EP0773718A1 - Oxydierende zusammensetzungen - Google Patents

Oxydierende zusammensetzungen

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Publication number
EP0773718A1
EP0773718A1 EP95927860A EP95927860A EP0773718A1 EP 0773718 A1 EP0773718 A1 EP 0773718A1 EP 95927860 A EP95927860 A EP 95927860A EP 95927860 A EP95927860 A EP 95927860A EP 0773718 A1 EP0773718 A1 EP 0773718A1
Authority
EP
European Patent Office
Prior art keywords
activator
product
peroxygen source
biocide
reaction
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.)
Ceased
Application number
EP95927860A
Other languages
English (en)
French (fr)
Inventor
Vincent Brian Croud
Stephen James 5 Lower Bonc Terrace TOMPSETT
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.)
Warwick International Group Ltd
Original Assignee
Warwick International Group 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 Warwick International Group Ltd filed Critical Warwick International Group Ltd
Publication of EP0773718A1 publication Critical patent/EP0773718A1/de
Ceased legal-status Critical Current

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Classifications

    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/16Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group; Thio analogues thereof

Definitions

  • This invention relates to products for forming biocidal compositions, their reactions and uses.
  • the invention relates to the formation of a biocide for killing bacteria, viruses, fungi, micro ⁇ organisms and bio-films from an oxidation reaction in which a peroxygen compound is the oxidant.
  • a peroxygen compound is the oxidant.
  • It is known for example from GB-A-2219790 to form biocidal compounds by oxidising halide ions in situ.
  • This reference relates to a method for sanitising water, such as swimming pool water by introducing a bromide or iodide ion and oxidising the bromide or iodide ion using hypochlorite, ozone or potassium peroxymonosulphate.
  • a contact lens disinfectant provides active iodine by in situ reaction of iodide and a peroxygen source in aqueous solution.
  • Bleaching compositions comprising bromide ions are described in EP-A-24368.
  • the compositions also include a precursor which forms a peracid anion in aqueous solution and the compositions are used as laundry detergents under highly alkaline conditions. It is postulated that the peracid anion generated by the reaction of an activator and a peroxygen source reacts in situ with bromide ions to oxidise them to form hypobro ite and that the hypobro ite acts as the active bleaching component. Bromide regenerated by the bleaching reaction is again oxidised to OBr ' .
  • alkaline bleaching liquors produced by dissolution of compositions containing a peroxygen source and an activator have been described as having biocidal properties, for instance by virtue of the presence of peracid anion generated by reaction of activator and peroxygen source.
  • peracid anion generated by reaction of activator and peroxygen source For instance such utility is disclosed in GB-A-1337858.
  • other biocides can be added to the composition to supplement the bactericidal effects of the peracid anion.
  • the by-product of the reaction creating the peracid formed by hydrolysis of an ester of an aryl hydroxyl group, that is a benzoic acid derivative with a hydroxyl substituent in the ring has biocidal properties.
  • Caro's acid is mentioned as one of the peroxygen sources.
  • enol ester activators are used in combination with peroxygen sources as a bleaching composition.
  • the utility of the composition includes biocidal properties and it may be used in recirculating water systems.
  • the compositions may be supplemented with additional biocidal components and in the recirculating water system, as well as acting as a biocide the composition may oxidise other oxidisable components present in the water which it is desired to remove.
  • WO-A-9418299 (not published at the priority date of the present application) , the use of an acyl donor activator in combination with a peroxygen source under acidic conditions is described. It is suggested that co- disinfectants, co-biocides and slimicides may be useful additives for compositions based upon those components.
  • WO-A-9418297 describes similar products and processes. Worked examples include surfactant-containing compositions as well as citric acid. Citric acid can act as a virucide. S ⁇ FW-Journal, 118 Gonzgang 9/92, p 556-562, describes the study of enzyme mediated generation of microbial compounds in mammalian systems.
  • lactoperoxidase uses hydrogen peroxide from lactobacilli or other contaminating microorganisms in milk to oxidise thiocyanate ions to form anti-microbial hypothiocyanate anion.
  • the finding has been used to produce anti-microbial compositions which are described in WO91/11105.
  • the compositions contain iodide and thiocyanate ions which are oxidised in situ using hydrogen peroxide which is produced in situ by an oxidoreductase enzyme, glucose oxidase with its corresponding oxidisable substrate, glucose. It is reported in the article mentioned above that for efficacy an enzymic source of hydrogen peroxide must be used.
  • Enzymes may provide handling difficulties and efforts must be taken to ensure that they do not lose their activity. Enzymes systems are also very limiting because it is not possible to obtain high concentrations of oxidising agent.
  • a biocidal composition which is a composite product comprising a peroxygen source, an activator for the peroxygen source which is an acyl donor, the acyl group of which has 2 or more carbon atoms, a biocide precursor which is a different compound to the peroxygen source, the activator and the product of the reaction between the peroxygen source and the activator in aqueous solution and which reaction with the reaction product of the peroxygen source and the activator in aqueous solution produces a biocidally active species ("a co-biocide”) and if necessary, a pH-modifying component such that when all of the components of the composition are dissolved in aqueous solution, the pH is less than pK,(l), where pK,(l) is the pH of the percarboxylic acid corresponding to the acyl group of the activator.
  • a co-biocide a biocidally active species
  • the co-biocide produced in situ broadens the biocidal spectrum of the species produced in situ by reaction of the activator and the peroxygen source.
  • the activator may be an N-acyl or an O-acyl derivative.
  • the activator is a compound of the formula I
  • the leaving group L is preferably a compound the conjugate acid of which has a pK a in the range 4 to 13, preferably 7 to 11, most preferably 8 to 11. It is preferred that R is an aliphatic group preferably a . u alkyl group, a C ⁇ -alkenyl or an aryl group, most preferably a methyl group, a branched or straight chain C 6 . 1 ⁇ -alkyl group or a phenyl group.
  • alkyl and alkenyl groups may be straight, branched or cyclic.
  • L and R may be joined to form a cyclic compound, usually a lactone or a lactam.
  • cyclic groups may include heteroatoms, for instance oxygen or optionally substituted nitrogen atoms, carboxyl groups as well as -CH 2 - groups or substituted derivatives thereof. They may be saturated or unsaturated.
  • Substituents on R 1 and L can include hydroxyl,
  • R 2 is selected from any of the groups represented by R 1 and is preferably lower alkyl, a ine, acyl, acyloxy, alkoxy, aryl, aroyl, aryloxy, aroyloxy. halogen, amido, and imido groups and the like as well as other groups not adversely affecting the activity of the compound.
  • the compound of the formula I can be any N-acyl or O-acyl acyl-donor compound, which has been described as a bleach activator for use in laundry detergents.
  • the compound of the formula I may be an anhydride, but is preferably an ester or, even more preferably, an amide derivative.
  • Amide derivatives include acyl imidazolides and N,N-di acylamines, such as TAED.
  • Other examples of N-acyl derivatives are: a) l,5-diacetyl-2, 4-dioxohexahydro-l,3,5-triazine
  • N-alkyl-N-sulphonyl carbonamides for example the compounds N-methyl-N-mesyl acetamide, N-methyl-N-mesyl benzamide, N-methyl-N-mesyl-p-nitrobenzamide, andN-methyl-
  • N-mesyl-p-methoxybenzamide c) N-acylated cyclic hydrazides, acylated triazoles or urazoles, for example monoacetyl aleic acid hydrazide; d) ⁇ ,N,N-trisubstituted hydroxylamines, such as O-benzoyl- N,N-succinyl hydroxylamine, 0-p-nitrobenzoyl-N,N-succinyl hydroxyla ine and ⁇ ,N,N-triacetyl hydroxylamine; e) N,N'-diacyl sulphurylamides, for example N,N'-dimethyl- N,N'-dimethyl-N,N'-diacetyl sulphury1 amide and N,N'- diethy1-N,N'-dipropionyl sulphurylamide; f) l,3-diacyl-4,5-diacyloxy
  • k 0,N,N-trisubstituted alkanolamines, such as 0,N,N- triacetyl ethanolamine.
  • Cyanamides such as those disclosed in DE-A-3,304,848.
  • N-acyl lactams such as N-benzoyl-caprolactam, N-acetyl caprolactam, the analogous compounds formed from C 4 . 10 lactams.
  • the compound may be an ester, for instance n) sugar esters, such as pentaacetylglucose, o) esters of imidic acids such as ethyl benzimidate, p) triacylcyanurates, such as triacetylcyanurate and tribenzoy1cyanurate, q) esters giving relatively surface active oxidising products for instance of C j . ⁇ -alkanoic or -aralkanoic acids such as described in GB-A-864798, GB-A-1147871 and the esters described in EP-A-98129 and EP-A-106634, for instance compounds of the formula I where L comprises an aryl group having a sulphonic acid group (optionally salified) substituted in the ring to confer water solubility on a benzyl group, especially nonanoyloxy- benzenesulphonate sodium salt (NOBS) , isononanoyloxy- benzenesulphonate sodium salt (NO
  • activator is an anhydride it is preferably an intra-molecular anhydride, or a polyacid polyanhydride.
  • anhydride compounds are more storage stable than liquid anhydrides, such as acetic anhydride.
  • Anhydride derivatives which may be used as activator include v) intramolecular anhydrides of dibasic carboxylic acids, for instance succinic, maleic, adipic, phthalic or 5- norbornene-2,3-dicarboxylic anhydride, w) intermolecular anhydrides, including mixed anhydrides, of mono- poly-basic carboxylic acids, such as diacetic anhydride of isophthalic or perphthalic acid x) isatoic anhydride or related compounds such as described in WO-A-8907640 having the generic formula II
  • Q is a divalent organic group such that Q and N together with the carbonyl groups and oxygen atom of the anhydride group form one or more cyclic structures and R is H, alkyl, aryl, halogen or a carbonyl group of a carboxyl containing function; or benzoxazin-4-ones as described in WO-A-8907639, that is compounds of the formula III
  • Q' is selected from the same groups as Q and R ..3 J is H, alkyl, aryl, alkaryl, aralkyl, alkoxyl, haloalkyl, a ino, aminoalkyl, carboxylic group or a carbonyl- containing function; preferably 2-methyl-(4H)3,l- benzoxazin-4-one (2MB4) or 2-phenyl-(4H)3,l-benzoxazin-4- one (2PB4); y) polymeric anhydrides such as poly(adipic) anhydride or other compounds described in our co-pending application WO- A-9306203.
  • the upper limit of the pH specified for the invention is the higher of the pK a 's of the peracids corresponding to the two acyl groups, if they are different to one another.
  • a mixture of one activator which is an acetyl derivative with one activator which is a higher alkanoyl or aryl derivative might be useful.
  • the pK a of peracetic acid is, for example 8.2, whilst that of performic acid is 7.1 and that of peroxy benzoic acid is 7.6.
  • the activator may be a compound which is a solid at room temperature, for instance which has a melting point of at least 40°C, preferably at least 50°C, for instance higher than 60°C.
  • the peroxygen source may be hydrogen peroxide itself, or an inorganic persalt, for instance a percarbonate or, a perborate, for instance sodium perborate, or an organic peroxide such as benzoyl peroxide or urea peroxide.
  • Particularly preferred peroxygen sources are sodium perborate, sodium percarbonate, or even Caro's acid (monopersulphuric acid) or salts thereof. Where Caro's acid is the biocide precursor another compound must be used as the peroxygen source.
  • the biocide precursor is any component which can be reacted with the product mixture of the reaction between the peroxygen source and the activator to provide a biocidally active species, the co-biocide.
  • the benefit of this is that one can use a biocide precursor which does not react or not at a significant rate, with the either the peroxygen precursor itself or the activator especially at ambient temperatures.
  • the reaction of the biocide precursor is believed to be with the stronger oxidising compound formed upon the reaction between the peroxygen source and the activator (which product is believed to be the percarboxylic acid derived from the acyl group of the activator, or its anion) is believed to be an oxidation reaction.
  • a halide ion is oxidised to form an active halogen species Hal 3 , or hypohalite OHal " , which are potent disinfecting agents.
  • the biocide precursor may itself have some biocidal properties, but such properties are generally less potent than the biocidal properties of the biocidal species i.e. the co-biocide formed upon its reaction with the product of the reaction between the activator and the peroxygen source or else are not exhibited for at the pH's specified for the use step of the present process.
  • Caro's acid acts as a biocide precursor but has some biocidal properties itself.
  • biocide precursor may also be Caro's acid (monoperoxysulphate) which reacts with the product of the reaction between an activator and a peroxygen source, though not with either compound individually, to form a product which is a highly potent biocide.
  • the activator is TAEO.
  • the peroxygen source may be hydrogen peroxide or a solid peroxygen compound.
  • the activator is any other activator which is solid at ambient temperatures.
  • the present invention also includes a process comprising reacting a peroxygen source with an activator compound which is an acyl donor the acyl group of which preferably has at least 2 carbon atoms in a first step in aqueous solution to form a product solution comprising an oxidising product which is a stronger oxidising agent than the peroxygen source itself, and in a second step, a biocide precursor is oxidised by the oxidising product to form a biocidal species in a final solution and in a third step, using the final solution as a biocidal composition at a pH below pK a (l) where pK a (l) is the pK a of the percarboxylic acid corresponding to the acyl group of the activator.
  • the biocide precursor is present in the first step, during the reaction between the peroxygen source and the activator compound.
  • the peroxygen source and activator compound are reacted in aqueous solution.
  • the first step is also at a pH below pK a (l) .
  • the present invention is particularly advantageous because a wider range of biocidal species formed by oxidation are made available and can be made in situ from storage stable compositions.
  • the pH in the first and third steps is preferably acidic, more preferably less than 6.5.
  • the pH in the perhydrolysis step is usually more than 2.0.
  • the composite product which may provide the components for the first step may contain a pH-adjusting component usually an acidifying component.
  • an additional acidifying component it may be an acid and/or buffering material.
  • the component may comprise a polybasic organic acid, such as a polybasic carboxylic acid such as succinic or adipic acid, in addition to citric and/or sulphamic acid.
  • the component may react with a by-product of the perhydrolysis reaction to increase the acidity in use.
  • perborate is used, borate is a by ⁇ product and so any component known to react with borate to drop the pH, e.g. cis-l,2-diols, such as glycols and polyols, boric acid or sodium dihydrogen phosphate can be used.
  • the composition may also comprise an additional biocidal component, such as silver salt.
  • the silver salt is preferably present in concentrations less than the solubility limit of silver.
  • the silver ions may be present as silver complexes which are stable and soluble in aqueous solution.
  • Silver salts are particularly preferred as an additional biocidal component as they increase the range of biocidal activity of the solutions produced and provide a synergistic biocidal effect when used in combination with the biocidal species formed from a halide ion or from thiocyanate.
  • Particularly preferred silver salts for incorporation into the product solution include silver thiocyanate, silver ammonium iodide or any other soluble silver halide complex.
  • the additional biocidal components if present in the first step, in which the peroxygen source and activator compound are reacted.
  • the concentration of silver ions or other additional biocidal components will be such as to produce a biocidal effect in the final solution.
  • their concentration may be from O.OOlg/1, generally from 0.01, or even O.lg/1.
  • their concentration will not exceed 50g/l or most preferably 20g/l.
  • Stabiliser may also be included in the compositions and processes of the invention, which will increase the storage stability of the peroxide and/or the silver ions which may be light sensitive.
  • the amount of water present is preferably at least as much (in terms of moles) as the peroxygen source.
  • the concentration of hydrogen peroxide is preferably less than 70% weight/volume (that is weight of hydrogen peroxide based on volume of water plus hydrogen peroxide plus other components in the mixture concerted) .
  • the concentration is less than 60% weight by volume and more preferably less than 30% w/v.
  • the concentration is preferred for the concentration to be less than 15% or even 10% w/v or less than 5% w/v.
  • the concentration is preferably such as to give the equivalent available oxygen as the quoted concentrations of hydrogen peroxide.
  • the pH in the second step is usually also in the same range.
  • the pH may vary, usually becoming more acid as the reaction between the various components takes place.
  • the present invention allows the formation of an aqueous biocidal liquor containing a blend of biocidally active species, one of which is the oxidising product from the first step.
  • the activator and peroxygen source are therefore present in amounts so as to form the oxidising product in a stoichiometric excess over the biocide precursor so that there will be at least some biocide which is the oxidising product formed in the first step and at least some co-biocide which is formed from the biocide precursor by its reaction in the presence of the product mixture of the first step of the process of this invention.
  • the biocidal liquor obtained in this way has improved properties.
  • the combination of biocidal components can give a broader spectrum of activity against microbes, for example against bacteria with potential to cause infection. It also allows the compositions to have utility over a wider range of use conditions, than the individual biocides, such as of temperature components. The compositions are therefore highly effective.
  • the biocidal activity of the final solution may be optimised for a particular application by changing the relative amounts of peroxygen source, activator, biocidal precursor and optional additional biocidal component.
  • the temperature is preferably in the range 0 to 95°C, more preferably in the range 10 to 80°C.
  • the invention is most useful when the temperature is less than 60°C, or even less than 50°C, for instance less than 40 ⁇ C or even around room temperature.
  • the temperature is often above 20°C.
  • the temperature in the second and third steps is likely to be somewhat lower than the temperature in the first step, due to cooling either prior to or on application of the product of the third step to a substrate to be treated with biocide.
  • Preferred temperatures for the third step are preferably in the same ranges as the temperature during the perhydrolysis (first) step and is preferably substantially the same temperature.
  • a particular advantage of using activators for the peroxygen source is that the oxidising product tends to be formed at a relatively low temperature, for instance at temperatures around ambient and less than hand hot which is advantageous from a safety point of view. Also the rate of perhydrolysis reaction can be controlled by adjusting the temperature.
  • the peroxygen source and the bleach activator may be allowed to react in aqueous conditions in the presence of the biocide precursor for at least five minutes, up to one or two days, suitably in the range ten minutes to one day such that the second step takes place and there is a time delay before the third step ie the use as a biocidal composition of the final solution.
  • the biocidal species may be relatively short lived and if so, there is preferably no greater than a short time delay between the second and third steps.
  • the biocide precursor must not be added to the product solution until shortly before use, or the time delay between the second and third steps must not be so long that the biocidal species produced has substantially lost its biocidal properties.
  • the biocide precursor is present in the first step so that the first and second steps are substantially simultaneous.
  • the time delay between the second and third steps is preferably no greater than 2 hours, preferably less than 1 hour or even 30 minutes.
  • the peroxygen source, bleach activator and biocide precursor may be mixed together and added to water simultaneously, or alternatively they may be added to water one after the other or in various combinations. They may be added to water and used immediately.
  • the third step in accordance with the process of the present invention in which the final solution is used as a biocidal composition may comprise application in any situation where a disinfectant or biocidal cleaning step is required usually of hard surfaces.
  • the final solutions prepared according to the invention may be used in domestic or institutional applications, for example in kitchens and bathrooms or, may be used in medical applications. Further examples are given below.
  • the composite product may contain the individual components each in separate compositions, for instance one of which contains the peroxygen source, another of which contains the activator and another of which contains the pH-modifying component, it is preferred to provide at least the activator and pH-modifying component as a mixture in a single composition in a form in which they are stable.
  • a composition which does not contain peroxygen source may, for instance, be added to an aqueous solution of peroxgyen source such as aqueous hydrogen peroxide, which is readily commercially available, in the form of, for instance 60%, 20%, 10% or, preferably, 5% w/v or less solution. It is most preferred for all of the components to be provided in a single composition, in which the components do not react.
  • the produc (s) may be in liquid form, for instance in a non-aqueous liquid medium, in which the components may be dissolved or dispersed.
  • particles of activator with protective coatings for instance produced by microencapsulation techniques or spray coating of solid activator, may be suspended in an aqueous, or non aqueous, solution of peroxygen source.
  • particles of solid peroxygen source optionally being coated with a protective coating. Coated particles of either peroxygen source or activator may be disrupted or diluted in to water or with abrasion.
  • composition or each composition of the composite product is in a solid form, for instance as a mixture of particles of the individual components or, more preferably, comprising particles each of which comprise all of the components.
  • particles may be provided by techniques similar to those used in the laundry detergent industry, for instance including particles produced by spray drying liquid slurries, by granulation techniques using binders (for instance synthetic or natural polymers or derivatives) or by melt blending followed by extrusion or other techniques.
  • the product contains the active ingredients in appropriate relative quantities so that when the composition is diluted (or the compositions are mixed) with water the first step of the reaction proceeds at the optimal rate and at the desired pH.
  • the activator and peroxygen source are for instance present in relative amounts such that up to 150%, preferably up to 100%, or most preferably up to 80% of the stoichiometric amount of activator (for complete reaction with the peroxygen source) is provided.
  • the product solution may require surface active properties.
  • the composite product may comprise a surfactant. Any conventional surfactant may be used, selected from non-ionic, anionic, cationic, and amphoteric surfactants. However, non-ionic and amphoteric surfactants are preferred as they are more resistant to changing conditions of pH.
  • Suitable nonionic surfactants include for example alkanolamides (such as CIO to C20) and/or ethoxylated alcohols, carboxylic acids, amines, alcohol amides, alcohol phenol, glyceryl esters, sorbitan esters, phosphate esters etc.
  • Suitable amphoteric surfactants include for example betaines, such as alkyl betaines, sulphobetaines, and also imidazoline derivatives.
  • Suitable cationic surfactants include for example quaternary amines, imidizolines and quaternised imidizolines.
  • a biocidal cationic surfactant is used which provides an additional biocidal species in the final use liquor the product of the third step.
  • a cationic surfactant may, for instance, have a halide counterion associated with it and the halide counterion can act as the biocide precursor required in the present invention. This embodiment thus gives a highly advantageous combination of active ingredients.
  • Suitable anionic surfactants include any surfactant useful in a detergent for example salts of sulphonic or monoesterified sulphuric acids, fatty alkyl ether sulphosuccinates, acyl sarcosinates, acyl taurides and paraffin sulphonates.
  • the preferred anionic surfactants are salts of alkali metals or alkaline earth metals, preferably sodium.
  • the composite product may include other additives, for instance stabilisers which stabilise the composite product on storage as well as stabilisers for the oxidising species formed in the first step of the process, such as a heavy metal sequestrant chelating agent.
  • a heavy metal sequestrant chelating agent such as a heavy metal sequestrant chelating agent.
  • Particularly preferred chelating agents are alkylene poly(amine carboxylic acids), alkylene poly(alkylene aminophosphonic acids) and their salts especially ethylenediamine tetraacetic acid (EDTA) , diethylene triamine pentaacetic acid (DTPA) , diethylenetriamine penta( ethylene phosphoric acid) (DTPMP) and ethylenediamine tetra(methylene phosphonic acid) (EOTMP) .
  • EDTA ethylenediamine tetraacetic acid
  • DTPA diethylene triamine pentaacetic acid
  • DTPMP diethylenetriamine penta( ethylene phosphoric acid
  • inorganic salts for instance which affect the physical properties of the solid form or act as diluent may also be incorporated.
  • Other ingredients may be included depending upon for example the mode of use of the composition. Examples are perfumes, or agents to assist dissolution or dispersion of the product into water or inorganic or enzymatic catalysts.
  • reaction product of the reaction in the first and second steps is preferably used immediately, without removal of any by-products or addition of other materials, in the third step in which it is used as a biocide.
  • the composite product of the present invention may be provided in a form which is suitable to be diluted directly into water to allow the first and second steps of the reaction to proceed without further additions.
  • the composite product of the present invention may be either solid or liquid.
  • they may be pourable liquids which are aqueous or non-aqueous.
  • Thickeners may be included in a liquid product to increase viscosity, such as those which are well known in the art, including gums, electrolytes (in combination with surfactant) , urea, triethanolamine and polyacrylates.
  • process steps of the present invention can be carried out at a relatively low concentration they can be carried out without special precautions, for instance in a domestic or institutional environment.
  • the composite products themselves prior to dissolution or dispersion in water may be non-hazardous to handle.
  • compositions which are suitable to be diluted direct into water to allow the first and second steps of the reaction to proceed without further additions may be categorised in four convenient categories.
  • the first category comprises liquid formulations which include a surfactant.
  • These compositions will be suitable for use as hard surface cleaners and other uses where surface active disinfection is required, for instance floor cleaning compositions, domestic and institutional hard surface cleaners, toilet disinfectants, general toiletries disinfectant, sanitising bottles, including glass and plastic bottles, and pipe cleaning compositions.
  • floor cleaning compositions for instance floor cleaning compositions, domestic and institutional hard surface cleaners, toilet disinfectants, general toiletries disinfectant, sanitising bottles, including glass and plastic bottles, and pipe cleaning compositions.
  • the composition will be relatively low foaming, although for some, for instance toilet disinfecting and general toiletries disinfectant, it may be desirable for the composition to have a relatively high foam.
  • suitable surfactants which will foam is well known in the art.
  • anti-foaming agents for instance soap or silicone anti- foams.
  • a second category of composition comprises liquid formulations but which contain no surfactants. These may be useful where no surface activity is necessary, for instance in effluent and water treatment, in toilet disinfectants, for use as a swimming pool treatment in general industrial sterilisation and in some domestic sterilisation situations, for instance as a general toiletry disinfectant, in denture cleaning compositions, in sanitising glass and plastic bottles or other containers, as well as in certain environmental clean-up operations.
  • the liquid formulations mentioned above may be pourable liquids, which are aqueous or non-aqueous, or may be in gel or paste form. Furthermore the compositions may be two-phase, for instance a cream form. Alternatively the compositions could be in the form of a mousse (where the composition contains surfactant) by the injection of a gas, especially for domestic hard surface cleaning operations. A further category of composition is in solid form and includes a surfactant. The general uses of these compositions are similar to those for which the liquid formulations including a surfactant are useful, as mentioned above.
  • a further category of formulation comprises a solid composition but without surfactant. These compositions are useful in the same categories of uses as the liquid formulations without surfactant.
  • the compositions may, in solid form, be more storage stable, since it is in general easier to keep the bleach activator and peroxygen donor compound in separate particles and prevent them coming into contact with one another during storage. It is furthermore easier to isolate other components of the composition from one another and from the bleach components, especially where storage sensitive compounds such as enzymes, other biocides or perfumes are present.
  • Solid compositions may be in the form of particulate mixtures or may be tabletted. Tabletted formulations, or even granular formulations, may include agents to increase the dissolution rate of the compositions upon addition to water.
  • suitable components known for incorporation into tablets can be used to aid disintegration of a composite product which is a tablet.
  • Such ingredients may create effervescence, for instance; a suitable component is sodium bicarbonate, or other alkali metal bicarbonate, optionally in combination with an acid.
  • the compositions may also contain ingredients to assist in their application or stability or which improve their appearance, for instance thickeners, dispersants, opacifiers, hydrotropes, dyes, perfumes etc.
  • the present invention may be used to provide a biocidal effect against micro-organisms such as bacteria, fungi, yeasts, moulds and/or viruses.
  • Example 1 The final solutions prepared from the biocidal compositions and the processes of the present invention have been found to be surprisingly beneficial across a wide range of bacteria. This is due to the synergistic effect which results from the combination of peroxygen and other, generally halogen-based biocidal species.
  • the present invention is illustrated in the following examples: Example 1
  • Aqueous solutions of mixtures of ingredients in the amounts specified in Table 1 below were made up. The solutions were immediately subjected to the British Standard BS6905 Modified Kelsey-Sykes tests for determining disinfection efficacy under dirty Hospital conditions.
  • a bacteria culture in this case Staph. aureus, is added to solutions of test mixtures at a range of concentrations, five samples are removed at 8, 18 and 28 minutes and placed in a nutrient broth.
  • a sample of denatured yeast and a further aliquot of bacterium are added to the test solution.
  • the tubes of nutrient broth are assessed for growth or not growth after incubation. For a pass there must be growth in three or fewer of the tubes containing sample removed at 8 and 18 minutes at the recommended dilution.
  • CTAB Cetyltri ethyl ammonium bromide (cetrimide) a cationic surfactant.
  • Formulation 2.1 which contains no biocide precursor was not effective against either test bacterium.
  • Formulations 2.2 and 2.3 were both very effective, producing a kill in excess of 99.99% against both test bacteria.
  • the following formulations exhibit effective peracid release and biocidal activity.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Detergent Compositions (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
EP95927860A 1994-08-05 1995-08-04 Oxydierende zusammensetzungen Ceased EP0773718A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB9415906A GB9415906D0 (en) 1994-08-05 1994-08-05 Oxidising compositions
GB9415906 1994-08-05
PCT/GB1995/001865 WO1996003873A1 (en) 1994-08-05 1995-08-04 Oxidising compositions

Publications (1)

Publication Number Publication Date
EP0773718A1 true EP0773718A1 (de) 1997-05-21

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EP95927860A Ceased EP0773718A1 (de) 1994-08-05 1995-08-04 Oxydierende zusammensetzungen

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EP (1) EP0773718A1 (de)
JP (1) JPH10504028A (de)
KR (1) KR970704345A (de)
AU (1) AU3185395A (de)
BR (1) BR9508529A (de)
GB (1) GB9415906D0 (de)
WO (1) WO1996003873A1 (de)

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ATE269616T1 (de) 2000-04-25 2004-07-15 Nortel Networks Sa Drahtloses telekommunikationssystem mit einer reduzierten verzögerung für die datenübermittlung
EP1375634A1 (de) * 2002-06-26 2004-01-02 Tevan B.V. Wässrige Desinfektionszusammensetzungen mit schneller antibakterieller Wirkung
EP1382666A1 (de) * 2002-06-21 2004-01-21 Tevan B.V. Wässrige Desinfektionszusammensetzungen mit schneller antibakterieller Wirkung
US7033511B2 (en) * 2004-01-20 2006-04-25 A-Dec, Inc. Sustained water treatment in dental equipment
GB0411304D0 (en) * 2004-05-21 2004-06-23 Fellows Adrian N An antimicrobial composition
DE102007034639A1 (de) * 2007-07-23 2009-01-29 Antiseptica Chemisch-Pharmazeutische Produkte Gmbh Mehrteiliges Medizinprodukt
US20110177145A1 (en) * 2009-07-27 2011-07-21 E.I. Du Pont De Nemours And Company In situ preparation of peracid-based removable antimicrobial coating compositions and methods of use
WO2019213483A1 (en) * 2018-05-04 2019-11-07 Ecolab Usa Inc. Non-chlorinated oxidizing biocide chemistries, their methods of production, application and methods of feed thereof

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ZA804930B (en) * 1979-08-16 1982-03-31 Unilever Ltd Bleach composition
US4923677A (en) * 1985-08-07 1990-05-08 Roy T. Witkin Chemical sterilization
US4738840A (en) * 1986-03-03 1988-04-19 Simon Gilbert I Presurgical sterilization method
DE3615787A1 (de) * 1986-05-10 1987-11-12 Fresenius Ag Desinfektionsmittel
GB9002422D0 (en) * 1990-02-03 1990-04-04 Boots Co Plc Anti-microbial compositions

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Title
See references of WO9603873A1 *

Also Published As

Publication number Publication date
GB9415906D0 (en) 1994-09-28
KR970704345A (ko) 1997-09-06
AU3185395A (en) 1996-03-04
JPH10504028A (ja) 1998-04-14
BR9508529A (pt) 1997-12-23
WO1996003873A1 (en) 1996-02-15

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