalyst provided as a separate component that, in use, is contacted with the aqueous solution.
According to another aspect of the invention there is provided a bleaching composition wherein the heterogeneous catalyst is impregnated into a cloth, a door handle, the delivery system of a triggerspray, or a cartridge containing the catalyst.
Preferably there is provided a bleaching composition wherein the chlorine based oxidising agent is sodium hypochlorite.
According to another aspect of the invention there is provided the use of a bleaching composition as a stain remover.
According to another aspect of the invention there is provided the use of a bleaching composition as described above as an anti-microbial.
According to another aspect of the invention there is provided the use of a bleaching composition as described above as an anti-microbial preparation. Such an anti-microbial preparation may be used for the treatment of infections of the skin or to prevent the infection of cuts and the like. The anti microbial may be provided in the form of a solution or an ointment.
With respect to the use of the bleaching compositions disclosed above, it has been observed that the use of an accelerator greatly enhances the efficacy of said compositions when they are used as anti microbials or as destainers.
Detailed Description of the Invention
In order that the invention may be more clearly understood embodiments thereof will now be described, by way of example only.
According to a first embodiment of the present invention there is provided a bleaching composition comprising of an Enediol, a catalyst, and oxidising agent and an accelerator. The catalyst is a metal or metal salt and initiates the bleaching reaction. The oxidising agent is a bleaching agent present at a lower level than normally used for bleaching in presently available bleaching compositions.
In existing bleaching systems where hydrogen peroxide is used as a bleaching agent, the level of hydrogen peroxide used is normally in excess of 3%.
The accelerator is chosen from a number of compounds which have been found to greatly increase the bleaching performance derived from a bleaching system in accordance with the present invention that comprises the Enediol, catalyst and oxidising agent alone. Further performance gains can be made by the addition of a suitable electrolyte.
In all embodiments the inclusion rates are specified as percent by weight (%wt) unless otherwise stated, the %wt figures used relate to aqueous systems wherein water is added to the components of the bleaching system to give a total weight to the system of lOOg.
Enediols are a class of chemical compounds characterised by having two alcohol (OH) groups on adjacent carbon atoms which are linked by a double bond. Enediols are inherently reactive molecules so very few exist in a stable form. However the most common Enediol, Ascorbic acid, is commercially available and its structure is shown below in Figure 1. Ascorbic acid is commercially available in the form of a number of derivatives which have also been tested for bleaching performance, some of which have indeed been shown to possess bleaching performance in a formulation relating to the present invention. In order to provide clarity on which derivatives have been tested the Carbon atoms in Figure 1 have been numbered for ease of reference. It will be shown that the providing the enediol functional group remains in the molecule bleaching performance is maintained. Enediols can also be made in-situ as transient molecules, particularly with certain sugar molecules, known as reducing sugars, which under alkaline conditions can undergo a process known as Enediol rearrangement, as shown in Figure 2. An example of a transient Enediol has also been tested and demonstrated to provide bleaching performance.
The bleaching composition (solution) contains an Enediol, which may be present as a transient molecule formed by the dissolution and rearrangement of another molecule, preferably a molecule derived from Ascorbic acid or a reducing sugar, such as Fructose, especially preferred is Ascorbic acid or Fructose. The Enediol is present between 0.01 %wt and 10 %wt in the final bleaching solution, preferably between 0.1 %wt and 3 %wt, especially preferred is between 0.3 %wt and 1 %wt.
Figure 1 Ascorbic Acid
OH Figure 2
Illustrates a reducing sugar undergoing a rearrangement reaction through the transient Enediol form. The lower halves of the molecules are not shown for the sake of clarity.
It is believed that the catalyst initiates the bleaching effect of the bleaching compositions disclosed herein. Tests have demonstrated that the solutions exemplified later, in the absence of the catalyst can be stable in solution for hours without producing any commercially useful bleaching agent/effect. Once the catalyst is introduced to the solution the reaction that leads to the generation of bleaching agent occurs rapidly.
In one embodiment the catalyst is homogenous. The catalyst being substantially water soluble is supplied in the form of a salt of a transition metal. Preferred is a metal or metal salt taken from the list of Cobalt, Copper, Iron, Manganese, Silver, Titanium, Vanadium and Zinc. Especially preferably is copper salt, such copper sulphate. The catalyst is present between 0.00001 %wt and 1 %wt in the final bleaching solution. Preferably, the catalyst is present between 0.0001 %wt and 0.1 %wt, i.e. O. lmg (0.0001 %wt) of catalyst is present in an aqueous bleaching solution that has a total weight of lOOg . Especially preferred, the catalyst is present between 0.0008 %wt and 0.01 %wt.
The solution contains an oxidising agent, that may be an oxygen based or chlorine based oxidising agent. Oxygen based oxidising agent, are especially preferred as they are generally less hazardous and more environmentally friendly agents. A particularly preferred oxygen based oxidising agent is Hydrogen peroxide which may be present as a Hydrogen peroxide releasing agent such as Sodium percarbonate or Sodium perborate. The oxidising agent is present between 0.001 %wt and 5 %wt in the final bleaching solution, preferably between 0.01 %wt and 1 %wt. Especially preferred is between 0.08 %wt and 0.3 %wt; for reference purposes it is noted that 1 mg (of the oxidising agent) per 100 g of aqueous bleaching solution = 0.001 %, 0.1 mg/lOO g = 0.000 1 %, and 0.01 g/lOO g = 0.000 01 %.
A group of compounds referred to herein as accelerators have surprisingly been found to greatly enhance the bleaching performance of the formulation. When an accelerator is combined with the Enediol, a catalyst and oxidising agent it dramatically increases the ability of the formulation to kill bacteria or decolourise dye. Preferentially the accelerator contains at least one alcohol group or at least one ether group or at least one cyano group, more preferred is an accelerator which contains both an alcohol and at least one ether group, especially preferred is an accelerator taken from the list: Ethylene glycol butyl ether, Diethylene glycol butyl ether, Glucose, Acetonitrile, Hexylene glycol, PPG-2 methyl ether, Dipropylene glycol, 1 -Propanol, Ethylene glycol, Butyronitrile, Acetone, Ethylene glycol propyl ether, Ethanol, Butoxy diglycoh Dipropylene glycol mono methyl ether, Diethylene glycol, Fructose.
Accelerators which contain both alcohols and ether groups are commonly known as Glycol ethers. Unexpectedly many such Glycol ethers exist and have been demonstrated to be effective in increasing the bleaching power of the formulation. The final choice of accelerator may also depend on other factors, such as price, odour, flammability and solubility in the final formulation. The accelerator is present in the final bleaching solution between 0.1 %wt and 10 %wt preferably between 0.3 %wt and 5 %wt, especially preferred between 0.5 %wt and 2.5 %wt.
It has further been discovered that even greater bleaching power can be obtained by the addition of a suitable electrolyte, preferably a halide salt of an alkaline metal or a halide salt of an alkaline earth metal, most preferably Sodium chloride. The electrolyte provides a reasonable boost to the bleaching performance of the bleaching composition made up (for use) as a solution in water, i.e. improves the ability of the composition to remove stains and to act as an anti-microbial, see table 13. The use of an electrolyte in the bleaching system is particularly beneficial, (the electrolyte provides a particular benefit/advantage) when a stubborn stain needs to be removed and when an interfering substance is present, such as the protein BSA which is commonly used to mimic soil in disinfectant test standards. When stains are easy to remove there may be no reason to include an electrolyte. The electrolyte is present at a level between 0.1 to 10 %wt in the final aqueous bleaching solution, preferably between 0.1 %wt and 5 %wt, especially preferred between 0.25 %wt and 2 %wt. Higher levels are generally used to overcome the inhibiting effects of proteins in dirty conditions.
Those skilled in the art will be aware that a challenge in formulating bleaching systems is achieving suitable stability of both the item transported and the in-use bleaching solution. It is commonplace for such reactive products to be sold in a predominantly anhydrous form, such as a powder or solid tablet, or in the form of a substantially water free slurry which can be supplied with a dosing system or as a single or multi-compartment liquitab. The greatest flexibility in the present formulation comes from the choice of accelerator and the final product format may influence the chosen accelerator. For example, whilst Hexylene glycol may not have the most powerful bleach boosting effect it is often the choice of carrier in a liquitab contained in a water soluble film. Those skilled in the art will realise that Glucose contains the necessary functional groups (both ether and alcohol groups) to act as an accelerator and can be supplied cheaply in a solid form, making it an ideal choice for the accelerator component if the product were (is) to be supplied as a powder or tablet. It has been shown that both Hexylene glycol and Glucose provide a boost to bleaching performance, albeit not to the extent of the more effective Glycol ethers, such as Butoxy ethanol. Those skilled in the art will also realise that compounds exist that contain the necessary functional groups to act as an accelerator and/or to additionally act as a provider of a transient Enediol molecule, such as the aforementioned Fructose illustrated in Figure 2. It is well known that the Enediol rearrangement referred to in Figure 2 above preferentially occurs in alkaline pH so in the formulations exemplified in this invention it is to be assumed that such sugars are acting as accelerators unless specific reference is made to the formulation having an alkaline pH.
The percentage ranges given refer to the final ready to use bleaching solution, i.e. the %wt of a component in a solution comprising the components of the bleaching composition made up to a total weight of 100 g with water. If, as anticipated, the product is supplied in substantially anhydrous form for the purpose of storage stability, then the ranges should be scaled to allow for the subsequent addition of water.
It is common in bleaching formulations to also incorporate other non-active ingredients to improve the physical characteristics, performance or stability of the bleaching product. Examples include pH regulators, dyes, diluents, perfumes, surfactants, rheology modifiers, suspending agents, corrosion inhibitors, water softeners, processing aids, defoamers.
The choice of surfactant can have an influence on performance. It is known that low levels of surfactant can aid the biocidal efficacy of formulations by increasing the permeability of the cell membrane to the biocidal active. Fikewise, the surfactant has the potential to improve the wetting of the heterogeneous catalyst, thereby improving the contact between the formulation and the catalyst. Surfactants reduce the surface tension of the liquid (a bleaching composition), making it easier for the bleaching composition to interact with a stain or a pathogen.
However, it is also known that higher levels or unfavourable surfactants may inhibit the biocidal efficacy of the formulation, by preferentially locking an essential component of the formulation inside a micelle. They may also bind to the catalyst surface and reduce its activity. There may be other factors to consider when choosing the type and inclusion level of the surfactant, such as the requirement to solubilise perfume or disperse fatty stains, which may in some part be either synergistic or detrimental to the bleaching performance. Therefore the choice of surfactant, if one is used, is broad. Those skilled in the art will note that contained in the structure of some surfactants are functional groups detailed in the present application as accelerators. Such surfactants include Fatty alcohol alkoxylates and Alkyl poly glucosides. These have been tested as accelerators and data is provided herein to demonstrate their relative efficacy. Generally, surfactants with shorter hydrophobic chains and containing chemical groups listed as accelerators, such as Alcohol alkoxylates and Alkyl polyglucosides where the hydrophobes contain around 10 carbons in the main chain of the surfactant, are favoured. A further benefit of the present invention is that many of the stability issues common with bleaching systems can be overcome by supplying the catalyst in a heterogeneous form. In this way, the catalyst can be provided as a separate part of the system and therefore does not exert an influence on the formulation during storage. This benefit may be utilised to provide superior long term storage of a concentrated liquitab or powder, similar to that described in the first embodiment, or enable a diluted bleaching solution to retain its bleaching properties for a longer period of time at the point of use by delaying activation of the bleaching solution until it is applied to the surface to be disinfected. A preferred application of the heterogeneous catalyst is to impregnate part of the delivery system of a triggerspray bottle (container) such that the bleaching solution passes over the catalyst on the way out of a container onto, for example, a wine stain on a carpet. A similar preferred application is to pass the solution through a cartridge containing the catalyst in a low or high pressure spraying device which may be used to bleach a larger area, such as to disinfect a food production line. Another preferred example is to impregnate the catalyst into a cloth so that the bleaching solution is sprayed onto a surface, such as kitchen work surface, and the action of wiping the surface with the impregnated cloth activates the solution containing the remaining components of the formulation and thus creates the desired bleaching effect which disinfects the surface. Likewise, the catalyst could be impregnated into an object, such as washroom door handle, so that the remaining components of the formulation could be sprayed or wiped onto the object and activated by the catalyst embedded in the object. A further preferred example is to supply the product in a flexible vial and squeeze the product through a small opening impregnated with catalyst onto skin or a wound.
In this second embodiment the formulations are substantially similar to the first embodiment but the transition metal salt is removed and replaced by a solid heterogeneous catalyst incorporated into the delivery mechanism, as described above.
It has been found that suitable heterogeneous catalysts include transition metals and transition metal salts, preferably metals, metal oxides and metal phosphates taken from the list comprising of Cobalt, Copper, Iron, Manganese, Silver, Titanium, Vanadium and Zinc. Especially preferred is catalyst containing Copper or an oxide of Copper. Those skilled in the art may also dope the catalyst with further metals and/or their salts.
Those skilled in the art will appreciate that the activity of the heterogeneous catalyst will in part be related to its surface area, the surface structure, the wetting of the catalyst by the solution and the dwell time on the catalyst surface. As a result, simple factors such as the weight of the catalyst are of little relevance. In the data provided below weights are included for consistency, but those skilled in the art will be careful not to infer that one catalyst has superior chemical activation of the bleaching system as physical characteristics described above may be a greater contributor to the observed differences. In these examples the heterogeneous catalyst is supplied as a powder or granules. Those skilled in the art may choose to support the catalyst, or impregnate the catalyst, into any one of a wide variety of structures to increase its surface area, to prevent its leaching or facilitate the placing of to the catalyst in a commercial device.
Bleaching compositions have a variety of uses. Those skilled in the art could readily make variations to the bleaching compositions disclosed herein such that they are suitable for stain removal on hard or fabric surfaces, disinfection of hard or fabric surfaces, disinfection of human or animal skin, disinfection of food, removal of moss or algae.
The flexibility of the invention matches the multiple and varied uses of bleaching formulations. The efficacy requirements for disinfection can vary significantly according to the task being undertaken. Examples of which will be illustrated below.
A food production line may be cleaned and disinfected at the end of each production run, with no intention of using the line again before the next day. The disinfection requirements of the product therefore are not particularly onerous, killing only bacteria in clean conditions over a prolonged contact time. Of greater significance are the requirements to reduce contamination of the next food produced with the disinfectant, so in such a case either weak solutions of the most effective ingredients may be favoured, or selecting the accelerator and optional surfactant may be selected from food grade ingredients (see table 12). Suitable formulations for such an application are given in formula references Xld (see table 10) and XIIc (see table 12).
For disinfection, the formulations disclosed in the present invention have been tested to the disinfectant test standard EN 1276 or EN 13697, incorporated herein by reference. The EN 1276 test requires mixing a solution of disinfectant in standardised hard water with a suspension of bacteria in the presence of an artificial soil for a set period of time. After this set period of time a separate solution is added to inactivate the disinfectant to prevent any more bacteria being killed. The surviving bacteria are then counted to determine the reduction in bacteria caused by the disinfectant. The EN 13697 test is similar, except the bacteria and artificial soil are placed on a disc and the disinfectant is placed on top, again for a set period of time before the addition of an inactivator to stop the bactericidal action of the disinfectant. This EN 13697 is known as a‘surface’ test and can be significantly harder to pass than the EN 1276‘suspension’ test. Both tests require the product to be evaluated against four stipulated bacteria: Psuedomonas aeruginosa, Escherichia coli, Staphylococcus aureus, and Enterococcus hirae.
Those skilled in the art will routinely test a solution of disinfectant against all four bacteria, determine which is the most resistant to the disinfectant, herein referred to as the‘limiting organism’ and then continue to perform development work using solely this strain of bacteria. For routine disinfection of washroom surfaces the requirements are to pass EN 1276, against bacteria in dirty conditions within 5 minutes. In these cases the requirements may be more driven by cost and user friendliness (both in terms of ease of handling and stability of the working (disinfecting solution) Suitable formulations are given in formula references Xlle and XHIb see below.
In some applications products need to work in dirty conditions in much shorter contact times. Suitable formulations are given in formula reference XVIc see below.
The data requirements for different end users may vary. Whilst some end users will be satisfied with efficacy data based on the EN 1276 test, others may require the efficacy data to be based on the EN 13697 test. Suitable formulas to meet the efficiency requirements of EN 13697 are given in formula references Xlle, XVIIIa, XVIIIb and XVIIIc, see below.
It is described in the literature that many organisms are much harder to kill than bacteria. In particular, non-enveloped viruses, mycobacteria and spores pose a significant challenge to disinfectants. Likewise, shorter contact times, low temperatures (for chilled or outdoor environments) and high levels of soiling all contribute to raising the quantity of the disinfectant that must be used and influence the choice of active substances in the formulation. Whilst the data provided herein is based on bactericidal tests, it is common sense that greater concentrations would be required in such challenging applications.
Likewise, for bleaching stains the requirements of the product may vary considerably. In a commercial laundry dealing with predominantly white bed sheets, the product (bleaching composition system/solution/formulation) may be applied to a particularly stubborn stain shortly before the sheet goes into a washing machine, such that the bleaching solution washed out when a laundry cycle is started. In such an application it may be favourable to use a particularly fast acting version of the formulation or formulations developed for high levels of interfering substances or difficult stains. Suitable formulations are given in formula references IVb, Va, Vc. see below.
Alternatively, the product may be used to remove a wine stain on a sensitive rug. In such a case, it would be favourable to use a far weaker bleaching solution as the risk of damage to the fabric is of far greater concern. In such an example, it may also be beneficial to use a formulation which dries to a powder so that it can be vacuumed away once dried. Suitable formulations are given in formula references Id, Illb and Hid, see below.
Whilst the formulations detailed herein illustrate the breadth of suitable formulations provided by the invention disclosed herein, the skilled addressee will appreciate that various modifications may be made to said formulations, and alternative formulations based on the disclosure herein may be perfectly suitable for use as bleaching compositions even in respect of further tougher tasks. There may also be commercial factors to take into consideration when considering formulations, e.g. it may be desirable from a marketing perspective to select naturally occurring ingredients and alter the concentrations to obtain a desired efficacy.
Unless stated otherwise, the reagents herein used were sourced from Sigma Aldrich.
Bactericidal efficacy data was conducted to the EN 1276 disinfectant test standard against Staphylococcus aureus, which had been shown to be the limiting organism in the EN 1276 test. The pass criteria is a log reduction in bacteria of greater than 5. Staphylococcus aureus was also shown to be the limiting organism in the aforementioned EN 13697 test.
Dye decolourisation measurements were taken using an X-rite i5 Colorimeter under D65 daylight with UV-excluded. Absolute L* values were used as an indication of dye breakdown with L* = 100 being the lightest. This was considered the best indicator of dye breakdown as it was the parameter least influenced by pH and various additives. An L* reading of 78 was given for a solution containing lmg of dye (half of that added for the test) therefore this value was used as a benchmark for 50% dye destruction.
To test the heterogeneous catalyst solutions for decolourisation, to a jar containing 49g of test solution, l3mg of catalyst were added and the solution simply inverted a single time. The figures shown in the tables are scaled up to lOOg for ease of comparison.
To test the heterogeneous catalyst solutions for bactericidal efficacy a syringe was used to pass the test solutions through a capsule containing 75mg of catalyst granules and a filter.
Example 1
A number of formulations of a bleaching composition in accordance with the first embodiment of the invention disclosed herein, with and without accelerators were tested in their ability to bleach the colour out of a common textile dye, Acid Red 14. The data in Table 1 demonstrates the beneficial effect of adding accelerator to a formulation containing the Enediol, Ascorbic acid; the catalyst, Copper sulfate; and the oxidising agent, Hydrogen peroxide. The efficacy of the accelerator can be observed irrespective of catalyst concentration, as demonstrated by the use of a lower level of catalyst in Table 2. As stated above, some surfactants contain the necessary functional groups to act as accelerators and this is demonstrated below. Most of the accelerators listed are included by molarity for ease of comparison. Commercially available surfactants are by their very nature complex mixtures so molarity is not a useful tool for comparison, therefore they have been added by weight. Table 1
Demonstration of the effect of accelerators in the bleaching composition.
The data in table 1 provided clearly shows that the inclusion of an accelerator in the bleaching composition leads to much more rapid destruction of the dye. It will be noted that the time of destruction for 50% of the dye was still less than 5 minutes when using a bleaching composition in accordance with the invention disclosed herein.
In the examples provided herein water is added to the other components of the bleaching composition to give a total final weight for the aqueous bleaching solution of lOOg (as indicated by“Water (To lOOg) - l00g”and“To lOOg”. 3
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Example 2 - Different catalysts were evaluated in the solution (bleaching composition/in accordance with the invention disclosed herein). Where heterogeneous catalysts were used, the powder or granules were placed in the jar with the dye containing solution freely able to diffuse over them. The catalysts were evaluated with differing levels of hydrogen peroxide. Although some catalysts are less effective than others their performance can be boosted with the addition of electrolyte, as exemplified in Tables 3 and 4, wherein an electrolyte is included in the form of Sodium chloride, or by using a higher temperature.
Table 3 - Evaluation of different catalysts in the bleaching composition with a higher level of hydrogen peroxide.
The data in able 3 demonstrates that a number of different catalysts can be used, both homogenously and heterogeneously. The data also demonstrates that a relative shortfall in the performance of some catalysts can be overcome by the addition of an electrolyte, in this case sodium chloride. Example Ilf shows that even with the Enediol, accelerator and electrolyte the catalyst is still an essential component. 3
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Example 3
Many of the accelerators of choice are multifunctional, in that they will contribute significantly to the cleaning process in addition to bleaching property of the bleaching composition/solution. It may therefore be preferable to use higher levels of accelerators which have the additional advantage that lower levels of the Enediol or oxidising agent will be needed to maintain bleaching performance.
Table 5
Varying levels of the Enediol, Ascorbic acid and the oxidising agent, Hydrogen peroxide.
The date in table 5 demonstrates that an effective bleaching system may be provided wherein reduced levels of Ascorbic acid and Hydrogen peroxide may be used by the utilisation of an accelerator in the examples disclosed herein. The accelerator used is Ethylene glycol butyl ether.
Example 4
Example 1 as disclosed above is a relatively straightforward test of bleaching performance and demonstrates how the product can be formulated for favourable conditions. In practice, there are normally interfering substances present which can make the task of bleaching stains significantly harder. In Table 6 an interfering protein, Bovine Serum Albumin (BSA) was added to demonstrate the greater levels of accelerators and electrolytes required to maintain adequate bleaching performance when the compositions disclosed herein are to be used to remove more stubborn stains. In such cases the level of the accelerators and/or electrolytes may be increased to ensure that the compositions bleach the required stains in a period of time of less than 30 minutes as exemplified by the time it takes a composition. Table 6
Demonstrating efficacy in the presence of an interfering substance.
The data in table 6 demonstrates that the addition of a small amount of BSA prevented the formulation where no accelerator was present from effectively bleaching the dye. The addition of the accelerator, Ethylene glycol butyl ether, alone was sufficient to overcome the adverse effects of this level of BSA. Raising the level of BSA further reduced the bleaching performance of the bleaching composition, but this could be overcome by the addition of the electrolyte, Sodium chloride.
Example 5
The above examples demonstrate the bleaching power of the compositions disclosed herein against a common dye. In practice, stains tend to be complex mixtures of naturally occurring substances. To demonstrate the performance against more realistic stains, swatches of standard stains commonly used for laundry detergent testing were obtained, see below in Table 7. The stains were supplied by C.F.T (Center for Testmaterials B.V., located in Vlaardingen, The Netherlands) and selected based on the standard stains specified in the AISE laundry detergent testing guidelines for stain removal. AISE is the International Association for Soaps, Detergents and Maintenance Products (located in Brussels, Belgium) and as part of its activities develops detergent testing guidelines and protocols. 5ml of product was applied to the stain and left for 3 hours before being rinsed with cold water and allowed to air dry, away from direct sunlight. The stains were measured using an X-rite i5 colorimeter in reflectance mode under D65 daylight with 25mmol UV excluded. For each stain, two measurements were taken perpendicular to each other and the average calculated. The % stain removed was calculated using the difference between the absolute L* values of the unwashed stain and the treated stain. Table 7 - Demonstrating decolourising using an alternative test method.
The data in Table 7 demonstrates that the earlier formulation with a relatively low level of accelerator is capable of reasonably decolourising two common stains: fruit juice and red wine. However, decolourising a stain impregnated into the fabric is a significantly harder task than decolourising solutions of dye, so higher levels of active ingredients are required to improve the bleaching efficacy of the bleaching composition. Those skilled in the art will not be surprised that differing stains behave differently to the active ingredients of the new bleaching composition disclosed herein so the formulation can be tailored towards the desired application.
Example 6
Alternative Enediols were investigated. Some of the commercially available Enediols are derivatives of Ascorbic acid. In Table 8 these derivatives are identified by referring to the position of the Alcohol (OH) group modified according to the Carbon numbering system shown in Figure 1. Some of the derivatives are not water soluble and led to the solution becoming opaque. For these samples the exact L* values could not be determined by the analytical equipment so a visual indication has been given in such cases. An example of a molecule which forms a transient Enediol group is exemplified in Table 8 as Fructose, and the pH of the bleaching composition disclosed below (see Vid) was modified accordingly to an alkaline pH of 10.8 using solid sodium hydroxide. Table 8
The data in table 8 shows that providing the molecule contains two alcohol groups linked by a double bond, even if the structure is only transient, then it can be used as a bleaching agent. Clearly, some molecules are more effective than others but the differences in performance can be overcome using differing levels of the other components of the bleaching solution.
Example 7
The oxidising agent is thought to initiate the bleaching effect. It is present at a lower level than that normally required to produce an effective bleaching effect. In table 9 a number of different oxidising agents were evaluated. Table 9
Table 9 shows that a number of different oxidising agents may be used.
Example 10
The bactericidal efficacy of the bleaching composition as illustrated was tested and the performance of the compositions was compared with and without various accelerators in Table 10. In this table the oxidising agent is Sodium percarbonate.
Table 10
Demonstrating the enhanced bactericidal effect obtained from using an accelerator.
The data in table 10 demonstrates that the accelerators greatly increase the bactericidal efficacy of the bleaching composition comprising of Ascorbic acid, Sodium percarbonate and Copper sulphate. It can also be seen that Ethylene glycol butyl ether has no efficacy as a bactericide on its own.
Example 11
It is noted above that certain surfactants containing both alcohol and ether groups, such as Alcohol alkoxylates and Alkyl poly glucosides, can act as accelerators for the bleaching compositions disclosed herein in accordance with the present invention; in systems where the level of bleaching required is not significantly high they can be sufficient to act as the sole accelerator. However, providing the necessary bleaching power to bleaching compositions (in accordance with the invention) to pass an EN 1276 test in a commercially relevant time requires higher levels of performance from the accelerator and so normally a Glycol ether is chosen. Tables 11 and 12 demonstrate the benefit of increasing the quantity of Ethylene glycol butyl ether in the bleaching compositions. Irrespective of the bleaching power, it is still normal to add a small amount of surfactant to increase the permeability of the cell membrane which can contribute to a loss of membrane function, resulting in cell death and thereby maximise the efficacy of the formulation.
Table 11
A comparison is provided below of the effectiveness of the accelerator, Ethylene glycol butyl ether, and a surfactant containing the functional group of an accelerator, Glucopon CS 215 in a bleaching composition according to the invention.
The results in table 11 above show that the surfactant containing the functional group of an accelerator does indeed improve the bleaching performance, of bleaching compositions but to meet the efficacy standards required of this particular test a more preferred accelerator such as Ethylene glycol butyl ether is required.
Table 12
Provides data demonstrating that higher amounts of accelerator enable the formulation (bleaching compositions) to pass the efficacy requirements of more challenging test tests. As previously mentioned, some applications for the bleaching composition may only require the product to disinfect in clean conditions over prolonged contact times, whereas other applications may require shorter contact times or the ability to still disinfect in the presence of interfering substances.
In Table 12 (see above) the conditions are progressively made more challenging to meet the log 5 reduction required to pass the test. The data demonstrates that to compensate for the shorter contact times and increased levels of interfering substance (BSA), greater levels of the accelerator Ethylene glycol butyl ether can be used in the bleaching composition.
Example 12
It has been noted that electrolytes can improve the bleaching power of the formulation. In Table 13 (see below) progressively more challenging conditions are again used to demonstrate the benefits of incorporating an electrolyte. The electrolyte can be an alkali metal halide or an alkali earth metal halide.
Similar performance benefits for disinfecting bacteria could be achieved by simply raising the concentration of the other active ingredients, but the option of using electrolytes such as Sodium chloride, Magnesium chloride or Potassium iodide can bring significant commercial benefits in areas which can tolerate high electrolyte levels.
Table 13 -see the next page
Demonstrating the improved bleaching efficacy of the bleaching composition provided by adding an electrolyte.
The data in table 13 above demonstrates that the electrolytes Sodium chloride, Magnesium chloride and Potassium iodide all can enable the formulation (bleaching composition) to pass the EN 1276 bactericidal efficacy test in more challenging conditions. The enhanced bacterial efficacy afforded by the electrolyte is demonstrated irrespective of the amount of accelerator incorporated into the bleaching formulation.
Example 13
The necessity of the essential components was investigated as illustrated in Table 14. Table 14
The data in Table 14 demonstrates that removing any of the essential components (i.e. an Enediol, an oxidising agent or a catalyst significantly adversely affects the bactericidal efficacy of the bleaching composition. Example 14
The choice of catalyst has been explored in Tables 15 and 16, see below.
In Table 15 the use of a number of other water soluble transition metal salts were evaluated.
In Table 16 a metal or metal oxide was contained in a capsule and the Ascorbic acid / activator / oxidiser solution passed through the capsule so that the catalyst could act heterogeneously. The solution was then passed through a filter before exiting the capsule and entering the vial containing the components for the EN 1276 test.
Table 15
Evaluating water soluble transition metal catalysts.
The data demonstrates in table 15 that Iron (II) sulfate is a suitable catalyst in this formulation (bleaching composition). Table 16
This table provides data relating to the evaluation of the use of water insoluble metal catalysts.
The data in table 16 shows that a number of transition metals and their oxides can make suitable catalysts in the bleaching compositions of the patent invention.
Example 15
In Table 17, see below, the quantity of catalyst was explored to see if greater quantities of catalyst enabled the formulation to work in more challenging conditions. Table 17 provides data in respect of varying the catalyst concentration.
The data in table 17 shows that the formulation can be extremely efficient (with respect to its bactericidal properties), requiring only very small quantities of the catalyst, Copper sulfate, to disinfect under favourable conditions of long contact times and clean conditions. Yet the formulation (bleaching composition) has the flexibility to work under more challenging conditions simply by raising the quantity of catalyst that is used in the bleaching composition. Example 16
The data provided above demonstrates the range of formulation possibilities for the bleaching composition disclosed herein) to kill bacteria in varying conditions. It is acknowledged that bacteria are one of the easier microorganisms to kill. It can be seen that the formulation (bleaching composition disclosed herein) is capable of killing more difficult microorganisms by raising the concentrations of some of the components. In Table 18, the performance against the yeast Candida albicans according to an EN 1650 test (included herein by reference) is compared against the bacteria Staphylococcus aureus according to the EN 1276 test. EN 1650 is very similar to the aforementioned EN 1276 but is tailored to test for yeasts and fungi rather than bacteria. The pass criteria for EN 1650 is a log reduction of greater than 4, rather than the log 5 required for EN 1276.
Table 18 provides data demonstrating bleaching efficacy (of bleaching compositions according to the invention) against yeasts.
The data in table 18 shows that, as expected, the yeast Candida albicans is a more challenging microorganism to disinfect than the bacteria Staphylococcus aureus. However, formulations disclosed herein demonstrate that acceptable performance can be achieved by raising the concentration of the catalyst, Copper sulfate, that is used in the bleaching compositions.
Example 17
The above disinfectant efficacy tests are known as Suspension tests. As previously described, another class of test, the Surface test can also be used to demonstrate efficacy. The commonly used Surface test is EN 13697 (included herein by reference), which in some cases can be significantly harder to pass than the EN 1276 test.
Table 19 demonstrates the higher levels of substances used to pass this test (EN 13697) in the desirable short contact time of 1 minute. Note that the pass criteria for EN 13697 is a log reduction of greater than 4.
Table 19 - Evaluating the efficacy of the bleaching composition using the alternative disinfectant test method, EN 13697.
The data in table 19 shows that the bleaching composition can meet the efficacy requirements of the more challenging EN 13697 test method using higher levels of the Enediol Ascorbic acid; the accelerator Ethylene glycol butyl ether, or the electrolyte, sodium chloride.
In a further embodiment of the invention the components used to provide a bleaching composition were initially supplied in a substantially water free formulation to improve the shelf-life of the product (bleaching composition disclosed herein). It is not always necessary to remove every trace of water to improve stability. Indeed some common ingredients are supplied in a form known as a hydrate in which water is bound to their structures even in the solid form; in such formulations it is believed that the water content of the formulation comprises less than 25 %wt of the total weight of the formulation that is stored and subsequently added to water to provide a bleaching composition in accordance with the present invention.
The formulations were made up in a substantially water free form, a set weight of the formulation was then dissolved in water to the concentration indicated in the table below. To lOOg of this solution 2mg of Acid red 14 dye was added and the same technique as detailed above was used to measure the time required for half the dye to be destroyed.
Table 21
In table 21 a simple formulation comprising the three essential components of the bleaching composition, an Enediol (Ascorbic acid - AA), an oxidising agent (Sodium percarbonate) and a catalyst (Copper sulfate) was tested for dye destruction in varying ratios.
*In example 1B, the 1% solution of the bleaching composition comprises lg of a formulation (wherein the ratio of AA to sodium percarbonate is 83.3 to 16.7 respectively) to which 99 g of water was added to provide a solution comprising a total weight of lOOg, subsequently 0.0008g of copper sulfate and 2 mg of acid red were added to the solution and the time taken for half of the dye to be destroyed was determined (as shown in the table). This is how the test samples were made up in respect of tables 21 to 25.
The data shows that optimal bleaching performance is obtained between a ratio of Ascorbic acid : Sodium percarbonate of 1:2 and 49: 1, i.e. the ratio of the enediol to oxidising agent is in the rangel:2 and 49: 1. Table 22
A favourable ratio from Table 21 was re-tested using a heterogenous catalyst, in this case Copper (I) oxide.
The data shows that the heterogenous catalyst works effectively in such a system. Whilst the time to reach 50% stain removal may be longer than the time for a corresponding system comprising the homogeneous, this feature may be advantageous where a bleaching composition is to be used to treat delicate materials.
Table 22a
In table 22a an iron based catalyst was used instead of copper.
The data in table 22a shows that iron is a suitable catalyst for use in the bleaching compositions disclosed in accordance with the present invention.
The formulations disclosed above are provided as powders that can be added to water to form a solution (bleaching composition) in accordance with the invention disclosed herein. The choice of accelerators for a powdered formulation is limited since many of the desirable chemicals are present in a liquid state at room temperature. However, the use of the powdered accelerator, glucose, is tested below (see Table 23).When dry formulations for the bleaching compositions (as disclosed herein) are formulated the metal catalyst is preferably copper or iron. Table 23
The data in table 23 demonstrates that the accelerator glucose gives a mild boost to performance when compared to a formulation of Ascorbic acid and Sodium percarbonate in the same ratio (1F). Furthermore, glucose is a relatively cheap ingredient and the data shows that this improved performance can be maintained with much lower levels of Sodium percarbonate and Glucose.
Table 24
A reducing sugar, fructose, was used as the Enediol.
The data in table 24 shows that optimal bleaching performance is obtained between a ratio of Fructose : Sodium percarbonate of 5: 1 and 300: 1, i.e. when the ratio of the reducing sugar, (in this case fructose) that is used as the Enediol is between 5: 1 and 300: 1 relative to the oxidising agent (sodium percarbonate - an oxygen based oxidising agent). Table 25
A liquid accelerator was used to make a slurry of powdered Ascorbic acid and Sodium percarbonate dispersed in the accelerator glycerine. On this occasion the heterogenous catalyst Copper (I) oxide was used.
The data demonstrates that the accelerator glycerine enhances the performance of the heterogenous system in Table 22. Glycerine was used to provide a slurry of a dry mixture that is water free (the water content of the slurry being less than 1 wt% of the total mass of the slurry). Such a slurry may be added to water to provide a bleaching composition and such slurries may be stored for prolonged periods prior to their use.
Various preferable features of the bleaching composition disclosed above in accordance with the present invention are detailed below:
A bleaching composition containing an Enediol, an oxidiser, a catalyst and an accelerator. The oxidiser may be present as an impurity in the accelerator.
A bleaching composition wherein the Enediol is a molecule derived from Ascorbic acid or more preferably Ascorbic acid.
A bleaching composition according to claim 1 where the Enediol is a transient molecule formed during the rearrangement of another molecule, preferably a reducing sugar or derivative thereof. Especially preferred is Fructose or a derivative of Fructose.
A bleaching composition wherein the oxidiser is Hydrogen peroxide, or a Hydrogen peroxide adduct such as Sodium percarbonate.
A bleaching composition wherein the catalyst contains at least one transition metal or at least one salt formed from a transition metal or a combination of at least one transition metal and one salt formed from a transition metal.
A bleaching composition wherein the metal or the salt formed from the metal is taken from the group of period 4 transition metals, preferred is a metal or metal salt taken from the list of Cobalt, Copper, Iron, Manganese, Silver, Titanium, Vanadium and Zinc, especially preferred is a metal or metal salt containing Copper.
A bleaching composition wherein the catalyst is substantially insoluble in water, preferably the catalyst is a metal oxide.
A bleaching composition wherein the catalyst is substantially soluble in water, more preferably the salt is a metal halide or sulphate.
A bleaching composition wherein the accelerator contains at least one alcohol group or at least one ether group or at least one cyano group, more preferred is an accelerator which contains both an alcohol and at least one ether group, especially preferred is an accelerator taken from the list Ethylene glycol butyl ether, Diethylene glycol butyl ether, Glucose, Acetonitrile, Hexylene glycol, PPG-2 methyl ether, Dipropylene glycol, 1 -Propanol, Ethylene glycol, Butyronitrile, Acetone, Ethylene glycol propyl ether, Ethanol, Butoxy diglycol. Dipropylene glycol mono methyl ether, Diethylene glycol and Fructose.
A bleaching composition which additionally contains an electrolyte, preferably an alkali metal halide.
A bleaching composition which additionally contains a surfactant, preferably an Alcohol alkoxylate or an Alkyl poly glucoside.
A bleaching composition which additionally contains any one of a pH regulator, dye, diluent, perfume, surfactant, rheology modifier, suspending agent, corrosion inhibitor, water softener, processing aid or defoamer.
A bleaching composition according to claim 1 where the Ascorbic acid is present in the in-use bleaching solution at a concentration between 0.01% and 10% by weight. The use of ascorbic acid at levels between 5 and 10 wt% may be required when the bleaching composition is to be used to kill viruses and spores.
A bleaching composition wherein the oxidiser is present in the in-use bleaching solution at a concentration between 0.005% and 5% by weight.
A bleaching composition wherein the catalyst is substantially water soluble and is present in the in- use bleaching solution at a concentration between 0.0001% and 1% by weight. The use of the catalyst at higher levels (e.g. 0.1 to 1 %wt) may be required when the bleaching composition is to be used to kill viruses and spores.
A bleaching composition wherein the Accelerator is present in the in-use bleaching solution at a concentration between 0.1% and 20% by weight. The use of the accelerator at higher levels (e.g. 10 to 20 %wt) may be required when the bleaching composition is to be used to kill viruses and spores. A bleaching composition wherein an Electrolyte is present in the in-use bleaching solution at a concentration of up to 10% by weight. The use of the electrolyte at higher levels (e.g. 2.5 to 10 %wt) may be required when the bleaching composition is to be used to kill viruses and spores.
A bleaching composition wherein the catalyst is substantially water insoluble and is contained in part of the delivery mechanism such as part of a spraying device, embedded in a wiping device or impregnated into a surface onto which or through which the remaining components of the bleaching solution can be applied.
A bleaching composition wherein the catalyst is substantially water and mixed with the remaining components of the bleaching solution at the point of use through a dosing device, or is contained as a powder within a substantially anhydrous formulation which is dissolved in water immediately prior to use.
A bleaching composition wherein at least one of the essential components of the bleaching composition is present in a powdered form and suspended in a slurry of one of the other essential components or an additional substance, as referred to immediately above, to prevent premature activation of the bleaching composition.

Claims

Claims
1. A bleaching composition comprising: an enediol; an oxidising agent; and a, a catalyst.
2. A bleaching composition as claimed in claim 1 wherein the bleaching composition further comprises an accelerator.
3. A bleaching composition as claimed in claim 1 or 2 wherein the bleaching composition further comprises an electrolyte.
4. A bleaching composition as claimed in any preceding claim wherein the enediol is chosen from the group comprising one or more of: ascorbic acid; derivatives of ascorbic; an enediol formed from the rearrangement of a reducing sugar; and an enediol formed from the rearrangement of a derivative of a reducing sugar.
5. A bleaching composition as claimed in claim 4 wherein the enediol is chosen from the group of ascorbic acid derivatives comprising one or more of: 5,6-isopropylidene-L-ascorbic acid; 6-0- palmitoyl-L-ascorbic acid.
6. A bleaching composition as claimed in claim 4 wherein the enediol is ascorbic acid.
7. A bleaching composition as claimed in any preceding claim wherein the enediol is present at a level in the range of 0.01 to 10 %wt when the bleaching composition is in the form of an aqueous solution.
8. A bleaching composition as claimed in any of claims 1 to 6 wherein the enediol is present at a level in the range of 0.1 to 3 %wt when the bleaching composition is in the form of an aqueous solution.
9. A bleaching composition as claimed in any of claims 1 to 6 wherein the enediol is present at a level in the range of 0.3 to 1 %wt when the bleaching composition is in the form of an aqueous solution.
10. A bleaching composition as claimed in any preceding claim wherein the oxidising agent is chosen from the group comprising one or more of: a chlorine based oxidising agent; and, an oxygen based oxidising agent.
11. A bleaching composition as claimed in claim 10 wherein the oxygen based oxidising agent is chosen from the group comprising one or more of: Peracetic acid; tertiary butyl hydroperoxide, hydrogen peroxide; and an agent that releases hydrogen peroxide.
12. A bleaching composition as claimed in any of claims 1 to 10 wherein the oxidising agent is hydrogen peroxide.
13. A bleaching composition as claimed in any preceding claim wherein the oxidising agent is present in the range of 0.001 to 5 %wt when the bleaching composition is in the form of an aqueous solution.
14. A bleaching composition as claimed in any one of claims 1 to 12 wherein the oxidising agent is present in the range of 0.005 to 1 %wt when the bleaching composition is in the form of an aqueous solution.
15. A bleaching composition as claimed in one of claims 1 to 12 wherein the oxidising agent is present in the range of 0.005 to 0.3 %wt when the bleaching composition is in the form of an aqueous solution.
16. A bleaching composition as claimed in any preceding claim wherein the catalyst is chosen from the group comprising one or more of: a transition metal; an oxide of a transition metal; and a salt of a transition metal.
17. A bleaching composition as claimed in claim 16 wherein the transition metal(s) is/are chosen from the group comprising one or more of: Cobalt; Copper; Iron; Manganese; Silver; Titanium; Vanadium; and Zinc.
18. A bleaching composition as claimed in claim 16 or 17 wherein the salt of the transition metal is chosen from the group comprising one or more of: a metal halide; and, a metal sulphate
19. A bleaching composition as claimed in claim 16 to 18 wherein the catalyst is chosen from the group comprising one or more of: metallic copper; an oxide of copper; a salt of copper; metallic manganese; an oxide of manganese; a salt of manganese; metallic iron; an oxide of iron; and, a salt of iron
20. A bleaching composition as claimed in claim 19 wherein the oxide of copper is chosen from the group comprising one or more of: copper (I) oxide; and, copper (II) oxide.
21. A bleaching composition as claimed in claim 16 to 18 wherein the metal salt is chosen from the group comprising one or more of: a copper salt; and a manganese salt, and an iron salt.
22. A bleaching composition as claimed in claim 21 wherein the copper salt is chosen from the group comprising one or more of: copper sulphate; and, copper chloride.
23. A bleaching composition as claimed in claim 21 wherein the manganese salt is manganese sulphate.
24. A bleaching composition as claimed in any preceding claim wherein the catalyst is present in the range of 0.00001 to 1 %wt when the bleaching composition is in the form of an aqueous solution.
25. A bleaching composition as claimed in any of claims 1 to 23 wherein the catalyst is present in the range of 0.0001 to 0.1 %wt when the bleaching composition is in the form of an aqueous solution.
26. A bleaching composition as claimed in any of claims 1 to 23 wherein the catalyst is present in the range of 0.0008 to 0.01 %wt when the bleaching composition is in the form of an aqueous solution.
27. A bleaching composition as claimed in any of claims 2 to 26 wherein the accelerator is chosen from the group of organic compounds comprising one or more of: one or more alcohol groups; one or more ether groups; and one or more cyano groups.
28. A bleaching composition as claimed in claim 2 to 26 wherein the accelerator comprises at least one alcohol and at least one ether group.
29. A bleaching composition as claimed in claim 28 wherein the accelerator is a glycol ether.
30. A bleaching composition as claimed in any of claims 27 to 29 wherein the accelerator is chosen from the group comprising one or more of the following: ethylene glycol butyl ether; diethylene glycol butyl ether; glucose; acetonitrile; hexylene glycol; PPG-2 methyl ether; dipropylene glycol; 1 -propanol; ethylene glycol; butyronitrile; acetone; ethylene glycol propyl ether; ethanol; butoxy diglycol; dipropylene glycol mono methyl ether; diethylene glycol; and fructose.
31. A bleaching composition as claimed in any of claims 27 to 30 wherein the accelerator is chosen from the group comprising one or more of the following: glucose; hexylene glycol; and fructose.
32. A bleaching composition as claimed in any of claims 2 to 31 wherein the accelerator is present in the range of 0.1 to 10 %wt when the bleaching composition is in the form of an aqueous solution.
33. A bleaching composition as claimed in any of claims 2 to 31 wherein the accelerator is present in the range of 0.1 to 5 %wt when the bleaching composition is in the form of an aqueous solution.
34. A bleaching composition as claimed in any of claims 2 to 31 wherein the accelerator is present in the range of 0.25 to 2 %wt.
35. A bleaching composition as claimed in any of claims 3 to 34 wherein the electrolyte is chosen from the group comprising one or more of a halide salt of an alkaline metal and/or a halide salt of an alkaline earth metal.
36. A bleaching composition as claimed in 35 wherein the alkaline metal salt or alkaline earth metal salt is chosen from the group comprising: a chloride salt; and an iodide salt.
37. A bleaching composition as claimed in 35 or 36 wherein the electrolyte is preferably chosen from the group comprising one or more of: sodium chloride; potassium iodide; and magnesium chloride.
38. A bleaching composition as claimed in any of claims 3 to 37 wherein the electrolyte is present at a level of up to 10 %wt when the bleaching composition is in the form of an aqueous solution.
39. A bleaching composition as claimed in any of claims 3 to 37 wherein the electrolyte is present in the range of 0.1 to 10 %wt when the bleaching composition is in the form of an aqueous solution.
40. A bleaching composition as claimed in any of claims 3 to 37 wherein the electrolyte is present in the range of 0.1 and 5 %wt when the bleaching composition is in the form of an aqueous solution.
41. A bleaching composition as claimed in any of claims 3 to 37 wherein the electrolyte is present in the range of 0.25 and 2 %wt when the bleaching composition is in the form of an aqueous solution.
42. A bleaching composition as claimed in any preceding claim wherein the catalyst is only added to the bleaching composition immediately prior to the composition being mixed for use.
43. A bleaching composition as claimed in any preceding claim wherein the catalyst further comprises a heterogeneous solid in an aqueous bleaching composition.
44. A bleaching composition as claimed in any preceding claim wherein the catalyst is in the form of a powder or granules.
45. A bleaching composition as claimed in any preceding claim wherein the catalyst is provided separately to the other components of the bleaching composition, and the other components of the bleaching composition are exposed to the catalyst as they are poured or sprayed from a container.
46. A bleaching composition as claimed in any preceding claim wherein the bleaching composition, following its use, dries to form a powder.
47. A bleaching composition as claimed in any preceding claim wherein the composition further comprises one or more performance enhancers chosen from the group comprising pH regulators; dyes; diluents; perfumes; surfactants; rheology modifiers; suspending agents; corrosion inhibitors; water softeners; processing aids; and, defoamers.
48. A bleaching composition as claimed in any of claims 1 to 46 wherein the composition further comprises performance enhancers in the form of one or more surfactants.
49. A bleaching composition as claimed in claims 48 wherein the surfactant is an alcohol alkoxylate and/or an alkyl poly glucoside.
50. A bleaching composition as claimed in any preceding claim wherein the composition is provided as a powder, as a tablet or as a water free slurry.
51. A bleaching composition as claimed in any of preceding claim wherein the composition is provided as an aqueous solution.
52. A bleaching composition as claimed in any preceding claim wherein the bleaching composition is provided as an aqueous solution and wherein the catalyst is provided as a separate component that is added immediately prior to the use of the composition.
53. A bleaching composition as claimed in any preceding claim wherein the bleaching composition is provided as an aqueous solution, with the catalyst provided as a separate component that, in use, is contacted with the aqueous solution.
54. A bleaching composition as claimed in any preceding claim wherein the heterogeneous catalyst is impregnated onto a cloth, a door handle, the delivery system of a triggerspray, or a cartridge containing the catalyst.
55. A bleaching composition as claimed in any of claims 10 to 54 wherein the chlorine based oxidising agent is sodium hypochlorite.
56. A bleaching composition as claimed in any of claims 16 to 18, 21, and 24 to 55 wherein the iron salt is chosen from the group comprising one or more of; iron chloride; and, iron sulphate.
57. A bleaching composition as claimed in any of claims 16 to 18, 19, 21 and 24 to 55 wherein the catalyst is copper.
58. A bleaching composition as claimed in any of claims 16 to 18, 19, 21 and 24 to 56 wherein the catalyst is iron.
59. A bleaching composition as claimed in any of claims 11 to 58 wherein the agent that releases hydrogen peroxide is chosen from the group comprising one or more of; sodium percarbonate; and, sodium perborate
60. Use of a bleaching composition as claimed in any preceding claim as a stain remover.
61. Use of a bleaching composition as claimed in any one of claims 1 to 59 claim as an anti-microbial.
62. Use of a bleaching composition as claimed in any of claims 1 to 59 for use as an anti-microbial preparation.
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GB2572364B (en) 2023-04-12
GB2572364A (en) 2019-10-02
WO2019186159A1 (en) 2019-10-03

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