EP1624755A1 - Composition contenant un copolymere acide et un agent antimicrobien, et son utilisation - Google Patents

Composition contenant un copolymere acide et un agent antimicrobien, et son utilisation

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Publication number
EP1624755A1
EP1624755A1 EP04732135A EP04732135A EP1624755A1 EP 1624755 A1 EP1624755 A1 EP 1624755A1 EP 04732135 A EP04732135 A EP 04732135A EP 04732135 A EP04732135 A EP 04732135A EP 1624755 A1 EP1624755 A1 EP 1624755A1
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EP
European Patent Office
Prior art keywords
formula
acidic
polymer
composition according
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.)
Withdrawn
Application number
EP04732135A
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German (de)
English (en)
Inventor
David John Hodge
David Alan Pears
John Jeffrey Gerrard
Paula Louise Mcgeechan
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Arch UK Biocides Ltd
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Arch UK Biocides Ltd
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Priority claimed from GB0311166A external-priority patent/GB0311166D0/en
Priority claimed from GB0325238A external-priority patent/GB0325238D0/en
Application filed by Arch UK Biocides Ltd filed Critical Arch UK Biocides Ltd
Publication of EP1624755A1 publication Critical patent/EP1624755A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
    • A61L2/16—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using chemical substances
    • A61L2/18—Liquid substances or solutions comprising solids or dissolved gases
    • A61L2/186—Peroxide solutions
    • 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
    • A01N25/08—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 solids as carriers or diluents
    • A01N25/10—Macromolecular compounds
    • 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
    • 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
    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/02—Amines; Quaternary ammonium compounds
    • A01N33/12—Quaternary ammonium compounds
    • 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
    • A01N47/42—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides containing —N=CX2 groups, e.g. isothiourea
    • A01N47/44—Guanidine; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
    • A61L2/16—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using chemical substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical

Definitions

  • the present invention relates to a method for inhibiting the growth of micro-organisms on surfaces by means of a composition comprising an acidic vinyl comb type co-polymer and an antimicrobial agent.
  • the anti-microbial agent is controllably released from the acidic co-polymer over time thereby providing effective anti-microbial control.
  • Micro-organisms can be found on many inanimate and animate surfaces. The presence of such micro-organisms can result in unhygienic conditions in hospitals and medical environments, kitchens, bathrooms, toilets and in the preparation and packaging of foodstuffs leading to health risks and contamination.
  • anti-microbial agents exist which are effective against many of the virulent forms of micro-organisms found in the food and health-care environments.
  • the activity of such agents is insufficient in terms of providing a sustained, surface hygienic effect. This may be due to the high water solubility and/or the lack of substantivity of the anti-microbial agent on a surface which means that the anti-microbial agent is readily displaced.
  • an anti-microbial agent or an anti-microbial agent in combination with a delivery system which provides a high degree of anti-microbial kill over a sustained period of time.
  • the literature describes various cases where micro-organisms and in particular bacterial fouling may cause damage or lead to contamination of surfaces including for example swimming pools, industrial pipes, architectural structures, ships hulls, hospital theatres, teeth and kitchen surfaces. Indeed, there have been many attempts and approaches to overcome the micro-biological problems associated especially with bacterial growth on inanimate and animate surfaces.
  • European Patent 0182523 describes how certain polymeric compositions are effective at preventing oral bacteria from colonisation on the surface of teeth.
  • an anti-staining composition comprising polymers with anti-bacterial agents were shown to be effective against bacteria found in an oral environment.
  • WO/02449 describes a process for the biocidal treatment of textiles and surfaces comprising high molecular weight grafted co-polymers.
  • none of the above documents describe an anti-microbial system which has the ability to eliminate micro-organisms effectively and has a sustained, surface hygienic effect.
  • the term 'sustained' used hereinafter refers to an anti-microbial agent which is still active even after the surface to which the agent has been applied has been cleansed for example by wiping, rinsing or washing the surface.
  • acidic co-polymers provide effective and sustained anti-microbial activity when used to inhibit the growth of micro-organisms on surfaces.
  • the present invention therefore provides compositions for the treatment of surfaces based on acidic co-polymers with varying functionality in both the backbone and the side chain in combination with an anti-microbial agent, especially a biocide.
  • composition comprising:
  • an anti-microbial agent comprising a polymeric biguanide, alone or in combination with at least one other microbiologically active component selected from the group consisting of quaternary ammonium compounds, monoquaternary heterocyclic amine salts, urea derivatives, amino compounds, imidazole derivatives, nitrile compounds, tin compounds or complexes, isothiazolin-3-ones, thiazole derivatives, nitro compounds, iodine compounds, aldehyde release agents, thiones, triazine derivatives, oxazolidine and derivatives thereof, furan and derivatives thereof, carboxylic acids and the salts and esters thereof, phenol and derivatives thereof, sulphone derivatives, imides, thioamides,
  • [B] is of Formula (10),
  • T is an optionally substituted substituent
  • L and G each independently is an optionally substituted linking group;
  • R ⁇ R 2 and R 3 are each independently H, optionally substituted C ⁇ -20 -alkyl or optionally substituted C 3-2 o-cycloalkyl;
  • R 4 and R 5 are each independently H or d-4-alkyl; q is 15 to 1000; p is 3 to 50;
  • J is an optionally substituted hydrocarbyl, group
  • F is an acidic substituent; b is 0, 1 , or 2; m is 0 to 350; n is 1 to 75; v is 1 to 100; and w is 1 to 4; provided that at least one of R 4 and R 5 is H and provided that R ⁇ R 2 , R 3 , T, L, J and G do not contain a basic group; and wherein the pka value of the acidic substituent F on the monomer from which [C] is derived is less than 5.5.
  • a preferred anti-microbial agent for use in the composition according to the first aspect of the present invention is an anti-bacterial agent, more preferably a polymeric biguanide.
  • polymeric biguanide comprises at least two biguanide units of Formula (2):
  • the bridging group preferably includes a polymethylene chain, optionally incorporating or substituted by one or more hetero atoms such as oxygen, sulphur or nitrogen.
  • the bridging group may include one or more cyclic moieties which may be saturated or unsaturated.
  • the bridging group is such that there are at least three, and especially at least four, carbon atoms directly interposed between two adjacent biguanide units of Formula (2).
  • the polymeric biguanide may be terminated by any suitable group, such as a hydrocarbyl, substituted hydrocarbyl or an amine group or a cyanoguanidine group of the Formula (3): — NH— C— H— CN II NH
  • the terminating group is hydrocarbyl, it is preferably alkyl, cycloalkyl, aryl or aralkyl.
  • the hydrocarbyl group is alkyl it may be linear or branched but is preferably linear.
  • Preferred alkyl groups include C ⁇ . 8 -alkyl.
  • Examples of preferred alkyl groups include for example methyl, ethyl, n-propyl, isopropyl, n-pentyl, n-butyl, isobutyl, ferf-butyl and n-octyl.
  • the hydrocarbyl group is cycloalkyl, it is preferably cyclopropyl, cyclopentyl or cyclohexyl.
  • the hydrocarbyl group is aralkyl, it preferably contains from 1 to 6, more preferably 1 or 2 carbon atoms in the alkylene group attaching the aryl group to the biguanide.
  • Preferred aralkyl groups include benzyl and 2-phenylethyl groups.
  • Preferred aryl groups include phenyl groups.
  • the terminating group is substituted hydrocarbyl, the substituent may be any substituent that does not exhibit undesirable adverse effects on the microbiological properties of the polymeric biguanide. Examples of such substituents are aryloxy, alkoxy, acyl, acyloxy, halogen and nitrile.
  • the biguanide is a bisbiguanide.
  • the two biguanide groups are preferably linked through a polymethylene group, especially a hexamethylene group.
  • the polymeric biguanide preferably contains more than two biguanide units of Formula (1 ) and is preferably a linear polymeric biguanide which has a recurring polymeric chain represented by Formula (4) or a salt thereof:
  • Formula (4) wherein d and e represent bridging groups which may be the same or different and in which together the total of the number of carbon atoms directly interposed between the pairs of nitrogen atoms linked by d plus the number of carbon atoms directly interposed between the pairs of nitrogen atoms linked by e is more than 9 and less than 17.
  • the bridging groups d and e preferably consist of polymethylene chains, optionally interrupted by hetero atoms, for example, oxygen, sulphur or nitrogen, d and e may also incorporate moieties which may be saturated or unsaturated, in which case the number of carbon atoms directly interposed between the pairs of nitrogen atoms linked by d and e is taken as including that segment of the cyclic group, or groups, which is the shortest. Thus, the number of carbon atoms directly interposed between the nitrogen atoms in the group
  • linear polymeric biguanides having a recurring polymer unit of Formula (4) are typically obtained as mixtures of polymers in which the polymer chains are of different lengths.
  • Formula (5a) Formula (5b) is, together, from 3 to about 80.
  • the preferred linear polymeric biguanide is a mixture of polymer chains in which d and e are identical and the individual polymer chains, excluding the terminating groups, are of the Formula (6) or a salt thereof:
  • n 1 is from 4 to 20 and especially from 4 to 18. It is especially preferred that the average value of n 1 is about 16.
  • the average molecular weight of the polymer in the free base form is from 1100 to 4000.
  • the linear polymeric biguanides may be prepared by the reaction of a bisdicyandiamide having the Formula (7):
  • polymer chains of the linear polymeric biguanides may be terminated either by an amino group or by a cyanoguanidine group of Formula (9):
  • This cyanoguanidine group can hydrolyse during preparation of the linear polymeric biguanide yielding a guanidine end group.
  • the terminating groups may be the same or different on each polymer chain.
  • a small proportion of a primary amine R-NH 2 may be included with the diamine H 2 N-e-NH 2 in the preparation of polymeric biguanides as described above.
  • the primary amine acts as a chain-terminating agent and consequently one or both ends of the polymeric biguanide polymer chains may be terminated by an -NHR group.
  • These -NHR chain-terminated polymeric biguanides may also be used.
  • the polymeric biguanides readily form salts with both inorganic and organic acids.
  • Preferred salts of the polymeric biguanide are water-soluble.
  • the polymeric biguanide used in accordance with the present invention is a mixture of linear polymers, the individual polymer chains of which, excluding the terminating groups, are represented by Formula (6) in the hydrochloride salt form.
  • This poly(hexamethylenebiguanide) compound is commercially available from Avecia Limited under the trademarks VantocilTM, CosmocilTM and ReputexTM .
  • the acidic co-polymers of the present are as illustrated in the following Empirical Structural Formula.
  • acidic co-polymer referred to herein is used to describe a co-polymer which can be derived from an addition polymerisation reaction (that is, a free radical initiated process which can be carried out in either an aqueous or non aqueous medium) of two or more olefinically unsaturated monomers. Therefore, the term vinyl monomer used throughout refers to an olefinically unsaturated monomer.
  • Sulphonic, phosphonic or phosphoric acid-bearing monomers are also suitable, for example 4-styrene sulphonic acid (or the corresponding 4-styrene sulphonyl chloride).
  • Acid bearing monomers can be polymerised as the free acid or as a salt, for example, the ammonium or alkali metal salts of ethylmethacrylate-2-sulphonic acid (available from Laporte as Bisomer SEM), sodium 1-allyloxy-2-hydroxy propane sulphonate, 2-acrylamido-2-methylpropane sulphonic acid, sodium acrylate or the corresponding free acids.
  • Vinyl esters such as vinyl acetate, vinyl propionate, vinyl laurate, and the vinyl esters of versatic acid (available from Resolution Performance Products under the tradename VeoVa), vinyl ethers of heterocyclic vinyl compounds, alkyl esters of mono-olefinically unsaturated dicarboxylic acids (such as di-n-butyl maleate and di-n-butyl fumarate) and in particular, esters of acrylic acid and methacrylic acid, vinyl monomers with additional functionality for subsequent crosslinking of the films, such as diacetone acrylamide, glycidyl methacrylate, aceto acetoxy ethyl methacrylate, hydroxy ethyl acrylate and 2-(trimethylsiloxy)ethyl methacrylate may also be used.
  • a particularly preferred acidic co-polymer of the present invention is an acrylic co-polymer, derived from acrylic or methacrylic monomers in the form of esters, free acids or salts of the free acids.
  • the acidic co-polymers of the present invention comprise at least one polymer which comprises one or more repeating units of Formula (1):
  • [A] is of Formula (9),
  • [B] is of Formula (10),
  • T is an optionally substituted substituent
  • L and G each independently is an optionally substituted linking group
  • R ⁇ R 2 and R 3 are each independently H, optionally substituted C 1-20 -alkyl or optionally substituted C 3- 2o-cycloalkyl;
  • R 4 and R 5 are each independently H or C ⁇ - -alkyl; q is 15 to 1000; p is 3 to 50;
  • J is an optionally substituted hydrocarbyl, group
  • F is an acidic substituent
  • b is 0, 1 , or 2
  • m is 0 to 350
  • n is 1 to 75
  • v is 1 to 100
  • w is 1 to 4; provided that at least one of R 4 and R 5 is H and provided that R 1 , R 2 , R 3 , T, L, J and G do not contain a basic group; and wherein the pka value of the acidic substituent F on the monomer from which [C] is derived is less than 5.5.
  • [A] is derived from any olefinically unsaturated polymerisable monomer which does not contain an ionisable or ionised functional group.
  • [B] provides the pendant polyether functionality of the acidic co-polymer and [C] provides the acidic functionality either in free acid or salt form.
  • the acidic co-polymer of Formula (1) comprises a backbone with both pendant polyalkylene oxide and acidic functionalities wherein the pka value of the acidic substituent F on the monomer from which [C] is derived is less than 5.5.
  • the acidic co-polymers of the present invention commonly comprise [B] in the range of from 20 to 95 weight %, more preferably from 30 to 80 weight % and most preferably from 40 to 70 weight % and [A] in the range of from 0 to 45 weight %.
  • [C] is preferably present in the range of from 1 to 80 weight %, more preferably from 1 to 60 weight % and most preferably from 5 to 50 weight %.
  • the molar ratios of [A] to [B] to [C], (m:n:v) respectively, are chosen such that the cloud point of the acidic co-polymer is greater than 0°C more preferably greater than 15°C and most preferably greater than 25°C.
  • the cloud point value is related to the solubility of the polymer in water and refers to the boundary at which liquid-liquid phase separation takes place in a mixture of two or more components indicated by a cloudiness of the solution due to the formation of aggregates that scatter light.
  • the temperature at which a 1% by weight solution of a polymer in distilled water becomes cloudy is the cloud point temperature.
  • the acidic co-polymers of the present invention comprise from 40 to 90% by weight polyethylene oxide introduced by [B], more preferably from 50 to 80% by weight polyethylene oxide introduced by [B].
  • the exact level of polyethylene oxide required to achieve a cloud point in the preferred range depends on a number of factors.
  • the anti-microbial agent/acidic co-polymer compositions of the present invention form a clear solution. That is, that the cloud point of the acidic co-polymers in the presence of an anti-microbial agent for example poly(hexamethylene biguanide) (PHMB), is preferably above 15°C and more preferably above 25°C. Whilst the value of q is preferably 15 to 1000, q is most preferably 20 to 400.
  • an anti-microbial agent for example poly(hexamethylene biguanide) (PHMB)
  • R ⁇ R 2 and R 3 are each independently H, optionally substituted C ⁇ -20 -alkyl or C 3- 2o-cycloalkyl, it is preferred that R ⁇ R 2 and R 3 are each H, unsubstituted, Ci- 1 0-alkyl or Ca-s-cycloalkyl. Most preferably R 1 is H or CH 3 , R 2 is H or CH 3 , and R 3 is H or unsubstituted C ⁇ -6 -alkyl, especially H or CH 3 .
  • R 4 and R 5 in repeating monomer units of X maybe the same or different, and are each independently H or C ⁇ -alkyl so long as at least one of R 4 and R 5 is H.
  • R 4 and R 5 is H and the other is -CH 3 or -C 2 H 5 with the result that X comprises oxyethylene units or a mixture of oxyethylene, oxypropylene and, or oxybutylene units. Most preferably R 4 and R 5 are both H, with the result that X comprises oxyethylene units.
  • the value of p in Formula (10) is preferably 3 to 50, most preferably 3 to 40 and most especially 3 to 25.
  • T is an optionally substituted substituent examples of which include CN, OH, F, CI, Br, -OR 6 , -C(O)R 6 , -OC(O)R 6 , -C(O)OR 6 , -C(O)NR 7 R 8 and aryl optionally substituted by -OC(O)R 6 , F, CI, Br, C 1-6 -alkyl , - CH 2 CI or -C(O)OR 6 .
  • R 6 is Ci-io-alkyl more preferably C ⁇ - 8 -alkyl for example methyl, ethyl, propyl, butyl, isopropyl, isobutyl or tert-butyl optionally substituted by a ketone, ether, epoxide, silane or ketoester group.
  • R 7 and R 8 are each independently H, C -8 -alkyl or C 3 . 8 -cycloalkyl optionally substituted by -OH, ketone or alkyl ether groups, most preferably R 7 and R 8 are H, -CH 3 or C 2 H 5 .
  • T is of the formula C(O)OR 6 , -C(O)NR 7 R 8 or -OC(O)R 6 and most preferably T is C(O)OR 6 , wherein R 6 , R 7 and R 8 are as previously described.
  • Each L is an optionally substituted linking group which joins X to the hydrocarbyl polymer backbone of [B].
  • L can be a variety of linking groups and may be the same or different, examples of L preferably comprise one or more carbon and/or hetero atoms, for example nitrogen or oxygen.
  • Examples of preferred linking groups represented by L include:
  • each L is of formula: o II — c — o —
  • J is an optionally substituted hydrocarbyl group and may be the same or different.
  • Examples of J include (shown with reference to [G]):
  • J is of Formula:
  • F in Formula (12) is an acidic substituent.
  • Each F is joined either directly to the hydrocarbyl group J or is linked to J by one or more linking groups G.
  • G When w is 2 to 4 in Formula (12), F may be joined directly to J in which case b (representing the proportion of G) is zero.
  • F may be joined to the same or different carbon atoms of J by G.
  • G may be the same or different in the repeat units of [C].
  • G is present, it is preferably selected from linking groups which directly bond to J or by linking groups with one or more groups of atoms each group of which provides a chain of one or more atoms for linking [F] with [J] with the proviso that only one F can be directly linked to a single carbon atom in [J].
  • G represents one or more groups of atoms
  • G provides a linking chain of atoms.
  • the chain will normally comprise one or more carbon atoms (for example in the form of an alkyl and/or aryl group), which may be optionally substituted by hetero atoms such as -N, -O, -S or P, most preferably N or O.
  • G linking groups (shown with reference to [F]) include:
  • d' is 2 or more, preferably 2, 3, 4 and 5 and F is the acidic substituent. It is preferred that F is linked directly to J or that F is linked to J by one of the following preferred linking groups represented by G:
  • Examples of the acidic group F in Formula (12) include carboxylic acid, sulphonic acid, phosphonic acid and phosphoric acid. It is preferred that F comprises a carboxylic acid.
  • the values of m, n and v represent the molar composition of repeat units [A], [B] and [C] respectively in the polymer of Formula [1].
  • the value of m for [A] is preferably from 0 to 350, more preferably from 0 to 100 and most preferably from 0 to 50.
  • the value of n for [B] is preferably from 1 to 75, more preferably from 1 to 40 and most preferably from 1 to 10.
  • the value of v for [C] is preferably from 1 to 100, more preferably from 1 to
  • X and G do not contain a basic group. That is, for example, a primary, secondary or tertiary amine or salts or quaternised salts thereof, or any group that could be protonated by the acidic component F in [C]. Furthermore, it is a requirement of the present invention that the pka value of the acidic substituent [F] on the monomer from which [C] is derived is less than 5.5. Examples of olefinically unsaturated monomers which may be used for [A] in
  • Formula (1) include but are not limited to styrene, ⁇ -methyl styrene, acrylonitrile, methacrylonitrile, vinyl halides such as vinyl chloride, vinyl esters such as vinyl acetate, vinyl propionate, vinyl laurate, and vinyl esters of versatic acid such as VeoVaTM 9 and VeoVaTM 10 (available from Resolution Performance Products), vinyl ethers of heterocyclic vinyl compounds and in particular, esters of acrylic acid and methacrylic acid. Olefinically unsaturated monomers with additional functionality for subsequent crosslinking and/or adhesion promotion for use in the present invention may also be used.
  • Examples of such monomers include diacetone acrylamide, acetoacetoxy ethyl methacrylate, glycidyl methacrylate, 2-hydroxy ethyl (meth)acrylate, 4-hydroxy butyl (meth)acrylate, 3-hydroxy propyl (meth)acrylate and hydroxy stearyl (meth)acrylate.
  • olefinically unsaturated monomers which may be used for [B] in Formula (1) include but are not limited to vinyl polyethers of ethylene or propylene oxide, for example hydroxypolyethoxy (5) polypropoxy (5) monoallyl ether (BX-AA-E5P5 available from Bimax), methoxypolyethyleneglycol 350 methacrylate (available under the trade name from Laporte), methoxypolyethyleneglycol 550 methacrylate (available under the trade names Bisomer MPEG 350MA and Bisomer MPEG 550MA from Laporte), methoxypolyethyleneglycol 350 acrylate, polyethyleneglycol (6) methacrylate PEM6 and polyethyleneglycol (6) acrylate PEA6.
  • vinyl polyethers of ethylene or propylene oxide for example hydroxypolyethoxy (5) polypropoxy (5) monoallyl ether (BX-AA-E5P5 available from Bimax), methoxypolyethyleneglycol 350 methacrylate (available under
  • Examples of olefinically unsaturated monomers which may be used for [C] in Formula (1) include but are not limited to acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, ⁇ -carboxy ethyl acrylate, sodium 1 -allyloxy-2-hydroxy propane sulphonate. Sulphonic, phosphonic or phosphoric acid-bearing monomers may also be used, for example styrene p-sulphonic acid (or the corresponding styrene p-sulphonyl chloride).
  • An acid bearing monomer from which [C] is derived may be polymerised as the free acid or as a salt, for example, the ammonium or alkali metal salts of ethylmethacrylate-2-sulphonic acid (available from Laporte as Bisomer SEM), 2-acrylamido-2-methylpropane sulphonic acid.
  • Preferred acidic co-polymers for use in the present invention are based on acrylic co-polymers, that is polymers based on acrylic or methacrylic acid and esters thereof.
  • Preferably [A], [B] and [C] in Formula (1 ) have the Formulae (13), (14) and (15) respectively, wherein:
  • [A] is of Formula (13), CH 2 — c
  • [B] is of Formula (14), and
  • R 6 is Ci- 1 0-alkyl more preferably C 2 . -alkyl optionally substituted by a ketone, ether,
  • R ⁇ R 2 , R 3 , R 6 , m, n, v, X, and p are as hereinbefore defined.
  • Preferred olefinically unsaturated monomers which may be used for [A] in Formula (13) are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-propyl acrylate, n-propyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate and the corresponding acrylates.
  • Methacrylates or acrylates having optional substitution on R 6 such as for example epoxide, alkyl ether, and aryl ether groups, hydroxyalkyl groups for example hydroxyethyl, hydroxy propyl or hydroxy butyl and modified analogues may also be employed as part of [A] of Formula (13).
  • Ketofunctional monomers for example the acetoacetoxy esters of hydroxyalkyl acrylates and methacrylates for example acetoacetoxyethyl methacrylate as well as silane functional monomers for example 2-(trimethylsiloxy)ethyl methacrylate may also be used.
  • the advantages of using a functionalised monomer is that it provides subsequent crosslinkability or adhesion promotion in the resulting polymer.
  • Examples of the preferred acrylic monomers which may be used for monomer [B] of Formula (14), include methoxypolyethyleneglycol 350 methacrylate, methoxypolyethyleneglycol 550 methacrylate (available from Laporte under the trade name Bisomer MPEG 350MA and Bisomer MPEG 550MA), methoxypolyethyleneglycol 350 acrylate, polyethyleneglycol (6) methacrylate PEM6 and polyethyleneglycol (6) acrylate PEA6.
  • Examples of preferred acrylic monomers which may be used for [C] of Formula (15) include methacrylic acid, acrylic acid and ⁇ -carboxy ethyl acrylate.
  • the acidic co-polymers of the present invention comprise a vinyl backbone with pendant side-chains.
  • Preferred acidic co-polymers of the present invention preferably comprise from 40% to 70% by weight of [B], from 5% to 50% of [C] and from 0 to 45% of [A].
  • the acidic co-polymers used in the present invention may be prepared by any co-polymerisation method known in the art.
  • the co-polymerisation reaction is carried out in water, an organic solvent or a mixture of water and organic solvent using a free radical initiator.
  • Suitable free-radical-yielding initiators include inorganic peroxides for example potassium, sodium or ammonium persulphate, hydrogen peroxide, or percarbonates; organic peroxides, for example acyl peroxides including for example benzoyl peroxide, alkyl hydroperoxides such as t-butyl hydroperoxide and cumene hydroperoxide; dialkyl peroxides such as di-t-butyl peroxide; peroxy esters such as t-butyl perbenzoate and mixtures thereof may also be used.
  • organic peroxides for example acyl peroxides including for example benzoyl peroxide, alkyl hydroperoxides such as t-butyl hydroperoxide and cumene hydroperoxide
  • dialkyl peroxides such as di-t-butyl peroxide
  • peroxy esters such as t-butyl perbenzoate and mixtures thereof may also be used.
  • the peroxy compounds are in some cases advantageously used in combination with suitable reducing agents (redox systems) such as sodium or potassium pyrosulphite or bisulphite, and iso-ascorbic acid.
  • suitable reducing agents such as sodium or potassium pyrosulphite or bisulphite, and iso-ascorbic acid.
  • Azo compounds such as azoisobutyronitrile or dimethyl 2.2'-azo bis-isobutylate may also be used.
  • Metal compounds such as iron.ethylene diamine tetracetic acid (EDTA) may also be usefully employed as part of the redox initiator system.
  • Other free radical initiators include cobalt chelate complexes and particularly Co(ll) and Co(lll) complexes of porphyrins, dioximes and benzildioxime diboron compounds.
  • initiator system partitioning between the aqueous and organic phases, for example a combination of t-butyl hydroperoxide, iso-ascorbic acid and iron.ethylene diamine tetracetic acid.
  • Preferred initiators comprise azo compounds such as azo-iso-butyronitrile or dimethyl 2,2'-azo bis-isobutylate and peroxides such as hydrogen peroxide or benzoyl peroxide.
  • the amount of initiator or initiator system conventionally used is for example within the range of from 0.05 to 6 weight %, more preferably from 0.1 to 3% and most preferably from 0.5 to 2% by weight based on the total vinyl amount of monomers used.
  • the organic solvent is preferably a polar organic solvent and may be a ketone, alcohol or an ether.
  • suitable polar solvents are methyl ethyl ketone, acetone, methyl isobutylketone, butyl acetate, ethoxyethylacetate, methanol, ethanol, n-propanol, iso-propanol, n-butanol, amyl alcohol, diethylglycol mono-n-butyl ether and butoxyethanol.
  • the polar organic solvent may also be used with a non-polar organic liquid. Suitable non-polar organic solvents include toluene-xylene mixtures and methylenechloride-dimethylformamide mixtures.
  • the co-polymerisation reaction is carried out in aqueous alcoholic solvents for example, methanol, ethanol, n-propanol, iso-propanol, n-butanol, amyl alcohol, diethylglycol or butoxyethanol, most preferably aqueous ethanol mixtures.
  • aqueous alcoholic solvents for example, methanol, ethanol, n-propanol, iso-propanol, n-butanol, amyl alcohol, diethylglycol or butoxyethanol, most preferably aqueous ethanol mixtures.
  • the number average molecular weight (Mn) of the polymer is typically in the range 5,000 to 200,000, more preferably 10,000 to 100,000.
  • the acidic co-polymers can also be made by aqueous emulsion or suspension polymerisation (as described in Principles of Polymerisation, G Odian, Wiley, Interscience, 3 rd edition, 1991), in which case the value of Mn may be higher and in the range 20,000 to 500,000.
  • a preferred anti-microbial agent for use in a composition with an acidic co-polymer of Formula (1) as hereinbefore described comprises an antibacterial agent, more preferably a linear polymeric biguanide which is a mixture of polymer chains in which the individual polymer chains, excluding the terminating groups are of Formula (6) or a salt thereof as hereinbefore described.
  • a preferred linear polymeric biguanide for use in the present invention is poly(hexamethylenbiguanide) hydrochloride (PHMB) available from Avecia Limited under the trade name VantocilTMIB.
  • the amount of polymeric biguanide used in the composition of the present invention relative to the amount of acidic co-polymer is dependent upon the end use of the composition, the conditions under which it will be stored and the nature of the surface to which the composition is to be applied.
  • the weight ratio of the linear polymeric biguanide to acidic co-polymer in the composition may vary over wide limits for example from 100:1 to 1 :1000, more preferably from 20:1 to 1 :500.
  • the ratio of linear polymeric biguanide group to acidic co-polymer in the antimicrobial composition is from 1 :1 to 1 :200.
  • the concentration of linear polymeric biguanide, for example poly(hexamethy!ene biguanide) (PHMB) used in the composition of the present invention is in the range of from 0.001 weight % to 25 weight %, preferably from 0.005 weight % to 10 weight %, and especially from 0.01% to 5 weight %.
  • the pH of the composition is typically chosen so that it is most appropriate for a particular application and is preferably in the range of from pH 1 to 12 most preferably from pH 3 to 9.
  • the composition of the present invention may also contain other additives depending upon the particular use intended for the composition.
  • Additional components optionally included in the composition may be for example additional polymeric materials, detergents, botanical extracts, perfumes, fragrances, thickeners, humectants, anti-corrosion agents, surfactants, colourants, chelating agents, buffers, acidity and alkalinity regulators, wetting agents, sequestering agents, hydrotropes, adjuvants, anti-soil agents and enzymes.
  • additional polymeric materials detergents, botanical extracts, perfumes, fragrances, thickeners, humectants, anti-corrosion agents, surfactants, colourants, chelating agents, buffers, acidity and alkalinity regulators, wetting agents, sequestering agents, hydrotropes, adjuvants, anti-soil agents and enzymes.
  • the carrier may be a solid but is preferably a liquid and the formulation is preferably a solution, suspension or emulsion of the anti-microbial composition in the liquid.
  • water is the preferred carrier for the composition
  • other solvents such as water miscible organic solvents may also be present in the composition.
  • suitable water-miscible organic solvents include, glycols such as ethylene glycol, propylene glycol, dipropylene glycol methanol, ethanol, propan-1-ol, propan-2-ol, Ci-s-alkyl esters for example butylethyl acetate, pentyl acetate, N-methyl-2-pyrrolidone and lower C 1-4 -alkyl carbitols such as methyl carbitol.
  • Preferred water-miscible organic solvents are glycols with 2 to 6 carbon atoms, poly-alkylene glycols with 4 to 9 carbon atoms or mono C 1-4 -alkyl ethers of glycols with 3 to 13 carbon atoms.
  • the most preferred water-miscible organic solvents are propylene glycol, ethyl hexyl glycol, ethanol, butyl ethyl acetate or pentyl acetate.
  • a formulation comprising: (i) a linear polymeric biguanide; (ii) an acidic co-polymer; and (iii) a carrier.
  • a preferred formulation of the final diluted application liquor according to a second aspect of the invention comprises from 0.01 to 5% by weight linear polymeric biguanide, more preferably from 0.1 to 1% by weight linear polymeric biguanide in the form of poly(hexamethylene biguanide) hydrochloride (PHMB).
  • the amount of acidic co-polymer in the formulation is preferably from 0.01 to 50% by weight, especially from 0.1 to 25% by weight.
  • the preferred carriers are water or water/alcohol mixtures.
  • the pH of the formulation is typically chosen to be most appropriate for the application and is preferably in the range of from 1 to 12. Most preferably the pH of the formulation is in the range of from 3 to 9.
  • An especially preferred formulation according to the second aspect of the present invention comprises a diluted application solution containing 0.5% by weight poly(hexamethylene biguanide) hydrochloride (PHMB) and from 2 to 15% by weight acidic co-polymer in the form of an aqueous solution.
  • PHMB poly(hexamethylene biguanide) hydrochloride
  • the formulation may also contain other additives depending upon the particular use intended for the composition. Additional components optionally included in the formulation are for example those disclosed for use in compositions according to the first aspect of the invention.
  • a composition comprising a linear polymeric biguanide and an acidic co-polymer is applied to a surface a susta lined anti-microbial effect against a broad range of micro-organisms including gram posit :iive bacteria, gram negative bacteria, pathogenic bacteria, yeasts, fungi and algae is achieved. Therefore, according to a further aspect of the present invention there is provided a method of treating a surface which comprises treating the surface with a composition or a formulation as hereinbefore described with reference to the first and second aspects of the present invention.
  • the preferred anti-microbial agent poly(hexamethylene biguanide) hydrochloride
  • other microbiologically active compounds may also be present in combination with the polymeric biguanides.
  • examples of other microbiologically active compounds include for example: quaternary ammonium compounds for example, N,N-diethyl-N-dodecyl-N-benzylammonium chloride,
  • N,N-dimethyl-N,N-didecylammonium chloride N,N-dimethyl-N,N-didodecylammonium chloride; N,N,N-trimethyl-N-tetradecylammonium chloride, N-benzyl-N,N-dimethyl-N-(Ci2-Ci8 alkyl)ammonium chloride,
  • N-(dichlorobenzyl)-N,-N-dimethyl-N-dodecylammonium chloride N-hexadecylpyridinium chloride, N-hexadecyl pyridinium bromide, N-hexadecyl-N,N,N-trimethylammonium bromide, N-dodecyl pyridinium chloride, N-dodecylpyridinium bisulphate,
  • N-benzyl-N-dodecyl-N,N-bis(beta-hydroxy-ethyl)ammonium chloride N-dodecyl-N-benzyl-N,N-dimethylammonium chloride, N-benzyl-N,N-dimethyl-N-(C ⁇ 2 -C ⁇ 8 alkyl) ammonium chloride, N-dodecyl-N,N-dimethyl-N-ethylammonium ethylsulphate, N-dodecyl-N,N-dimethyl-N-(1-naphthylmethyl)ammonium chloride,
  • 2-(methoxycarbonyl-amino)-benzimidazole (Carbendazim); nitrile compounds for example, 2-bromo-2-bromomethyl-glutaronitrile, 2-chloro-2-chloro-methylglutaro-nitrile, 1 ,2-dibromo-2,4-dicyanobutane or 2,4,5,6-tetrachloro-1 ,3-benzenedicarbonitrile
  • thiocyanate derivatives for example methylene(bis)thiocyanate or 2-(thiocyanomethylthio)-ben ⁇ othiazole
  • tin compounds or complexes for example, tributyltinoxide chloride, naphthoate, benzoate or 2-hydroxybenzoate
  • isothiazolin-3-ones for example 4,5-trimethylene-4-isothiazolin-3-one, 2-methyl-4,5-trimethylene-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one (MIT), 5-chloro-2-methyl-4-isothiazolin-3-one (CMIT), 2-octylisothiazolin-3-one (OIT) or 4,5-dichloro-2-octyl-4-isothiazolin-3-one (DCOIT); benzisothiazolin-3-one compounds for example 1 ,2-benzisothiazolin-3-one (BIT
  • 2-n-butylbenzisothiazolin-3-one N-ethyl, N-n-propyl, N-n-pentyl, N-cycIopropyl, N-isobutyl, N-n-hexyl, N-n-octyl, N-n-decyl and N-tert-buty!1,2-benzisothiazolinone;
  • thiazole derivatives for example, 2-(thiocyano methylthio)-benzthiazole or mercaptobenzthiazole; nitro compounds for example, tris(hydroxymethyl)nitromethane,
  • iodine compounds for example tri-iodo allyl alcohol
  • aldehydes and aldehyde release agents for example glutaraldehyde (pentanedial), formaldehyde or glyoxal
  • amides for example chloracetamide, N,N-bis(hydroxymethyl)chloracetamide, N-hydroxymethyl- chloracetamide or dithio-2,2-bis(benzmethylamide)
  • guanidine derivatives for example 1 ,6-hexamethylene-bis[5-(4-chlorophenyl)biguanide], 1 ,6-hexamethylene-bis[5-(4-chlorophenyl)guanide], bis(guanidinooctyl)amine triacetate, 1 ,6-D-(4'-chlorophenyldigu
  • PCMX 4-chloro-3,5-dimethyl-phenol
  • sulphone derivatives for example diiodomethyl-paratolylsulphone, 2,3,5,6-tetrachloro-4-(methylsulphonyl)pyridine or hexachlorodimethylsulphone
  • imides for example, N-(fluorodichloromethylthio)phthalimide (Preventol A3), N-(trichloromethylthio)phthalimide (Folpet) or
  • N-(trichloromethyl)thio-4-cyclohexene-1 ,2-dicarboxyimide Captan
  • thioamides the metal complexes and salts thereof for example dimethyldithiocarbamate, ethylenebisdithiocarbamate, 2-mercapto-pyridine-N-oxide (especially the 2:1 zinc complex and the sodium salt)
  • azole fungicides for example hexaconazole, tebuconazole, propiconazole, etaconazole or tetraconazole
  • strobilurins for example methyl-(E)-2-[2-(6-(2-cyanophenoxy)pyrimidin-4-yloxy)phenyl]-3-methoxyacrylate (Azoxystrobin), methyl-(E methoxyimino[ ⁇ -(o-tolyloxy)-o-tolyl]acetate,
  • IPBC 3-lodopropargyl-N-butylcarbamate
  • IPPC 3-lododpropargyl-N-phenylcarbamate
  • Thiram Bis-(diemthylthiocarbamoyl)-disulphide
  • pyridine derivatives for example sodium or zinc salt of 2-mercaptopyridine-N-oxide (Sodium or Zinc pyrithione)
  • compounds with activated halogen groups for example tetrachloroisophthalodintril (Chlorthalonil), 1 ,2-Dibromo-2,4-dicyanobutane (Tektamer 38)
  • organometallic compounds for example 10,10'-Oxybisphenoxyarsine (OBPA).
  • the amount of additional anti-microbial compound(s) in the composition will depend upon the nature of the additional anti-microbial compound and the surface to be protected against microbial degradation.
  • compositions or formulations of the present invention for disinfecting surfaces found in for example household, industrial or institutional areas.
  • the treatment can be applied to a wide variety of surfaces as exemplified as follows but not limited thereto.
  • Surface applications include for example, walls, floors, work surfaces, equipment found in domestic, industrial, food processing, sanitary, health and medical environments, skin, synthetic and natural textiles and fibres, stainless steel, polymer and polymeric coatings such as vinyl, polyvinyl chloride, polypropylene and polyethylene, wood, glass, rubber, paint surfaces, stone, marble, grouts, packaging and films.
  • the anti-microbial compositions and formulations according to the first and second aspects of the invention significantly reduces the levels of micro-organisms on surfaces treated with the anti-microbial compositions, which activity is sustained over a period of time.
  • a composition according to the first aspect of the present invention or the use of a formulation according to a second aspect of the present invention for the treatment of surfaces may also be used in combination with anti-fungal compounds. It has surprisingly been found that fungicidal compounds are also controllably released from the acidic co-polymers over time thereby providing sustained and effective anti-fungal control.
  • fungicides can be used in combination with the acidic co-polymers described above.
  • examples of such fungicides include but are not limited to: methoxyacrylates, for example, methyl (E)-2-2-6-(2-cyanophenoxy)pyrimidin-4-yloxyphenyl-3-methoxyacrylate; carboxamides and acetamides for example, 5,6-dihydro-2-methyl-N-phenyl-1 ,4-oxathiin-3-carboxamide and 2-cyano-N-[(ethylamino)carbonyl]-2-(methoxyamino)acetamide; aldehydes, for example cinnamaldehyde and 3,5-dichloro-4-hydroxybenzaldehyde; pyrimidines, for example 4-cyclopropyl-6-methyl-N-phenyl-2-pyrimidinamine and 5-butyl-2-ethylamino-6-methylpyrimidin-4-ol; morpholines for example,
  • C ⁇ -1 -alkyl-2,6-dimethylmorpholine-homologues such as (Tridemorph) and (+)-cis-4-[3-tert-butylphenyl)-2-methylpropyl]-2,6-dimethylmorpholine (Fenpropimorph);
  • guanidines for example 1-dodecylguanidine acetate
  • pyrroles for example 4-(2,2-difluoro-1,3-bezodioxol-4-yl)-1Hpyrrole-3-carbonitrile
  • imidazoles and benzimidazoles for example
  • Triazole fungicides can be present not only in the form of free bases but also in the form of their metal salt complexes or as acid addition salts, for example salts of metals of main groups II to IV and sub-groups I and II and IV to VII of the periodic table of elements, examples of which may include copper, zinc, manganese, magnesium, tin, iron, calcium, aluminium, lead, chromium, cobalt and nickel.
  • Possible anions of the salts are those which are preferably derived from the following acids: hydrohalic acids, for example, hydrochloric acid, hydrobromic acid, phosphoric acid, nitric acid and sulphuric acid. In cases where the compound has an asymmetric carbon atom, isomers and isomer mixtures are also possible.
  • fungicides include: oxazolidines for example, 3-(3,5-dichlorophenyl)-5-methyl-5-vinyl-1 ,3-oxazolidine-2,4-dione; p-hydroxybenzoates for example, benzoic acid, paramethylbenzoic acid, salicylic acid, dehydroacetic acid and salts thereof; isothiazolinones, for example 2-methylisothiazolin-3-one, 5-chloro-2-methylisothiazolin-3-one,
  • benzisothiazolin-3-one compounds for example 2-methylbenzisothiazolin-3-one, 2-n-butylbenzisothiazolin-3-one N-ethyl, N-n-propyl, N-n-pentyl, N-n-hexyl, N-cyclopropyl, and N-isobutylbenzisothiazolin-3-one;
  • quaternary ammonium compounds for example, cocoalkylbenzyl-dimethylammonium, tetradecylbenzyldimethylammonium chlorides, myristyltrimethyl ammonium, cetyltrimethylammonium bromides, monoquatemary heterocyclic amine salts, laurylpyridinium, cetylpyri
  • 3-iodo-2-propynyl-N-cyclohexylcarbamate, 3-iodo-2-propynyl-N-phenyl carbamate and thiocarbamates for example S-ethyl cyclohexyl(ethyl)thiocarbamate; sulphenamides for example, Dichlofluanid (Euparen), Tolyl luarid (Methyleuparen), Folpet, Fluorfolpet, tetramethyldiuramdisulfides (TMTD) and 2-methylbenzamide-1 , 1 'disulphide (available as DensilTMP from Avecia Ltd); thiocyanates for example, thiocyanatomethylthiobenzothiazole (TCMTB) and methylenbisthiocyanate (MBT); phenols for example, o-phenylphenol, tribromphenol, tetrachlorphenol, pentachlorphenol, 2-phenoxyethnaol 3-
  • pyridines for example, 1-hydroxy-2-pyridinthione or pyridine-2-thiol-1 -oxide (sodium, iron, manganese or zinc salts commercially available under the trademark Sodium Omadine from Arch Chemicals), tetrachlor-4-methylsulphonylpyridine, 2,3,5,6 tetrachloro-4(methyl sulphonyl)pyridine (available from Avecia Limited as DensilTM S); metallic soaps for example, tin, copper, zinc-naphthenate, octoate, 2-ethylhexanoate, oleate, -phosphate, benzoate, or oxides for example TBTO, Cu 2 O, CuO and ZnO; organic tin-derivatives, for example tributyltin naphthenate or tributyl tinoxide; dialkyldithiocarbamates for example sodium and zinc salts of dialkyldithio
  • Preferred antifungal compounds include quaternary ammonium compounds, isothiazolione and benzisothiazolinone compounds, carbamates and pyridine compounds.
  • composition comprising:
  • [A] is of Formula (9),
  • [B] is of Formula (10),
  • T is an optionally substituted substituent
  • L and G each independently is an optionally substituted linking group
  • R ⁇ R 2 and R 3 are each independently H, optionally substituted C ⁇ -2 o-alkyl or optionally substituted C 3-2 o-cycloalkyl;
  • R 4 and R 5 are each independently H or C-u-alkyl; q is 15 to 1000; p is 3 to 50;
  • J is an optionally substituted hydrocarbyl, group
  • F is an acidic substituent; b is 0, 1 , or 2; m is 0 to 350; n is 1 to 75; v is 1 to 100; and w is 1 to 4; provided that at least one of R 4 and R 5 is H and provided that R ⁇ R 2 , R 3 , T, L, J and G do not contain a basic group; and wherein the pka value of the acidic substituent F on the monomer from which [C] is derived is less than 5.5.
  • preferences for [A], [B], [C], m, n, v, q, T, L, X, J, G, F, R 1 , R 2 , R 3 , R 4 , R 5 , p, b and w are as hereinbefore defined with reference to the first aspect of the present invention.
  • Initiator solution (1) was prepared by dissolving dimethyl 2,2' azobis isobutyrate (2.3g) (0.01 moles) in solvent (92.7 g of a 50/50 mixture of ethanol/distilled water).
  • solvent 360g of a 50/50 mixture of ethanol/distilled water
  • monomer solution (2) (447g).
  • the monomer solution (2) was washed into the reactor with additional solvent (100 g of a 50/50 mixture of ethanol/distilled water).
  • additional solvent 100 g of a 50/50 mixture of ethanol/distilled water.
  • the reactor was heated to 75°C using a Haake circulating water bath and was stirred at 180 rpm under a nitrogen blanket.
  • At time zero initiator solution (1) (23.7g) was added to the reactor followed 30 minutes later by more initiator solution (47.5g).
  • the solution was left for 3 hours 30 minutes before increasing the reactor temperature to 80°C.
  • additional initiator solution (1) (11.9 g) was added to the reactor which was then stirred for a further two hours after which time the final aliquot of initiator solution (1) (11.9g) was added. After two hours the resultant co-polymer solution was cooled and removed from the reactor.
  • the total time of polymerisation was eight hours.
  • the final solution was water white and free of particulate matter.
  • the co-polymer was formed in greater than 99% yield as determined by weight difference following exhaustive evaporation from a sample of the co-polymer solution.
  • the molecular weight of the co-polymer was determined using gel permeation chromatography (GPC) with polyethylene oxide as molecular weight standards. NMR Analysis was used to confirm the ratio of the repeat monomer units [A], [B] and [C] and Dynamic Mechanical Thermal Analysis (DMTA) was used to determine the Tg of the co-polymer.
  • GPC gel permeation chromatography
  • DMTA Dynamic Mechanical Thermal Analysis
  • VinylPO3H Vinyl phosphonic acidPPG5MA Methoxypolypropylene glycol monomethacrylate with 5 propylene glycol units
  • PEG350MA Methoxy polyethylene glycol monomethacrylate with 7 to 8 ethylene oxide units.
  • PEG550MA Methoxy polyethylene glycol monomethacrylate with 12 to 13 ethylene oxide units. Determination of the Cloud Point of the Acidic Co-polymers of Table 1 and Cloud Point Changes with Co-polvmer Composition.
  • the cloud points of co-polymers (1 to 14 from Table 1) were determined by making 1% by weight solutions of the polymers in distilled water. Each polymer solution was heated and stirred until it became cloudy. The stirred solution was then allowed to cool whilst the temperature was monitored. The temperature at which the solution became clear is the cloud point.
  • the cloud point of Polymer 10 determined by this method was 33 °C (polyethylene oxide content 65 % by weight).
  • Graph 1 shows how the cloud point varies as a function of the polyethylene oxide (PEO) content in polymers 3, 7 and 8.
  • PED Polyethylene oxide
  • compositions 1 to 20 were prepared by mixing a 20% aqueous solution of poly (hexamethylene biguanide) hydrochloride (PHMB) (5g) (available from Avecia Limited as VantocilTMIB) to each of the polymers 1 to 20 from Table 1 as 20% solutions (in water/ethanol 1/1) in varying quantities as set out in Table 2.
  • the compositions were allowed to stand for 24 hours before being applied to substrates such as glass or ceramic tiles. All of the compositions were low viscosity colourless transparent solutions, free from sediment and with excellent storage stability. Storage stability was tested by storing the compositions for 2 months at 52°C and was considered excellent if the viscosity of the composition remained unchanged and there was no formation of precipitate or gel particles.
  • compositions 21-28 were prepared by mixing with various biocides. To a sample of the polymer solution the biocide was added at concentrations ranging from 0.1% - 0.5% wt/wt on total weight of the solution. The compositions were placed on a rotating mixer for 24 hours to form a homogenious composition and then applied to substrates such as glass or ceramic tile. The compositions were of low viscosity and free from sediment.
  • Biocide A n-Butyl 1 ,2, benzisothiazolin Biocide B Dodecylethyldimethylammonium bromide Biocide C 3-iodopropargylbutyl carbamate Biocide D 2-octylisothiazolin-3-one
  • PHMB Poly(hexamethylene biguanide)
  • UV absorbance at 236nm of a known concentration of poly(hexamethylene biguanide) (PHMB) dissolved in water was measured (Perkin Elmer Lambda 900 UV ⁇ is/NIR Spectrophotometer).
  • UV absorbance at 236nm was measured for a series of samples prepared from known dilutions of the original PHMB aqueous solution.
  • a calibration curve for PHMB concentration in aqueous solution was produced (Graph 2) by plotting UV absorbance against PHMB concentration.
  • Acidic co-polymer/PHMB Compositions 1 to 20 were separately applied to clean glass panels (150mm x 100mm) and films of the composition were drawn down using a
  • the water samples were analysed using a UV spectrophotometer and the absorbance of each sample measured at a specific peak corresponding to the ⁇ max of poly(hexamethylene biguanide) (PHMB).
  • the measured absorbance was directly related to the concentration of the PHMB in the beaker.
  • PHMB poly(hexamethylene biguanide) hydrochloride available from Avecia Limited as VantocilTM IB).
  • PHMB poly(hexamethylene biguanide) hydrochloride available from Avecia Limited as VantocilTM IB.
  • composition 14 which contains the slightly more hydrophilic polymer 7 with a PEO content of 65% releases PHMB slightly faster than a film of composition 14 containing Polymer 3 with a PEO content of 56 % .
  • composition 12 containing 16.7% by weight PHMB releases all its PHMB within 10 minutes whereas Composition 14 with just 5% by weight PHMB takes
  • the rate of dissolution of PHMB from the acidic co-polymer/PHMB could be controlled according to the structure of the acidic co-polymer and the PHMB content.
  • the above illustrates that stable solutions in both water and water/ethanol mixtures can be prepared with acid bearing co-polymers and polymeric biguanides.
  • compositions of co-polymer example 7 from table 1 with various levels of PHMB were evaluated by measuring the Minimum Inhibitory Concentrations (MICs):
  • Bacteria (Pseudomonas aeruginosa ATCC 15442) were grown on nutrient agar for 16 to 24 hours at 37°C (to give approximately 10 9 cells per ml).
  • the presence or absence of growth was determined by visual inspection after 24 hours incubation at 37°C.
  • the MIC is the lowest concentration of the sample required to inhibit bacterial growth.
  • Table 5 Intrinsic Activity of Acidic co-polymer.
  • Stable compositions could be prepared for all compositions used in the MIC's test protocol and as shown in the Table 5 an intrinsic activity could be achieved. Sustained Bactericidal Activity of Acidic co-polvmers with PHMB
  • Acidic co-polymer/PHMB compositions were prepared as previously described
  • the residual antibacterial activity of the samples was determined by the following methodology:
  • compositions were diluted to 0.5% active ingredient (PHMB). A 50 ⁇ l aliquot of each sample was placed in a ceramic tile well and allowed to dry for approximately
  • Bacteria Bacteria [Ps.aeruginosa ATCC 15442) were grown in nutrient broth at 37°C for 16-20 hours.
  • the RABITTM Rapid Automated Bacterial Impedance Technique measures the change in conductance of a bacterial suspension over time. Actively growing bacteria break down uncharged or weakly charged molecules in a defined media to give end products that are highly charged. The resultant increase in conductance can be directly related to bacterial concentration by the use of a calibration curve. (Further background relating to this known technique can be found in: Technical Reference Paper-RAB-03, Don Whitley Scientific, 14 Otley Road, Shipley, West Yorkshire, UK, BD17 7SE).
  • Table 6 summarises the sustained bactericidal activity of the Acidic co-polymer/PHMB formulations obtained using the above technique.
  • Table 6 Sustained Bactericidal Activity of Anionic Co-polvmers with PHMB.
  • composition 18 sustained its residual bactericidal effect compared with PHMB alone under the repeated washing regime used in the protocol.
  • Acidic co-poiymer/Biocide compositions were prepared as previously described (Table 2).
  • the residual antifungal activity of the compositions were determined by the following methodology:
  • Fungi ⁇ Aspergillus niger ATCC 16404) were grown on malt agar plates at 25° C for approx. 7 days.
  • samples were washed into a neutralising medium, serially diluted in physiological saline and plated out onto malt agar).
  • composition was then washed ten times by spraying with sterile distilled water.
  • composition was then re-inoculated and after 24 hours the number of viable organisms enumerated by the method described above.
  • Table 7 summarises the sustained fungicidal activity of the Acidic co-polymer/Biocide formulations obtained using the above technique.
  • Table 7 Sustained Fungicidal Activity of Acidic Co-polymers (Example 2) with Various Biocides.

Abstract

L'invention concerne une composition contenant (i) un agent antimicrobien et (ii) un copolymère acide de formule (1), dans laquelle [A] représente la formule (9), [B] représente la formule (10) et [C] représente la formule (12), [X] représentant la formule (11), [A], [B] et [C] pouvant se produire dans un ordre quelconque, T représentant un substituant substitué facultativement, L et G représentant respectivement et indépendamment un groupe de liaison substitué facultativement, R1, R2 et R3 représentant respectivement et indépendamment H, C1-20-alkyle substitué facultativement ou C3-20-cycloalkyle substitué facultativement, R4 et R5 représentant respectivement et indépendamment H ou C1-4-alkyle, q étant compris entre 15 et 1000, p étant un nombre compris entre 3 et 50, J représentant un groupe hydrocarbyle substitué facultativement, F représentant un substituant acide, b étant égal à 0, 1 ou 2, m étant compris entre 0 et 350, n étant compris entre 1 et 75, v étant compris entre 1 et 100, et w étant compris entre 1 et 4, à condition que R4 ou R5 représente H et à condition que R1, R2, R3, T, L, J et G ne contiennent pas un groupe basique. En outre, la valeur pka du substituant acide F sur le monomère, à partir duquel [C] est dérivé, est inférieure à 5,5.
EP04732135A 2003-05-15 2004-05-11 Composition contenant un copolymere acide et un agent antimicrobien, et son utilisation Withdrawn EP1624755A1 (fr)

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GB0311166A GB0311166D0 (en) 2003-05-15 2003-05-15 Composition and use
GB0325238A GB0325238D0 (en) 2003-10-29 2003-10-29 Composition and use
PCT/GB2004/002001 WO2004100664A1 (fr) 2003-05-15 2004-05-11 Composition contenant un copolymere acide et un agent antimicrobien, et son utilisation

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US10759949B2 (en) 2016-07-11 2020-09-01 Spartan Chemical Company, Inc. Antimicrobial sacrificial floor coating systems

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EA200900482A1 (ru) 2006-10-05 2009-10-30 Басф Се Гребенчатые полимеры и их применение для получения композиций действующего или эффективного вещества
JP5837346B2 (ja) * 2011-07-05 2015-12-24 攝津製油株式会社 ウイルス不活化組成物
JP2017206441A (ja) * 2014-09-22 2017-11-24 Jsr株式会社 殺菌性組成物

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