IMPROVED TREATMENT METHOD USING COATED TREATMENT BODIES

[0001] Field of the Invention

[0002] This invention relates to a method for the treatment of substrates using treatment bodies comprising an active agent. The invention is especially suitable for the laundering of textiles and for dishwashing. The invention also relates to the treatment bodies used in the method and to the method of preparing said treatment bodies.

[0003] Background

[0004] PCT patent publication WO2014/006424 discloses the use of cleaning formulations and methods for cleaning (e.g. textiles) using solid cleaning particles. In these formulations and methods, the solid cleaning particles comprises polymeric particles and at least one cleaning agent which is immobilised on the surface of the polymeric particles. This document provided formulations and methods which could much improve cleaning performance. That being said, it was seen that the cleaning performance tended not to be too long-lived when the solid cleaning particles were used a number of times. As an example, the improvements in cleaning performance were lost or substantially lost by the 6 ^th repeated use of the solid cleaning particles. In addition, the present inventors found that the amount of cleaning agent which could be immobilised onto the surface of the polymeric particles was not as much as might be desired and that further improvement would be advantageous. Furthermore, the present inventors found that some kinds of polymeric material were less easily modified chemically.

[0005] The present invention uses treatment bodies which can be, for example, solid particles or a material such as a textile or mesh.

[0006] The present inventors sought (among other things) to address one or more of the following technical problems:

To provide a method which is able to use interior materials which would otherwise be relatively inert.

II To provide a treatment method which retains activity and effectiveness for more than 6, and especially more than 10 re-uses of the treatment bodies;

III To provide a treatment method using treatment bodies which are especially active.

IV. To provide a treatment method which is less prone to microbiological fouling. v. To provide a treatment method which has good bleaching activity.

[0007] Summary of the Invention

[0008] In a first aspect of the present invention, there is provided a method for the treatment of a substrate comprising agitating a composition comprising one or more treatment bodies, the substrate, and a liquid medium, wherein said treatment bodies comprise an interior material which is coated with a surface polymer, the surface polymer being immobilised on the surface of the interior material, and wherein an active agent is covalently bonded to the surface polymer.

[0009] Figures

[0010] Figures 1a and 1 b show the Fourier Transform Infra Red (FTIR) spectrographs of firstly the interior material for use in the treatment body, and secondly the treatment body comprising the interior material and a surface polymer. Thus, Figure 1a is the FTIR spectrograph of the interior material which is a polyamide. Figure 1 b is FTIR spectrograph of the treatment body comprising an interior material which is a polyamide and a surface material which is a polymerised acrylic containing ester groups; demonstrating the desired ester group being present at the surface.

[0011] Active agent

[0012] The active agent preferably is or comprises an antimicrobial agent, an enzyme, a bleaching agent, a catalyst (especially a bleaching catalyst), a surfactant, a dye transfer inhibitor or a combination thereof.

[0013] The active agent can be or comprise an antimicrobial agent. The antimicrobial agent can have a cationic group. A preferred cationic group is a quaternary ammonium group. Other cationic groups include pyridinium, guanide and biguanide groups.

[0014] The antimicrobial agent can have a phenolic group. Preferred examples of antimicrobial agents having phenolic groups include tridosan; diclosan; dichlorophen; orthophenylphenol; orthobenzylparach!orophenoi, cresois and xylols.

[0015] The active agent can be or comprise a bleaching catalyst. Preferably, the bleaching catalyst comprises a cyclic ligand having at least one nitrogen atom.

[0016] Immobilised

[0017] The surface polymer is immobilised on the surface of the interior material. This preferably means that the surface polymer will not desorb or diffuse away from the interior material, especially when the liquid medium is water. By example the surface polymer will not simply desorb or diffuse into water. This distinguishes the surface polymer from (as an example) surfactants and dispersants which tend to coat interior materials but which readily also desorb from the surface of the interior material into water.

[0018] The present inventors found that especially by forming the surface polymer in the presence of the interior material the resulting surface polymer was effectively immobilised. This was especially so when the surface polymer was polymerised in the presence of the interior material and more especially when the polymerisation was initiated by a free radical initiator.

[0019] Whilst not wishing to be limited by any one theory it is considered that the polymerisation of monomers to form the surface polymer in the presence of the interior material tends to immobilise the surface polymer by any one or more of the following mechanisms:

i. The interior material and the surface polymer become entangled or intimately mixed at molecular level;

ii. The surface polymer locks into any pores or other surface structures at a macroscopic scale on the interior material which provides a highly effective bond very much akin to a gluing process;

iii. The polymerisation of monomers to form the surface polymer tends to reactively graft at least some of the surface polymer chains to the interior material.

[0020] Substrate

[0021] Optionally, the substrate is or comprises a metal, a metal alloy, a ceramic, glass, plastic, wood or a combination thereof. Optionally, the substrate is rigid. Optionally, the substrate is in the form pots, pans, trays, utensils, cups, jugs, glasses, plates, saucers, bowls and the like. Substrates of this kind are especially suitable for the treatment according to this invention which is or comprises dishwashing.

[0022] Preferably, the substrate is flexible. Preferably, the substrate is or comprises a textile, a fibre, a yarn, an animal hide or an animal skin. The substrate preferably is or comprises a textile. The animal hide or animal skin is preferably from a cow, pig, sheep or goat, more especially from a cow. The textile, fibre or yarn may be a natural, synthetic or semi-synthetic material. Suitable natural materials include cotton, wool and silk. Suitable synthetic materials include polyamides (e.g. Nylons), polyesters, acrylics and polyurethanes. Substrates of this kind are especially suitable for the treatment according to this invention which is or comprises laundering. [0023] The substrate is preferably soiled. By soiled we preferably mean stained with for example: foodstuffs, beverages, grass, dirt, animal fluids and secretions (including mucus, blood, urine, faeces and sweat).

[0024] The substrate is preferably coloured. The substrate is preferably not colourless or transparent. The substrate may be coloured by means of one or more pigments and/or one or more dyes. The colorant is preferably on the surface of the substrate. The colorant is preferably adhered, fused, immobilised, chemically fixed or bonded to the substrate.

[0025] Bleaching agent

[0026] When the active agent is a bleaching agent it preferably comprises a cyclic ligand having at least one nitrogen atom.

[0027] The one or more treatment bodies preferably comprise a plurality (two or more) of active agents (or cyclic ligands) as described above. When two or more cyclic ligands are present these can be the same or different. Preferably, every one of the treatment bodies comprises a plurality of cyclic ligands.

[0028] The one or more treatment bodies can comprise little or no active agent underneath the surface. More preferably, the interior material does not comprise any active agent.

[0029] Preferably, the cyclic ligand has at least two, more preferably at least three nitrogen atoms in its molecular structure.

[0030] Preferably, the cyclic ligand has no more than 20, more preferably no more than 15 and especially no more than 8 nitrogen atoms in its molecular structure.

[0031] The abovementioned preferences for the numbers of nitrogen atoms in the cyclic ligand preferably mean the numbers of nitrogen atoms within the cyclic structure of the cyclic ligand.

[0032] Preferably, the cyclic ligands are synthesized by the cyclisation of a diamine with a dihalo compound or a ditosylate. Preferred diamines include, propylenediamine, diethylenetriamine, triethylenetetramine, dipropylenetriamine, tripropylenetetramine or Ν,Ν'- bis(3-aminopropyl)-1 ,3-propanediamine and especially ethylenediamine. Preferred dihalo and ditosylate compounds include 1 ,2-haloethane, 1 ,3-dihalopropane and ethylene ditosylate.

[0033] The cyclic ligand may have one or more substituents at any points in the structure. The substituents can be on one or more nitrogen and or (when present) one or more carbon atoms. Examples of substituents include: alkyl, hydroxy, halo, -amine, acid (carboxylic, sulfonic or phosphonic), cyano, nitro, ester (carboxylic acid ester) and ether. Preferably, any carbon atoms present in the cyclic structure of the cyclic ligand are unsubstituted. Preferably, any nitrogen atoms present in the cyclic structure of the cyclic ligand are alkylated (especially methylated).

[0034] Preferably, the cyclic ligand comprises -CH2CH2- and/or -CH2CH2CH2- groups, more preferably -CH2CH2- groups. Preferably, these groups are comprised in the cyclic structure itself.

[0035] Preferably, the cyclic ligand comprises a -CH2CH2- group, more preferably at least two -CH2CH2- groups and especially at least three -CH2CH2- groups.

[0036] Preferably, the cyclic ligand comprises no more than 20, more preferably no more than 15 and especially no more than 6 -CH2CH2- groups.

[0037] An especially effective cyclic ligand has 3 -CH2CH2- groups.

[0038] Preferably, the -CH2CH2- are comprised in the cyclic structure of the cyclic ligand.

[0039] Preferably, both ends of the -CH2CH2- group are attached to a nitrogen atom.

[0040] Preferably, the above-mentioned number of -CH2CH2- groups present in the cyclic ligand are those which are comprised in the cyclic structure.

[0041] Preferably, the nitrogen atoms in the cyclic structure of the cyclic ligand belong to amine groups which are preferably secondary or tertiary amine groups.

[0042] Preferably, at least one of the nitrogen atoms in the cyclic ligand (especially comprised in the cyclic structure itself) is a tertiary nitrogen. The present inventors found that cyclic ligands of this structure tend to have better activity for bleaching and cleaning.

[0043] Preferably, the tertiary nitrogen is a -NR- group wherein R is an alkyl group. The alkyl group can be a Ci-Cs alkyl, but is more preferably propyl, ethyl and especially methyl.

[0044] Preferably, the cyclic ligand is or comprises 1 ,4,7-triazacyclononane or a derivative thereof. Said derivatives thereof preferably includes salts, metalised compounds and derivatives wherein one or more of the nitrogen atoms within the cyclic structure is bonded to an alkyl group.

[0045] Preferred cyclic ligands are those of Formulae (1) to (9) wherein, each R independently is H or alkyl (especially methyl) and the asterisk (*) represent the point of covalent bonding to the one or more treatment bodies:

[0046]

Formula (3)

Formula (4)

Formula (6)

10

10 Formula (9). [0047] Of these cyclic ligands, Formula (1) is especially preferred. This ligand was found to demonstrate superior performance at low temperatures, it could be covalently bonded readily to the treatment bodies and it retained its bleaching catalysts activity for especially long periods of re-use.

[0048] Metalisation of the cyclic ligand

[0049] The cyclic ligand can be metalised or substantially non-metalised prior to the treatment according to the first aspect of the present invention. By substantially non- metalised we preferably mean with the exception of trace levels of metalisation which are synthetically difficult to avoid.

[0050] When the cyclic ligand is metalised it is preferably metalised with a transition metal, more preferably a d-block transition metal.

[0051] Preferably, the metal for metalising the cyclic ligand is selected from the group consisting of Chromium, Manganese, Molybdenum, Iron, Cobalt, Copper, Zinc and Nickel.

[0052] Optionally, the metal for metalising is an alkali metal, especially lithium, potassium and sodium.

[0053] When the ligand is substantially non-metalised prior to the treatment it is preferred that the substrate supplies metals which can metalise the cyclic ligand during the treatment.

[0054] Conditions for the treatment

[0055] In order of increasing preference, the treatment is performed at a temperature of no more than 95°C, no more than 90°C, no more than 80°C, no more than 70°C, no more than 60°C, no more than 50°C, no more than 40°C, no more than 30°C and no more than 25°C.

[0056] The treatment is preferably performed at a temperature of at least 5°C or at least 10°C.

[0057] Preferably, the treatment is performed at a temperature of from 10 to 60°C.

[0058] Preferably, the treatment does not exceed a temperature of 50°C.

[0059] Preferably, the duration of the treatment is at least 1 second, more preferably at least 30 seconds, even more preferably at least 1 minute, especially at least 15 minutes and most especially at least 30 minutes.

[0060] Preferably, the duration of the treatment is no more than 5 hours, more preferably no more than 3 hours and even more preferably no more than 2 hours.

[0061] Attachment of the active agent to the surface polymer [0062] Preferably, the active agent is covalently bonded to the surface polymer via an amide group. The present inventors have found an amide group to be especially resistant to hydrolysis in an aqueous liquid medium. As a result, the active agent is able to stay covalently bonded to the surface polymer (and thereby to the treatment bodies) even after prolonged exposure to liquid media comprising water and so the activity from the active agent is retained after many re-uses of the treatment bodies.

[0063] Treatment bodies

[0064] Prior to the covalent bonding of the active agent to the surface polymer, the surface polymer preferably comprises one or more ester or carboxylic acid groups, more preferably one or more ester groups.

[0065] The surface polymer preferably is or comprises a poly(meth)acrylate. Suitable poly(meth)acrylates are obtained by polymerising or copolymerising monomers including: acrylic acid; methacrylic acid; methyl acrylate; methyl methacrylate; ethyl acrylate; ethyl methacrylate; propyl acrylate, propyl methacrylate, butyl acrylate; butyl methacrylate; tert- & sec- butyl methacrylate; benzyl methacrylate, 2-(dimethylamino)ethyl methacrylate, glycidyl methacrylate and combinations thereof.

[0066] More preferred surface polymers are obtained by copolymerising or polymerising a monomer composition comprising ethyl methacrylate.

[0067] A preferred surface polymer is or comprises the repeat units obtained from polymerising or copolymerising ethyl methacrylate.

[0068] Preferably, the treatment bodies are prepared by coating the interior material with the surface polymer. The coating can be performed once or it may be repeated several times, for example for 2, 3 or 4 times in total.

[0069] Preferably, the one or more treatment bodies are prepared by polymerising one or more monomers in the presence of the interior material.

[0070] Preferably, the coating is performed by polymerising or copolymerising monomers (especially the abovementioned (meth)acrylates) in the presence of the interior material and optionally a liquid medium. The liquid medium used during the polymerisation or copolymerisation preferably comprises a mixture of ethanol and water, preferably the weight ratio of the ethanol to water is from 10: 1 to 1 : 10, more preferably from 5: 1 to 1 :5 and most especially from 3: 1 to 1 :3.

[0071] Preferably, the polymerisation or copolymerisation described above is initiated using a free radical initiator which is more preferably a persulfate, which is preferably selected from potassium persulfate, sodium persulfate and ammonium persulfate. [0072] The polymerisation or copolymerisation is preferably performed in the presence of a thiosulfate. Thiosulfates have been found to be helpful in controlling and narrowing the polydispersity of the molecular weight distribution of the resulting polymer obtained by the polymerisation.

[0073] In order of increasing preference, the initiator is preferably present in the liquid medium at a concentration of at least 0.01 mM, at least 0.1 mM, at least 1 mM, at least 5mM, at least 10mM, at least 12mM, at least 14mM and at least 16mM.

[0074] In order of increasing preference, the initiator is preferably present in the liquid medium at a concentration of no more than 100mM, no more than 50mM, no more than 30mM and no more than 20mM.

[0075] Preferably, the initiator is present in the liquid medium at a concentration of from 0.1 to 50mM, especially from 1 to 30mM and more especially from 1 to 20mM.

[0076] The surface polymer, can be linear, branched, cross-linked or a mixture thereof.

[0077] The coating may also be performed by dissolving a polymer is in a suitable solvent, applying the solvent containing the polymer to the interior material and removing the solvent (e.g. by drying).

[0078] The interior material can be a non-polymeric material. Suitable non-polymeric materials include metals, alloys, ceramics and glass. Preferably, the interior material is or comprises a polymer, especially a polymer which is or comprises a polyamide, a polyalkylene, a polyurethane, a polyester or a mixture thereof.

[0079] The interior material preferably has no ester groups.

[0080] The interior material is preferably a metal, a metal alloy, a ceramic, glass, a polyamide, a polyalkylene or a mixture thereof. These materials were (prior to the present invention) more difficult to work with as they tended to be relatively inert. Preferably, the interior material is or comprises a polyamide or a polyalkylene or a combination thereof.

[0081] The interior material is preferably a polyamide, more preferably Nylon 6 or Nylon 6,6. The present inventors found it especially difficult to covalently bond active agents to a polyamide surface and the abovementioned surface polymer provides a more reactive surface to which the active agent can be covalently bonded.

[0082] When the interior material is a polymer it may be a thermoset but is more preferably a thermoplastic. The interior material may be prepared by extrusion, especially melt extrusion using interior material which is a thermoplastic. [0083] In a preferred embodiment, the one or more treatment bodies are or comprise a textile or a mesh. Preferably, the textile or mesh is flexible. Preferably, the textile or mesh is able to flex during the treatment.

[0084] Preferably the one or more treatment bodies do not in any way become permanently attached, affixed, integrated or associated with the substrate. To put this another way, the treatment bodies may be readily separated from the substrate at the end of the method according to the first aspect of the present invention.

[0085] Preferably, the treatment bodies comprise no borate, more preferably the treatment bodies comprise no boron compounds.

[0086] Solid Particles

[0087] In a further preferred embodiment, the one or more treatment bodies are solid particles.

[0088] Whilst the solid particles can be hollow, foamed or porous, they are preferably substantially non-porous.

[0089] In order of increasing preference, the solid particles preferably have a size of no more than 40mm, no more than 30mm, no more than 25mm, no more than 20mm, no more than 15mm or no more than 10mm.

[0090] In order of increasing preference, the solid particles preferably have a size of at least 2mm, at least 3mm or at least 4mm.

[0091] The solid particles preferably have a size of from 1 to 20mm, more preferably from 1 to 10mm.

[0092] The surface area of the solid particles is preferably from 10mm ² to 400mm ² , more preferably from 40 to 200mm ² and especially from 50 to 190mm ² .

[0093] The size is preferably an average size more preferably a number average size. The average is preferably taken from at least 100, at least 1000 or at least 10,000 solid particles.

[0094] The size is preferably the longest linear dimension of the solid particle. The method of measuring the particle size is preferably performed by using calipers or a particle size measurement using image analysis, especially dynamic image analysis. A preferred apparatus for dynamic image analysis is a Camsizer as provided by Retsch.

[0095] In order of increasing preference, the solid particles preferably have a density of at least 0.5g/cm ³ , at least 0.75g/cm ³ , at least 0.9g/cm ³ , at least 1.0 g/cm ³ , at least 1.1g/cm ³ , at least 1.2 g/cm ³ , at least 1.25 g/cm ³ , at least 1.30 g/cm ³ , at least 1.35 g/cm ³ , at least 1.40 g/cm ³ , at least 1.45 g/cm ³ , at least 1.50 g/cm ³ , at least 1.55 g/cm ³ , at least 1.60 g/cm ³ , at least 1.65 g/cm ³ , at least 1.70 g/cm ³ , at least 1.75 g/cm ³ , at least 1.80 g/cm ³ , at least 1.85 g/cm ³ or at least 1.90 g/cm ³ .

[0096] In order of increasing preference, the solid particles preferably have a density of no more than 10.0 g/cm ³ , no more than 8.0 g/cm ³ , no more than 6.0 g/cm ³ , no more than 4.0 g/cm ³ , no more than 3.0 g/cm ³ , no more than 2.5 g/cm ³ , no more than 2.2 g/cm ³ and especially no more than 2.0 g/cm ³ .

[0097] The density of the solid particle can be from 0.5 to 2.5 g/cm ³ , from 1.0 to 2.2 g/cm ³ or from 1.1 to 2.0 g/cm ³ .

[0098] Preferably, the solid particles are more dense than the liquid medium and especially more dense than water.

[0099] As described above, the interior material of the solid particles may be or comprise a polymeric material. In the case of solid particles in which the interior material is or comprises a polymeric material, a filler can be incorporated into said polymeric material. Thus, the interior material of the solid particle may be or comprise a polymeric material and a filler, which is preferably an inorganic filler.

[00100] The interior material of the solid particle can comprise at least 5, at least 10, at least 20, at least 30, at least 35, at least 40, at least 45 or at least 50wt% of filler, which is preferably an inorganic filler. In a preferred embodiment, the interior material of the solid particle comprises at least 20wt% filler, particularly where faster and/or more efficient separation of the solid particles from the substrate is desirable. The remainder of the interior material of the solid particle required to make 100wt% is preferably a polymeric material.

[00101] The interior material of the solid particle can comprise no more than 90wt%, no more than 80wt%, and no more than 70wt% of filler, which is preferably an inorganic filler. The remainder of the interior material of the solid particle required to make 100wt% is preferably a polymeric material.

[00102] Optionally, the interior material of the solid particle can comprise a polymeric material and up to 30wt% of a filler. Optionally, the interior material of the solid particle comprises a polymeric material and no filler (and in particular no inorganic filler). The solid interior material of the particle can consist (exclusively) of polymeric material.

[00103] The solid particle preferably has a mass of from about 1 mg to about 1000 mg, or from about 1 mg to about 700 mg, or from about 1 mg to about 500 mg, or from about 1 mg to about 300 mg. It is preferred that the solid particle has a mass of at least 10mg, more preferably 30mg and especially 50mg. [00104] Preferably, the solid particle has a shape which is ellipsoidal or spherical as these shapes tend to be kind to the substrate and they tend to separate from the substrate more readily.

[00105] Preferably, the solid particle(s) have an aspect ratio of no more than 1.5, more preferably no more than 1.4, especially no more than 1.3 and most especially no more than 1.2. The aspect ratio is the ratio of the longest linear dimension to the shortest linear dimension for each particle. Preferably the aspect ratio is an average, especially a number average. Preferably the average is of at least 100, more preferably at least 1000 and especially at least 10,000 solid particles.

[00106] It is preferred that the interior material has the same preferences as above described for the solid particles. In particular, the interior material has the same size, shape, density, surface area, porosity, mass and aspect ratio as the abovementioned solid particles. This arises because the surface polymer is typically a relatively thin layer which has little impact on these preferences.

[00107] When the one or more treatment bodies are in the form of solid particles it is preferred to use a plurality of solid particles. Typically, the treatment according to the first aspect of the present invention uses at least 100, more typically at least 1 ,000 and even more typically at least 10,000 solid particles.

[00108] In order of increasing preference, the weight ratio of the dry solid particles to the dry substrate is from 1 :5 to 100: 1 , from 1 :2 to 50: 1 , from 1 :1 to 30: 1 , from 1 : 1 to 20: 1 , from 1 : 1 to 10: 1 and from 2:1 to 10: 1.

[00109] Treatment

[00110] The treatment according to the first aspect of the present invention may be or comprise cleaning. Cleaning can be applied in laundering or dishwashing. Preferably, the treatment is or comprises laundering especially when the substrate is or comprises a textile, a fibre, a yarn, an animal hide or an animal skin, more especially a textile.

[00111] The treatment according to the first aspect of the present invention may be or comprise bleaching. Bleaching can be desirable for the removal or reduction of the appearance of stains and/or for fading or ageing the appearance of the substrate. Bleaching can be applied in laundering, dishwashing and substrate ageing (for example cotton or denim ageing).

[00112] Re-use

[00113] As mentioned above a significant advantage of the present invention is that the treatment bodies as described herein retain their activity for many re-use cycles. In particular, these treatment bodies maintain their effectiveness in cleaning and/or bleaching performance after many re-uses thereof.

[00114] Preferably, these one or more treatment bodies are re-used, more preferably re-used in subsequent methods which are preferably also according to the first aspect of the present invention. In order of increasing preference, the one or more treatment bodies are re-used for at least 1 , at least 2, at least 3, at least 4, at least 5, at least 6, at least 7, at least 8, at least 9, at least 10, at least 1 1 , at least 20, at least 30, at least 40, at least 50, at least 100, at least 200, at least 300, at least 400 and at least 500 treatments. Typically, the treatment bodies are not re-used for more than 10,000, more than 5,000 or more than 2,000 times.

[00115] Preferably, following the treatment, said one or more treatment bodies are separated from the substrate and these one or more treatment bodies are then re-used in one or more subsequent treatments, which are preferably also according to the first aspect of the present invention.

[00116] Preferably, the method according to the first aspect of the present invention additionally comprises the steps:

i. separating the substrate from the treatment bodies;

ii. re-using the one or more treatment bodies in the treatment method according to the first aspect of the present invention, preferably for the number of re-uses as mentioned above.

[00117] The preferences for the treatment method in step ii. are exactly as mentioned elsewhere in this invention.

[00118] Agitation

[00119] The agitation may be performed by shaking, oscillating, stirring, fluidizing, pulsing or more preferably by rotating (the composition).

[00120] Apparatus

[00121] Preferably, the agitation is performed within an apparatus comprising a treatment chamber. The treatment chamber may be shaken, oscillated, pulsed or more preferably rotated to provide the agitation. Of course, the composition is loaded into the treatment chamber prior to the agitation. The rotation may be at any suitable G force, however the preferred G force is from 0.05G to 2G, more preferably from 0.05G to 1.5G and especially from 0.05 to 0.95G. The G force is preferably calculated at the inner surface of the treatment chamber. The treatment chamber is preferably in the form of a drum or cylinder. The G force can be calculated by G=1.118x R x (RPM/1000) ² wherein R is the radius in millimeters and RPM is the rotation speed expressed in revolutions per minute. Apparatus wherein the treatment chamber is rotated are especially suitable for cleaning, laundering and ageing especially for textile substrates.

[00122] The apparatus may alternatively or additionally comprise one or more stirrers, fluidizing beds or jets configured so as to agitate the composition.

[00123] Optionally, agitation is performed in an apparatus configured such that it is able to provide a jet of the liquid medium directed so as to impinge upon the substrate. Optionally, the jet may comprise one or more treatment bodies which are especially in the form of solid particles. The apparatus may comprise one or more racks which are configured to hold the substrate(s) in place during the treatment. An apparatus of this kind is especially suitable as a dishwasher.

[00124] Liquid medium

[00125] The liquid medium is preferably aqueous. To put it another way, the liquid medium preferably is or comprises water.

[00126] Where water is used in conjunction with other liquids, these liquids may be organic liquids such as alcohols, esters, ethers, amides and the like.

[00127] In order of increasing preference, the liquid medium comprises at least 50wt%, at least 60wt%, at least 70wt%, at least 80wt%, at least 90wt%, at least 95wt% or at least 99wt% of water. Most preferably the liquid medium consists of water and no other liquid components.

[00128] Preferably, the pH of the liquid medium during the treatment is at least 7, more preferably at least 8, especially at least 9 and most especially at least 10.

[00129] Preferably, the pH of the liquid medium during the treatment is no more than 13, more preferably no more than 12 and especially no more than 11.

[00130] Preferably, the treatment comprises adding to the composition a detergent formulation which is able to provide the above preferred pH values in the liquid medium. Preferably, when the detergent formulation is added to the composition the liquid medium maintains the preferred pH values throughout the duration of the treatment. Preferably, the detergent formulation contains a buffer and/or a base. Preferably, the detergent formulation itself has the abovementioned pH values.

[00131] Preferably, the weight ratio of the liquid medium to the dry substrate is at least 1 :1 , more preferably at least 2: 1 and even more preferably at least 3:1.

[00132] Preferably, the weight ratio of the liquid medium to the dry substrate is no more than 100: 1 , more preferably no more than 50: 1 , especially no more than 20: 1 , more especially no more than 15: 1 and most especially no more than 10: 1. [00133] Optional components of the composition

[00134] The composition may additionally comprise solid particles which have not been functionalised in the way described hereinabove, i.e. solid particles which do not have covalently bonded thereto said active agent. Such optional solid particles are preferably independently selected from the materials described above for the solid particles which have been functionalised with said active agent. The optional particles preferably do not comprise said surface polymer layer or coating. The preferences described hereinabove for the properties of the functionalised solid particles (i.e. the treatment bodies of the present invention) otherwise also apply to said optional solid particles. Thus, said optional solid particles are suitably selected from said non-polymeric and said polymeric materials, and preferably from said polymeric materials, optionally comprising inorganic filler as described herein. Where a mixture of treatment bodies of the present invention and said optional solid particles is used, it is preferred that the amount of said treatment bodies of the present invention is at least 0.01wt%, preferably at least 0.1 wt%, preferably at least 1wt%, preferably at least 5wt%, preferably at least 10wt%, typically no more than 90wt%, or no more than 80wt%, or no more than 70wt%, or no more than 60wt%, or no more than 50wt%, or no more than 40wt%, or no more than 30wt%, by total combined weight of said treatment bodies and said optional solid particles. In this embodiment, the references herein to a plurality of solid particles, and to the weight ratio of dry solid particles to dry substrate, are applicable to the mixture of said treatment bodies of the present invention and said optional solid particles.

[00135] The composition may additionally optionally comprise one or more of the following: sequesterants, lubricants, anti-crease agents, pre-treatment agents, levelling agents, dispersants, antifoaming agents, desizing agents, mercerizing agents, optical brighteners, salts, buffers, biocides, acids, bases, surfactants, bleach catalysts, bleach activators, bleaching agents, enzymes and anti-redeposition agents.

[00136] Preferably, the composition additionally comprises a dispersant and/or surfactant.

[00137] When the treatment bodies comprise a bleaching catalyst as an active agent then preferably the composition is free from any bleach catalysts except for the bleaching catalyst which is covalently bonded to the surface polymer.

[00138] When the treatment bodies comprise a bleaching catalyst as an active agent then preferably, the liquid medium comprises no bleach catalyst, more preferably the liquid medium comprises no bleach catalyst and/or no bleach activators. The present inventors have found that the present invention works well without the use of e.g. detergent formulations which comprise bleach catalysts and/or bleach activators. [00139] Suitable bleach activators which are preferably absent from the liquid medium include Tetraacetylethylenediamine (TAED) and nonanoyloxybenzenesulfonate (NOBS) which is often in the form of the sodium salt.

[00140] Suitable bleach catalysts which are preferably absent from the liquid medium include those comprising transition metals, especially those comprising Manganese, Iron, Cobalt, Ruthenium and Molybdenum. More preferably, bleach catalysts comprising a transition metal in ligated form are preferably absent from the liquid medium.

[00141] Ligands which are also preferably absent from the liquid medium include triazacyclononane, saierv, saltrene- and ierpyridine containing compounds.

[00142] Preferably, the only bleaching catalyst in the composition is that present in the treatment bodies in the form of the previously described cyclic ligand.

[00143] When the treatment bodies comprise an antimicrobial agent as an active agent then preferably the composition is free from any antimicrobial agent except for that which is covalently bonded to the surface polymer. When the treatment bodies comprise an antimicrobial agent as an active agent then preferably the liquid medium comprises no antimicrobial agent, especially no cationic and/or phenolic antimicrobial agent.

[00144] Beaching agent

[00145] When the treatment bodies comprise a bleaching catalyst as the active agent then, the composition preferably comprises a bleaching agent. The bleaching agent is preferably one comprising a peroxide. The peroxide may be or comprise or generate hydrogen peroxide and/or an organic peroxide such as for example N,N- phthaloylaminoperoxycaproic acid (PAP). Typical bleaching agents comprise hydrogen peroxide, percarbonate and perborate.

[00146] In order of increasing preference the amount of bleaching agent in the composition is preferably at least 0.01 , at least 0.1 , at least 1 and at least 5g/L.

[00147] In order of increasing preference the amount of bleaching agent in the composition is preferably no more than 100, no more than 50, no more than 30, no more than 20 or no more than 10g/L.

[00148] Optional Method steps

[00149] The method according to the first aspect of the present invention may additionally comprise one or more of the following steps:

i) rinsing the substrate (for example any bleaching agents present on the substrate); ii) extracting the liquid medium;

iii) separating the substrate from the treatment bodies;

iv) drying the substrate;

v) ironing or pressing the substrate (especially wherein the substrate is a textile); vi) stitching, gluing, shape-forming and/or cutting the substrate, especially wherein the substrate is a textile;

vii) surface treating the substrate.

[00150] Treatment Bodies per se

[00151] According to a second aspect of the present invention there is provided a treatment body as defined in the first aspect of the present invention. The treatment body of the second aspect of the invention is as preferred and described hereinabove for the first aspect of this invention.

[00152] Method of preparing the treatment bodies

[00153] According to a third aspect of the present invention there is provided a method for preparing a treatment body as defined in the first aspect of the present invention or according to the second aspect of the present invention comprising covalently bonding a molecule comprising an active agent to the surface polymer immobilised on the surface of a treatment body.

[00154] The treatment bodies, interior material and surface polymer of the third aspect of the invention are as described and preferred hereinabove for the first aspect of this invention.

[00155] Preferably, the molecule (as mentioned above) is covalently bonded to a treatment body by a linking group which is or comprises an amide group. Preferably, a plurality of molecules are covalently bonded to each treatment body by a covalent bond which preferably is or comprises an amide group.

[00156] Preferably, the method according to the third aspect of the present invention is performed at a temperature of no more than 150°C, more preferably no more than 120°C, especially no more than 100°C and most especially no more than 90°C.

[00157] In order of increasing preference, the method according to the third aspect of the present invention is performed at a temperature of at least 20°C, at least 40°C, at least 50°C and at least 60°C.

[00158] The method according to the third aspect of the present invention is preferably performed at a temperature of from 60 to 90°C. [00159] Preferably, the molecule is covalently bonded to the surface polymer by reacting:

i. one or more first reactive groups selected from esters, carboxylic acids, carboxylic acid anhydrides, epoxides, isocyanates, aziridine, carbodiimide and oxetane groups with;

ii. one or more second reactive groups selected from amines, thiols and alcohols.

[00160] Preferably, the first reactive group is an ester, a carboxylic acid or a carboxylic acid anhydride, more preferably an ester (i.e. a carboxylic acid ester).

[00161] Preferably, the second reactive group is an amine which is preferably a primary or secondary amine.

[00162] The treatment body as defined in the first aspect or according to the second aspect of the present invention is preferably prepared by reacting asurface polymer having ester groups as the first reactive group with a molecule (as described above) having an amine group.

[00163] Preferably, the covalent bond is formed by the reaction between an ester group and an amine group.

[00164] When the active agent comprises a cyclic ligand as described above then, preferably, after the molecule is covalently bonded to the surface polymer the cyclic ligand within the molecule is alkylated, preferably methylated. The alkylation is preferably performed on the secondary amine groups within the cyclic ligand structure. The methylation is preferably performed using the Eschweiler-Clarke reaction. This reaction is performed in the presence of formic acid and formaldehyde.

[00165] A preferred method for preparing the treatment body comprises:

i. covalently bonding a molecule comprising an cyclic ligand having at least one nitrogen atom to the surface polymer;

ii. alkylating at least one of the nitrogen atoms in the cyclic ligand;

iii. optionally metalising the cyclic ligand.

[00166] The nitrogen atoms in the cyclic ligand which are alkylated preferably are comprised in the cyclic structure of the cyclic ligand, more preferably the nitrogen atoms are in the form of secondary amine group(s).

[00167] General [00168] Throughout the description and claims of this specification, the words "comprise" and "contain" and variations of them mean "including but not limited to", and they are not intended to (and do not) exclude other moieties, additives, components, integers or steps. Throughout the description and claims of this specification, the singular encompasses the plural unless the context otherwise requires. In particular, where the indefinite article is used, the specification is to be understood as contemplating plurality as well as singularity, unless the context requires otherwise. Thus, by example a cyclic ligand means one or more cyclic ligands and a substrate means one or more substrates.

[00169] Features, integers, characteristics, compounds, chemical moieties or groups described in conjunction with a particular aspect, embodiment or example of the invention are to be understood to be applicable to any other aspect, embodiment or example described herein unless incompatible therewith. All of the features disclosed in this specification (including any accompanying claims, abstract and drawings), and/or all of the steps of any method or process so disclosed, may be combined in any combination, except combinations where at least some of such features and/or steps are mutually exclusive. The invention is not restricted to the details of any foregoing embodiments. The invention extends to any novel one, or any novel combination, of the features disclosed in this specification (including any accompanying claims, abstract and drawings), or to any novel one, or any novel combination, of the steps of any method or process so disclosed.

[00170] The present invention will now be illustrated by reference to the following examples, without in any way limiting its scope.

[00171] Examples

[00172] Preparation of the Treatment Bodies having an active agent which is a bleaching catalyst

[00173] Interior material (designated IM1) in the form of polyamide particles was prepared by hot melt extrusion of a polyamide and an inorganic filler in the form of barium sulfate. The interior material which resulted was ellipsoidal in shape and had a particle size of around 4 mm. A three step synthesis route was used to prepare the treatment bodies as follows. The Fourier Transform Infra-Red spectrograph of the surface of the interior material (IM1) was measured and was as shown in Fig 1a.

[00174] Step 1 : Coating the interior material with a surface polymer

[00175] In step 1 the interior material was coated with a surface polymer by polymerising ethyl methacrylate which immobilised the surface polymer on the surface of the interior material. [00176] In step 1 deionised water (2.5 ml_), absolute ethanol (2.5 ml_) and the Interior Material (IM1) in the form of polyamide particles (2.5 g) were charged to a Schlenk flask. The flask was purged with argon, the contents of the flask were held at a temperature of 50°C for 30 mins and were then allowed to cool to room temperature for a further 20 mins. Copper acetate monohydrate (0.002 g, 0.004 %w/v) was added to the flask followed by potassium persulfate (21.6 mg, 0.1 mmol, 0.016M), sodium thiosulfate (12.6 mg, 0.1 mmol, 0.016M) and ethyl methacrylate (0.2853 g, 2.5 mmol, 0.5M). The flask was immersed in an oil bath and maintained at a temperature of 70°C. The contents of the flask were stirred at 1330 rpm for 1 hour. The resulting polymerisation reaction formed a surface polymer which coated the polyamide particles. The particles were then cooled, filtered and washed with acetone and transferred to a sealed vial containing 2-butanone. The vial was then rolled on tube rollers for 16 hours during which time the 2-butanone was removed and replaced with fresh 2-butanone every 4 hours. The particles were subsequently filtered and dried at 40°C overnight.

[00177] A Fourier Transform Infra-red (FTIR) spectrograph of the surface of the particles resulting from step 1 was taken. This was as shown in Figure 1 b. The FTIR shows an absorption band in the region of 1735 to 1750 cm ^-1 which corresponds to the ester group in poly ethyl methacrylate. This band is not seen in the initial polyamide particles forming the interior material (Fig 1a) prior to the surface coating step and hence the presence of these bands evidences the effectiveness of the coating step.

[00178] Step 2: Covalent bonding of the cyclic ligand (Bleaching catalyst)

[00179] In step 2 a molecule comprising a cyclic ligand was covalently bonded to the surface coated particles prepared in step 1.

[00180] In a 250 ml first round-bottomed flask 53 ml of sulphuric acid was stirred with 9.5 ml of deionised water. To this 50 g of a 0.085 mol of tri-tosylated 1 ,4,7-triazacyclononane (TS3-TACN) was added portion-wise at a temperature of 140 °C and stirred for a period of 6 hour.

[00181] In a separate second flask, 154 g of 50 % NaOH and 62.5 ml of water was stirred at a temperature of at 0 °C. The contents of the first round-bottomed flask were added to the second flask dropwise over a period of 45 min or until the contents of the second flask reached a pH of 7. The particles resulting from step 1 were added to the second flask and the resulting mixture was stirred and heated to 90°C for a period of 6 hours. The resulting particles were designated Treatment Bodies TB1.

[00182] Step 3: Methylation of the amine groups in the cycling ligand. [00183] Following this, the mixture in the second flask was cooled to 0 °C and 112.5 ml of 37 % formaldehyde solution and 1 12.5 ml of 88 % Formic acid were added sequentially. The mixture was heated to 90°C for 9 hours. At this stage the amount of CO2 released was observed, as this was an indication of the methylation of the amine groups. The mixture was then cooled and the resulting treatment bodies were filtered, washed with hexane and dried at 60 °C. This prepared Treatment Bodies - TB2 in the form of solid particles.

[00184] Example 1 : Re-usable treatment bodies

[00185] Tea-stained swatches having the dimensions 4cm by 4cm were used in the examples. The tea-stained swatches were purchased from Center for Testmaterials B.V. The swatches were made from cotton.

[00186] 36 particles of the Treatment Bodies TB2 as prepared above were placed into a jar along with 0.75g of sodium percarbonate (SPC), one tea stained swatch and water 50g. The jar and its contents were rolled for a period of 15 minutes at a temperature of 20°C. After this bleaching cycle, the bleached tea-stained swatches were removed from the jar, washed with cold water and then allowed to dry. The particles of the Treatment Bodies were recovered and re-used as indicated below.

[00187] Using the same TB2 particles (re-used) the bleaching cycle was repeated with fresh water, fresh SPC and a fresh tea-stained swatch a further 8 times.

[00188] Comparative Example 1

[00189] Comparative Example 1 was a repeat of Example 1 where everything was identical to Example 1 except that in place of Treatment Bodies TB1 the interior material (IM1 as defined above) was used. Of course, IM1 was a material which contained no cyclic ligands.

[00190] Measurement method

[00191] The bleaching of the tea stain on the swatch was quantified spectrophotometrically using a Konica Minolta CM-3600A spectrophotometer fitted with a D65 light source and using SpectraMagic NX Colour Data Software CM-S100w, Professional/Lite Ver2.2. The L*, a* and b* CIE colour space values were recorded at four different points on the tea stained area and the values recorded were the average of those four measurements. The delta E* values were calculated using Equation 1 :

[00192] Delta E*= [ (L* ₂ -L*i) ² + (a* ₂ -a*i) ² + (b* ₂ -b*i) ² ] ^{1 2} Equation 1

[00193] wherein L*i , a*i and b*i values are taken from the average colour space measurements of the tea-stained (initial swatch prior to bleaching) and L* ₂ , a* ₂ and b* ₂ are taken from the average colour space measurements of a bleached tea stained swatch. [00194] Results

[00195] Table 1 shows the results of the Delta E* from the tea stained swatches for each bleaching cycle. In this table the 2 ^nd , 3 ^rd and 4 ^th etc. bleaching cycles correspond to the 2 ^nd , 3 ^rd and 4 ^th etc. re-uses of the treatment bodies (TB1) or Interior material (IM1).

Table 1 : Delta E* obtained from bleached tea-stained swatches.

[00196] In Table 1 a larger Delta E* value corresponds to a stronger bleaching effect and a better reduction of the appearance of the tea stain. The bleaching effect was demonstrated by the higher values for Example 1 than for Comparative Example 1 across all of the 9 bleaching cycles. This evidenced that the bleaching effectiveness was retained over many re-use cycles. It was also noted that the advantage of Example 1 was evident even though the cyclic ligand had not been metallised prior to the first treatment. It was also noted that the difference between Example 1 and Comparative Example 1 increased as the treatment bodies were used in more and more bleaching cycles. Whilst not wishing to be limited by any theory it was hypothesized that this was observed because the cyclic ligand was slowly adsorbing traces of metals from the substrate and/or from the stain materials which improved the effectiveness as a bleaching catalysts with each bleaching cycle.

[00197] Example 2

[00198] Example 2 was the same as Example 1 except that only 12 particles of the Treatment Bodies TB2 were used and only the first bleaching cycle was performed on the tea-stained swatches. [00199] Example 3

[00200] Example 3 was the same as Example 2 except that in place of Treatment Bodies TB2 Treatment Bodies TB1 were used. That is to say that the cyclic ligand in the treatment bodies was not methylated (as per step 3).

[00201] Comparative Example 2

[00202] Comparative Example 2 was the same as Example 2 except that 12 particles of the Interior Material (IM1) were used in place of Treatment Bodies TB2.

[00203] Results

[00204] Table 2: Bleaching efficacy of methylated and non-methylated cyclic ligands in the Treatment Bodies.

[00205] In Table 2 higher delta E* values correspond to better bleaching and to a better reduction in the appearance of the tea stain. In Table 2 it was clearly evidenced that the treatment bodies of the present invention provided superior bleaching performance.

[00206] Similar results were obtained in the same example as Example 2 wherein smaller amounts (0.15g) of SPC were used and larger numbers of TB2 particles (72) were used. Thus, the present invention was seen to be effective over a range of bleaching agent concentrations.

[00207] Preparation of Manganese-metalized cyclic ligands

[00208] 72 particles of the treatment bodies TB2 were metalised prior to the treatment using a source of manganese namely (manganese (II) acetate). This was achieved by adding 10mg of manganese (II) acetate in water (5ml) to 72 treatment particles. The particles were then stirred for 2 hours at ambient temperature. The resulting particles were then rinsed with water. This prepared treatment bodies Mn-TB2.

[00209] Preparation of Iron-metalized cyclic ligands

[00210] 72 particles of treatment bodies TB2 were metalised prior to the treatment using a source of iron namely (iron (II) sulfate). This was achieved by adding 10mg of iron (II) sulfate in water (5ml) to 72 treatment particles. The particles were then stirred for 2 hours at ambient temperature. The resulting particles were then rinsed with water. This prepared treatment bodies Fe-TB2. [00211] 72 particles of treatment bodies TB2 as prepared in Steps 1-3 above were prepared by simply preparing 36 particles and then a further 36 particles.

[00212] 72 particles of Interior Material (IM 1) were prepared as a control.

[00213] Using the Mn-TB2, Fe-TB2, TB2 and IM1 particles the bleaching performance was assessed.

[00214] Examples 4 to 6 and Comparative Example 3

[00215] As before, tea-stained swatches having the dimensions 4cm by 4cm were used in the examples.

[00216] 72 particles of each of the particles (Mn-TB2 - Example 4, Fe-TB2 - Example 5, TB2 - Example 6 and IM1 - Comparative Example 3) as prepared above were placed into a jar along with 0.75g of sodium percarbonate (SPC), one tea-stained swatch and water 50g. The jar and its contents were rolled for a period of 15 minutes at a temperature of 20°C. After this bleaching cycle, the bleached tea-stained swatches were removed from the jar, washed with cold water and then allowed to dry.

[00217] The abovementioned spectroscopic measurement method was used on the bleached tea-stained swatches to assess the bleaching performance.

[00218] Table 3: Bleaching efficacy for pre-metalised treatment bodies at 20°C

[00219] In Table 3 higher delta E* values correspond to better bleaching and to a better reduction in the appearance of the tea stain. In Table 3 it was clearly evidenced that the all the Examples were superior in bleaching tea stains than the Comparative Example. In addition, the pre-metalisation was seen to even further improve the bleaching performance both with iron and manganese.

[00220] Example 7, 8 and Comparative Example 4

[00221] Example 7 was a repeat of Example 4 using the Mn-TB2 particles, Example 8 was a repeat of Example 5 using the Fe-TB2 particles and Comparative Example 4 was a repeat of Comparative Example 3 using IM1 particles. The examples were exactly the same except that the bleaching process was performed at a temperature of 40°C rather than 20°C. [00222] Table 4: Bleaching efficacy for pre-metalised treatment bodies at 40°C

[00223] In Table 4 higher delta E* values correspond to better bleaching and to a better reduction in the appearance of the tea stain. In Table 4 it was clearly evidenced that the all the Examples were superior in bleaching tea stains than the Comparative Example at a temperature of 40°C.

[00224] The above examples clearly evidenced the re-usability, the improved bleaching performance, the benefits of methylation of the cyclic ligand amine groups and the successful application to both cool (20°C) and warm (40°C) bleaching temperatures.

[00225] Preparation of Treatment bodies having active agents which are antimicrobial

[00226] Step 1 Coating of the Interior material

[00227] In step 1 deionised water (2.5 ml_), absolute ethanol (2.5 ml_) and the Interior Material (IM1) in the form of polyamide particles (2.5 g) were charged to a Schlenk flask. The flask was purged with argon, the contents of the flask were held at a temperature of 50°C for 30 mins and were then allowed to cool to room temperature for a further 20 mins. Copper acetate monohydrate (0.002 g, 0.004 %w/v) was added to the flask followed by potassium persulfate (21.6 mg, 0.1 mmol, 0.016M), sodium thiosulfate (12.6 mg, 0.1 mmol, 0.016M) and ethyl methacrylate (0.2853 g, 2.5 mmol, 0.5M). The flask was immersed in an oil bath and maintained at a temperature of 70°C. The contents of the flask were stirred at 1330 rpm for 1 hour. The resulting polymerisation reaction formed a surface polymer which coated the polyamide particles. The particles were then cooled, filtered and washed with acetone and transferred to a sealed vial containing 2-butanone. The vial was then rolled on tube rollers for 16 hours during which time the 2-butanone was removed and replaced with fresh 2-butanone every 4 hours. The particles were subsequently filtered and dried at 40°C overnight.

[00228] Step 2: Covalent bonding of an antimicrobial agent

62.58g of the particles prepared in Step 1 above were placed into a round bottomed flask along with 50 ml of ethanol and 3.09g 3-(Dimethylamino)-1 -propylamine (DMAPA). The contents of the flask were warmed to 60°C and held at that temperature for a period of 6 hours. The resulting particles were filtered, washed with water, dried and weighed.

[00229] Step 3: Quaternization

[00230] In a flask 200 of the particles from Step 2, were stirred in 50ml ethanol with 0.398g of benzyl bromide at a temperature of 60°C for a period of 14 hours. The resulting particles were filtered, washed with water, dried and weighed. This prepared Treatment bodies TB3 having an antimicrobial active.

[00231] Antimicrobial activity - Example 9 and Comparative Example 5

[00232] Method:

[00233] Test organism inocula were prepared to give approximately 10 ⁶ cfu/ml. Approximately 10g of particles were prepared for each sample type. To these were added sufficient inoculum to completely saturate the particles. Any excess liquid was drawn off. The inoculated particles were stored at 24°C±1 °C for 1 day of culturing. After 1 day of culturing particles plus liquid equating to 1 ml of the inoculum were removed and diluted with 9mls of water and allowed to stand for 30 minutes to allow resuspension of the test organisms. The samples were then shaken vigorously. The resulting suspensions were tested using a standard plate count method in Tryptone Soya Agar (TSA). Incubation was at 31 °C±1 °C for 5 days.

[00234] Test organisms:

[00235] The follow test organisms were used.

[00236] Pseudomona aeruginosa ATCC15442, Escherichia coli ATCC10536, Staphylococcus aureus ATCC6538, Enterococcus hirae NCIMB 8191 and Klebsiella pneumoniae NC09633.

[00237] Results:

[00238] Table 5: TSA Incubation results

[00239] Table 5 shows the results of the TSA incubation tests. Smaller numbers correspond to fewer bacterial colonies and therefore to better antimicrobial action. The results in Table 5 showed that the treatment bodies used in the method of the present invention provide a powerful and broad range antimicrobial action.