GB2304286A - Biocidal hard surface treatment with sustained effect based on use of a copolymer of hydrophilic oxyethylene/oxypropylene and hydrophobic ester chain units - Google Patents

Biocidal hard surface treatment with sustained effect based on use of a copolymer of hydrophilic oxyethylene/oxypropylene and hydrophobic ester chain units Download PDF

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Publication number
GB2304286A
GB2304286A GB9516966A GB9516966A GB2304286A GB 2304286 A GB2304286 A GB 2304286A GB 9516966 A GB9516966 A GB 9516966A GB 9516966 A GB9516966 A GB 9516966A GB 2304286 A GB2304286 A GB 2304286A
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United Kingdom
Prior art keywords
biocide
copolymer
units
composition according
polymer
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GB9516966A
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GB9516966D0 (en
GB2304286B (en
Inventor
Brian Davis
Peter Jordan
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Rhodia Chimie SAS
Rhodia Ltd
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Rhone Poulenc Chimie SA
Rhone Poulenc Chemicals Ltd
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Application filed by Rhone Poulenc Chimie SA, Rhone Poulenc Chemicals Ltd filed Critical Rhone Poulenc Chimie SA
Priority to GB9516966A priority Critical patent/GB2304286B/en
Publication of GB9516966D0 publication Critical patent/GB9516966D0/en
Priority to BR9610184-9A priority patent/BR9610184A/en
Priority to PL96325011A priority patent/PL325011A1/en
Priority to JP9509074A priority patent/JPH11514342A/en
Priority to EP96928515A priority patent/EP0863701A1/en
Priority to KR1019980701165A priority patent/KR19990037686A/en
Priority to HU9802409A priority patent/HUP9802409A3/en
Priority to TR1998/00249T priority patent/TR199800249T1/en
Priority to CN96197047A priority patent/CN1196656A/en
Priority to CA002228484A priority patent/CA2228484A1/en
Priority to PCT/GB1996/002025 priority patent/WO1997006675A1/en
Priority to IL12330796A priority patent/IL123307A0/en
Priority to AU68252/96A priority patent/AU711510B2/en
Publication of GB2304286A publication Critical patent/GB2304286A/en
Priority to NO980595A priority patent/NO980595L/en
Priority to MXPA/A/1998/001246A priority patent/MXPA98001246A/en
Application granted granted Critical
Publication of GB2304286B publication Critical patent/GB2304286B/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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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
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION 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
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION 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
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/24—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing ingredients to enhance the sticking of the active ingredients
    • 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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3715—Polyesters or polycarbonates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/507—Polyesters
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/507—Polyesters
    • D06M15/5075—Polyesters containing sulfonic groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/53—Polyethers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic

Abstract

The invention provides a composition suitable for application to a hard or textile surface which comprises an aqueous solution, suspension or dispersion of a biocide and a copolymer comprising chain units A1 of the formula -OC n H 2n -where n is 2 or 3 and chain ester units A2 of the formula where R is a hydrophobic group; where the mole ratio of units A1 to A2 is from 1:10 to 3000:1 and the copolymer has a molecular weight from 1000 to 100,000 and methods using a biocide and such a copolymer or using such compositions from controlling microorganisms. Such copolymers possess a hydrophobic part (A1) which will give some adherence to the surface (resisting removal on washing of the surface by water and weak surfactant solutions) and a hydrophilic part(A2) which will allow migration of the biocide through to the surface of the polymer, thus providing a sustained biocidal effect. The polymer is advantageously biodegradable by virtue of the ester linkage present in its backbone. The compositions may easily be removed from the surface to which they have been applied by the application of an alkali.

Description

BIOCIDAL HARD SURFACE TREATMENT The invention relates to biocidal compositions and methods for controlling micro organisms using such compositions.
Known biocidal compositions generally suffer from the disadvantage that they have no lasting effect. In other words, after they are applied to a surface their biocidal effect decreases rapidly, especially if the surface is washed.
According to the present invention there is provided a composition suitable for application to a hard surface which comprises an aqueous solution, suspension or dispersion of a biocide and a copolymer comprising chain units, Al, of the formula -OC,H,- where n is 2 or 3 and chain ester units, A2, of the formula
where R is a hydrophobic group; the mole ratio of units Al to A2 being from 1:10 to 3000:1 and the copolymer having a molecular weight from 1000 to 100,000.
R is preferably an alkylene group, a cycloalkylene group, or an arylene group. The alkylene group preferably has six or more carbon atoms, the cycloalkylene group preferably has 4 to 10 carbon atoms, especially cyclohexylene and the arylene group is preferably a metaor para- phenylene or naphthylene group. The groups represented by R may optionally be substituted. Suitable substituents include C1.6-alkyl, for example methyl, or hydrophilic groups such as sulphonic acid groups, optionally in alkali metal salt form, for example sodium sulpho-3,5-phenylene.
The copolymer preferably has a molecular weight from 2000 to 30,000. The molar ratio of units Al to A2 is preferably from 1:1 to 100:1.
It will be appreciated that such copolymers possess a hydrophobic part which will give some adherence to the surface, resisting removal by water and weak surfactant solutions, and a hydrophilic part which will allow migration of the biocide through to the surface of the polymer, particularly when the surface is rinsed with water or an aqueous solution. The chain units Al are generally hydrophilic while the chain ester units A2 are hydrophobic.
The copolymers used preferably comprise chain units of the formula
where m represents an integer from 12 to 230 and n and R are as defined above, especially polyoxyethylene terephthalate units, and chain units of formula:
where n and R are as defined above, especially polyethylene terephthalate units.
Preferred polymers are those having an A3:A4 molar ratio of from 1:10 to 10:1, preferably from 1:2 to 1:6.
The units A3 preferably contain (OCnH2n) groups having a molecular weight of from 500, preferably 1000, to 10,000, especially about 3400. The polymer preferably has a total molecular weight of from 1000 to 100,000, preferably from 15,000 to 35,000 especially about 20,000. Preferably m is an integer from 14 to 110, particularly about 75.
Thus typical copolymers which may be used are as follows: (i) polymers derived from ethylene terephthalate and polyethylene oxide terephthalate at mole ratio from about 1:10 to 10:1, said polyethylene oxide terephthalate containing ethylene oxide units with a number average molecular weight from about 500 to about 10,000, the polymer having a number average molecular weight of about 1,000, to 100,000: (ii) polymers derived from propylene terephtalate and polyethylene oxide terephthalate at a mole ratio from about 1:10 to about 10::1, said polyethylene oxide terephthalate containing ethylene oxide units with a number average molecular weight from about 500 to about 10,000, and the polymer having a number average molecular weight of about 1,000 to 100,000, or (iii) polymers derived from ethylene terephthalate and/or propylene terephthalate in any ratio and polyethylene oxide and/or polypropylene oxide in any ratio such that the mole ratio of ethylene terephthalate plus propylene terephthalate to polyethylene oxide plus polypropylene oxide is from about 1:10 to about 10:1, said ethylene oxide units and said propylene oxide units each having a number average molecular weight from about 250 to about 10,000, the polymer having a number average molecular weight of about 1,000 to about 100,000.
In one embodiment, in order to impart a slight ionic character, or increased hydrophilicity, to the polymer, the polymer is end-capped with a hydrophilic group. Suitable hydrophilic groups include those containing a sulpho group, for example those of formula (MO3S)(C6H4)C(0)- or (NO3S) (cH2)x(012CH20) (CflHO)y - where M is a suitable cation, for example an alkali metal ion especially sodium, X is O or 1, y is from 0 to 4 and n is as defined above, monoesters of ethylene glycol or propylene glycol. They may be added during the preparation of the base polyester.
Generally, the molar quantity of the hydrophilic group in the total molar quantity of units A2 used in such preparation is from 0 to 15%.
Suitable polymers include those disclosed in US-A4,770,666 in groups B, C and D, US-A-4,116,885, US-A3,962,152, GB-A-2,196,013, US-A-4,702,857, US-A-4,711,730, US-A-4,713,194, US-A-3,416,952, US-A-4,427,557 and US-A4,201,824, which also describe methods for their preparation which are, of course, well known.
The polymer is used as an aqueous solution, suspension or dispersion. It may optionally be solubilised or dispersed in water with the assistance of solubilising or dispersing agents such as non-ionic surfactants, in particular a fatty alcohol ethoxylate such as C12 or C14 alkyl ethoxylates. The use of a dispersion or suspension is generally preferred since such formulation will adhere better to the surface than solutions.
Biocides which may be used in the compositions of the present invention include: a) Ouaternarv ammonium and phosphonium biocides: Cocoalkyl benzyl dimethyl ammonium chloride; C12,14-alkyl benzyl dimethyl ammonium chloride; Lauryl Cl2/l4-alkyl-benzyl dimethyl ammonium chloride; Coco-alkyl 2,4-dichlorobenzyl dimethyl ammonium chloride; Tetradecyl benzyl dimethyl ammonium chloride; diisobutyl phenoxy-ethoxy-ethyl dimethyl-benzyl ammonium chloride; Lauryl pyridinium chloride; C12114-alkyl-benzyl imidazolinium chloride; Myristyl trimethyl ammonium bromide; Cetyl trimethyl ammonium bromide; Didecyl dimethyl ammonium chloride; Dioctyl dimethyl ammonium chloride; and Myristyl triphenyl phosphonium bromide.
b) Amnhoteric biocides: N-(N'-C8.18-alkyl-3-aminopropyl) - glycine derivatives such as (dodecyl)(aminopropyl)glycine; N- (N' - (N" -C8 18-alkyl-2 -aminoethyl) -2 -aminoethyl) -glycine derivatives such as (dodecyl)(di-ethylene diamine)glycine; and N, N-bis (N' -C8.18-alkyl-2-aminoethyl) -glycine derivatives.
c) Amines: N-(3-aminopropyl)-N-dodecyl-1,3 Propanediamine.
d) Phenolics: Parachlorometaxylenol, dichlorometaxylenol, phenol, m-cresol, o-cresol, p-cresol, o-phenyl-phenol, 4-chloro-m-cresol, chloroxylenol, 6-namyl-m-cresol, resorcinol, resorcinol monoacetate, p-tertbutyl-phenol and o-benzyl-p-chlorophenol or biologically active, water soluble salts of these compounds, e.g. the alkali metal salts; e) Chlorhexidine and its salts for example chlorhexidine gluconate; f) Iodophors, hypochlorite salts and chlorine release agents, e.g. sodium dichloroisocyanurate; g) Polvouaternarv ammonium biocides such as poly thydroxyethylene(dimethylimino) ethylene (dimethylimino) methylene dichloride), poly toxyethylene (dimethylimino) ethylene(dimethylimino) ethylene dichloride], polythydroxyethylene(dimethylimino)-2-hydroxypropyl (dimethylimino) methylene dichloride] and the polymer of IH-imidazole with (chloromethyl)oxirane.
The polymer is preferably used at a concentration of from 1 to 80% by weight, preferably from 5 to 50% more preferably from 10 to 30%, for example about 15%, by weight. The biocide is preferably used in a concentration range of from 0.1% to 20% by weight, preferably from 1 to 10%, more preferably from 1 to 5%, for example about 2.5%, by weight. The amount of solid active ingredient deposited on the hard surface per 2m is typically 0.01 to log, preferably O.lg to lg of the biocide and O.lg to 20g, preferably 1 to 5g of the polymer.
A particular advantage of the compositions according to the invention is that they provide a sustained biocidal effect when applied to a hard surface. This sustained effect is resistant to washing of the surface. The polymer used in the composition has the advantage that it is biodegradable by virtue of the ester linkage present in the backbone of the polymer. Another advantage of the compositions is that they may easily be removed from the surface to which they have been applied by the application of an alkali.
A further advantage of the compositions is that there is no need for the polymer to contain cationic grouping to enhance hydrophilicity. The presence of such grouping, especially cationic nitrogen groupings, tends to give rise to effluent problems because polymers with such groupings are frequently toxic to fish.
According to the present invention there is further provided a method of controlling microorganisms at a locus which comprises applying to the locus where such control is required a biocide and a copolymer as defined above, for example in the form of a composition according to the invention. A suitable locus is a hard surface for example glazed and unglazed ceramic, glass, PVC, formica and other hard plastics, stainless steel or other painted or unpainted metals, and painted or unpainted wood.
The compositions according to the present invention are preferably used in the method of the invention in diluted form at dilutions from 20 to 500 times, preferably 50 to 100 times.
The microorganisms which may be controlled by the method of the present invention include: (i) Gram negative bacteria: Pseudomonas veruainosa; Escherichia coli; and Proteus mirabilis.
(ii) Gram positive bacteria: Staphylococcus aureus; and Streatococcus faecium.
(iii) Other harmful food bacteria: Salmonella tyDhimurium; Listeria monocvtoaenes; Campylobacter neduni; and Yersinia enterocol itica.
(iv) Yeasts: Saccharomvces cerevisiae; and Candida albicans.
(v) Fungi: Asperaillus niger; Fusarium solani; and Pencillium chrvsoaenum.
(vi) Algae: Chlorella saccharophilia; Chlorella emersonii; Chlorella vulgaris; and Chlamvdomonas euaametos.
The microorganisms controlled by the method of the present invention are preferably Gram negative microorganisms, especially Pseudomonas aeruainosa, Gram positive microorganisms, especially Staphvlococcus aureus, and fungi e.g. Asperaillus niaer.
The following examples illustrate the invention. In the Examples the Gram negative bacteria Pseudomonas Aeroalnosa has been chosen as it is known to be difficult to kill. The positive results obtained using the compositions of the invention show that the compositions will be effective over a wide range of known microorganisms.
EXAMPLE 1 Two disinfectant concentrates (DC1 and DC2) were prepared each with the formulation shown in Table 1 below Table 1
Dc1 Dc2 Biocide 2.sot 2.5% Polymer 14.25% 0 Water to 100% to 100% In the above Table the biocide used was C12. 14-alkyl benzyl dimethyl ammonium chloride and the polymer was of the following formula:
having a molecular weight of about 20000g/mol. The percentages in the Table are percentages by weight.
A hard surface having an area of 25cm2 which had previously been sterilised by wiping with isopropyl alcohol was treated with 3ml of each of the disinfectant concentrates after appropriate dilution e.g. 100X and then dried at 45it. The tile is then washed consecutively with a water spray or sponge and dried again at 45it. 0.25ml of an aqueous medium containing about 108 cfu's/ml of the gram negative bacteria Pseudomonas Aeruainosa was then spread over the treated hard surface. The surface was then allowed to stand for the contact times shown in Table 2 below. This was to allow the biocide time to migrate through the polymer layer and kill the bacteria on the surface. The surfaces were then dried at 37 C.
The surviving organisms were recovered using a sterile cotton wool swab, previously wetted with a neutralising medium. The whole surface was carefully swabbed by wiping it across back and forth several times.
The swab was transferred to 9ml of neutralising medium comprising 3% Tween 80% and 2% soya lecithin which was then plated out using 10-fold serial dilutions onto nutrient agar. The plates were incubated at 37 C for 48 hours and the survivors were counted.
Control tests were carried out using a clean hard surface of the same area and using the same method except that no polyester or biocide was applied.
The sustained biocidal effect of the compositions of the invention was measured by washing the hard surface with a sponge before treating it with microorganisms using the method described above. The sponge treatment involved the use of a Gardener-Scrub washing machine, which pushes a sponge soaked in water across the surface, which is mounted horizontally, at a pressure of 5.6g/cm2. For each "wash" in Table 2 below, the sponge passed over the surface twice.
The results shown in Table 2 below were obtained: Table 2
Formulation Dilution Contact I Number of washes and used Time(h) Log10 Reduction obtained 1 a i DC1 lOOx 1 4.6 4.4 2.8 2.47 DC1 100x 3 6.0 DC2 lOOX 1 6.0 1.82 0.3 0.10 The Log10 reduction in the number of bacteria was calculated as follows: Log10 reduction = Loglo(N/n) where N represents the number of bacteria (cfu's/ml) recovered from the control and n represents the number of bacteria (cfu's/ml) recovered from the test sample.A Log10 reduction of 5 shows an excellent result particularly for food contact areas and a Log10 reduction of 3 shows a satisfactory result for general disinfection.
The results show that DC1 resists the abrasive sponge treatment very well. There is still a Log10 reduction of about 3 after two washes. The increase in contact time from 1 hour to 3 hours gives a higher kill factor, presumably because the polymer coating slows down the biocide action as the biocide must first diffuse through the polymer film before it can attack the bacteria. When a longer time of contact is used, the Logic reduction after two washes is likely to be above 3.
EXAMPLE 2 This Example was carried out in a manner identical to that of Example 1 (with dilution 100X) except that instead of washing with a sponge the surfaces were subjected to non abrasive washing with a water spray. This involved mounting the surface vertically and spraying it with lg of water from a hand held trigger spray for each wash.The results shown in Table 3 below were obtained: Table3
Formulation Contact Number of water sprays and LoglO Timefh) Reduction obtained I I I I I II D.C.1 1 4.6 4.52 6.0 3.6 2.16 1.46 D.C.l 3 6.0 D.C.2 1 6.0 5.82 3.4 0.8 0.05 0.0 The low values at washes 0 and 1 for formulation DC1 with a contact time of 1 hour are caused by the slowing of biocidal action by the polymer coating. By the second wash sufficient polymer is removed and the time delay is long enough to increase the rate of biocidal action.Further washes gradually remove biocide and the protecting polymer and so the kill rate decreases. The film still protects against at least four water sprays when it provides a Log10 reduction of 3 at least.
FXAMPLF 3 Disinfectant concentrates having the formulation shown in Table 4 below were prepared: Table 4
DOC3 DO Biocide 1.0% 1.0% Polymer 14.7% 0% Water to 100% to 100% The biocide used was Polythydroxyethylene(dimethyliminio)- 2-hydroxy propyl (dimethyliminio)methylene dichloride].
The polymer used was the polymer of formula (I) as in Example 1. The percentages are percentages by weight.
This Example was carried out in the same way as Example 2 except that disinfectant concentrates DC3 and DC4 were used. The results obtained are shown in Table 5 below: Table5
Formulation Dilution Contact Number of water sprays used Time(h) and Logs0 Reduction obtained
I 1 2 DC3 lOOx 24 6.0 6.0 4.9 0.19 DC4 100x 24 6.0 2.96 2.02 The polymer quaternary ammonium biocide is a relatively slow acting biocide and so testing was carried out after an 24 hour contact time. When the polymer is present, the biocide resists at least 2 water sprays before its effectiveness is greatly reduced.

Claims (17)

1. A composition suitable for application to a hard or textile surface which comprises an aqueous solution, suspension or dispersion of a biocide and a copolymer comprising chain units, Al, of the formula -OCnH2n- where n is 2 or 3 and chain ester units, A2, of the formula
where R is a hydrophobic group; the mole ratio of units Al to A2 being from 1:10 to 3000:1 and the copolymer having a molecular weight from 1000 to 100,000.
2. A composition according to claim 1 in which R is an alkylene group of six or more carbon atoms, a cycloalkylene group of 4 to 10 carbon atoms or an arylene group.
3. A composition according to claim 1 or 2 wherein the copolymer has a molecular weight from 2000 to 30,000.
4. A composition according to any one of claims 1 to 3 wherein the mole ratio of units Al to A2 is from 1:1 to 100:1.
5. A composition accoring to any one of the preceding claims wherein the copolymer comprises chain units A3:
where m represents an integer from 12 to 230 and n and R are as defined above1 and chain units of formula:
where n and R are as defined above.
6. A composition according to any one of claims 1 to 3 wherein the polymer is end capped with a hydrophilic group containing a sulfo group.
7. A composition according to any one of the preceding claims which is in the form of a dispersion or suspension.
8. A composition according to any one of the preceding claims in which the biocide is a quaternary ammonium or phosphonium biocide, an amphoteric biocide, an amine, a phenolic compund, chlorhexidine, an iodophor or a polyquaternary ammonium biocide.
9. A composition according to any one of the preceding claims which comprises 5 to 50% by weight of polymer and 1 to 10% by weight of a biocide.
10. A composition according to claim 9 which comprises 10 to 30% by weight of polymer and 1 to 5% by weight of biocide.
11. A composition according to claim 1 substantially as described in any one of the Examples.
12. A method of controlling micro-organisms at a locus which comprises applying to the locus where such control is required a biocide and a copolymer as defined in claim 1.
13. A method according to claim 12 wherein the biocide and copolymer are applied in the form of a composition as claimed in any one of claims 1 to 11.
14. A method according to claim 13 wherein the composition is diluted 50 to 100 times before use.
15. A method according to any one of claims 12 to 14 wherein the microorganism is a Gram negative microorganism.
16. A method according to any one of claims 12 to 15 wherein the locus is a glazed or unglazed ceramic, glass, PVC a hard plastics material, a painted or unpainted metal or a painted or unpainted wood.
17. A method according to claim 12 substantially as described in any one of the Examples.
GB9516966A 1995-08-18 1995-08-18 Biocidal hard surface treatment Expired - Fee Related GB2304286B (en)

Priority Applications (15)

Application Number Priority Date Filing Date Title
GB9516966A GB2304286B (en) 1995-08-18 1995-08-18 Biocidal hard surface treatment
CN96197047A CN1196656A (en) 1995-08-18 1996-08-19 Antibiotic agent
PCT/GB1996/002025 WO1997006675A1 (en) 1995-08-18 1996-08-19 Biocidal compositions
JP9509074A JPH11514342A (en) 1995-08-18 1996-08-19 Biocidal composition
EP96928515A EP0863701A1 (en) 1995-08-18 1996-08-19 Biocidal compositions
KR1019980701165A KR19990037686A (en) 1995-08-18 1996-08-19 Biological lethal composition and microbial remediation method using the same
HU9802409A HUP9802409A3 (en) 1995-08-18 1996-08-19 Biocidal compositions
TR1998/00249T TR199800249T1 (en) 1995-08-18 1996-08-19 Application of biocidal agents on hard surfaces.
BR9610184-9A BR9610184A (en) 1995-08-18 1996-08-19 Composition suitable for application to a hard or textile surface and process to control microorganisms in a specific location
CA002228484A CA2228484A1 (en) 1995-08-18 1996-08-19 Biocidal compositions
PL96325011A PL325011A1 (en) 1995-08-18 1996-08-19 Compositions for annihilating living organisms
IL12330796A IL123307A0 (en) 1995-08-18 1996-08-19 Biocidal compositions
AU68252/96A AU711510B2 (en) 1995-08-18 1996-08-19 Biocidal compositions
NO980595A NO980595L (en) 1995-08-18 1998-02-11 Biocidal compositions
MXPA/A/1998/001246A MXPA98001246A (en) 1995-08-18 1998-02-13 Compositions bioci

Applications Claiming Priority (1)

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GB9516966A GB2304286B (en) 1995-08-18 1995-08-18 Biocidal hard surface treatment

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GB2304286A true GB2304286A (en) 1997-03-19
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JP (1) JPH11514342A (en)
KR (1) KR19990037686A (en)
CN (1) CN1196656A (en)
AU (1) AU711510B2 (en)
BR (1) BR9610184A (en)
CA (1) CA2228484A1 (en)
GB (1) GB2304286B (en)
HU (1) HUP9802409A3 (en)
IL (1) IL123307A0 (en)
NO (1) NO980595L (en)
PL (1) PL325011A1 (en)
TR (1) TR199800249T1 (en)
WO (1) WO1997006675A1 (en)

Cited By (3)

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US6346125B1 (en) 1998-02-20 2002-02-12 Ciba Specialty Chemicals Corporation Process for the treatment of nonwovens with antimicrobial agents
WO2003014274A1 (en) * 2001-08-02 2003-02-20 Creavis Gesellschaft Für Technologie Und Innovation Mbh Antimicrobial cleaning agent
WO2006077049A2 (en) * 2005-01-21 2006-07-27 Henkel Kommanditgesellschaft Auf Aktien Antiadhesive polymer for prevention of adhesion of microorganisms to textiles and for prevention of laundry odours

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AU5038299A (en) * 1998-07-09 2000-02-01 Rhodia Chimie Process for the biocidal treatment of surfaces
EP1286589A2 (en) * 2000-06-08 2003-03-05 Rhodia Chimie Composition and method for biocide treatment of surfaces
US6897191B2 (en) 2003-04-30 2005-05-24 Specialty Construction Brands, Inc. Disinfecting, antimicrobial sealing compositions and methods of using the same
DE102005048955A1 (en) 2005-10-13 2007-04-26 Lanxess Deutschland Gmbh Active substance mixtures of OPP and amines

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EP0290676A2 (en) * 1987-05-12 1988-11-17 Ecolab Inc. Improved disinfectant polymeric coatings for hard surfaces
GB2228200A (en) * 1989-02-09 1990-08-22 Ici Plc Insecticidal fabrics

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6346125B1 (en) 1998-02-20 2002-02-12 Ciba Specialty Chemicals Corporation Process for the treatment of nonwovens with antimicrobial agents
WO2003014274A1 (en) * 2001-08-02 2003-02-20 Creavis Gesellschaft Für Technologie Und Innovation Mbh Antimicrobial cleaning agent
WO2006077049A2 (en) * 2005-01-21 2006-07-27 Henkel Kommanditgesellschaft Auf Aktien Antiadhesive polymer for prevention of adhesion of microorganisms to textiles and for prevention of laundry odours
WO2006077049A3 (en) * 2005-01-21 2006-10-26 Henkel Kgaa Antiadhesive polymer for prevention of adhesion of microorganisms to textiles and for prevention of laundry odours

Also Published As

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CN1196656A (en) 1998-10-21
KR19990037686A (en) 1999-05-25
JPH11514342A (en) 1999-12-07
AU6825296A (en) 1997-03-12
HUP9802409A2 (en) 1999-02-01
MX9801246A (en) 1998-10-31
AU711510B2 (en) 1999-10-14
PL325011A1 (en) 1998-07-06
NO980595L (en) 1998-04-16
GB9516966D0 (en) 1995-10-18
NO980595D0 (en) 1998-02-11
HUP9802409A3 (en) 2000-12-28
IL123307A0 (en) 1998-09-24
CA2228484A1 (en) 1997-02-27
GB2304286B (en) 1999-09-29
EP0863701A1 (en) 1998-09-16
WO1997006675A1 (en) 1997-02-27
BR9610184A (en) 1999-12-21
TR199800249T1 (en) 1998-05-21

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