GB2433510A

GB2433510A - A composition for use in the treatment of a surface.

Info

Publication number: GB2433510A
Application number: GB0625777A
Authority: GB
Inventors: Thomas David Evans; Timothy Mark Howe
Original assignee: ENDUROCIDE Ltd
Current assignee: ENDUROCIDE Ltd
Priority date: 2005-12-23
Filing date: 2006-12-22
Publication date: 2007-06-27
Also published as: WO2007072050A1; GB0625777D0; GB0526292D0

Abstract

A composition for use in treating a surface, comprising an active agent and at least one polyorganosiloxane polymer having a formula A: T1R1R2SiO(R3R4SiO)r(R5T2SiO)sSiR6R7T3 wherein, the symbols R1, R2, R3, R4, R5, R6 and R7, which are identical or different, represent a phenyl or a C1 to C6 alkyl radical, and the symbol T1, T2 and T3, which are identical or different, represent a phenyl or a C1 to C6 alkyl radical, or an akyl radical of the formula: ```-R8-O-R9-X wherein, the symbols R8 and R9, which are identical or different, represent a C1 to C6 alkyl radical, and the symbol X represent a primary alcohol, or a quaternary amine of the formula: -N(R10R11R12 )+Z- wherein, the symbols R10, R11 and R12, which are identical or different, represent a C1 to C19 alkyl or alkylene group, linear or branched chain, Z represent an acetate anion. The active agent in the composition can be a biocide, anti-microbial, bactericidal, fungicidal, germicidal, yeasticidal, moldicidal, algicidal or a virucidal agent. The active agent can be contained in a non-volatile carrier. The composition can comprise a surfactant.

Description

I

* A COMPOSITION FOR USE IN THE TREATMENT OF A SURFACE The present invention relates to a composition for use in the treatment of a surface, and particularly to a polymer composition and a process for use in disinfecting a surface or the like.

In certain environments, it is often required to disinfect surfaces, implements or the like. In the food industry, for example in food preparation and processing plants and restaurants, considerable time and effort is spent in disinfecting areas and surfaces for preparation of food products to prevent cross contamination from such areas or surfaces into the food products. Likewise, in other industrial or medical environments, for example in hospitals, it is particularly important to disinfect working surfaces and instruments so that medical operations and patient care can be carried out in a sufficiently sterile environment. In commercial or domestic environments, for example in offices or kitchens, it is equally important to be able to clean and disinfect suitable surfaces. Many compositions or reagents are known which contain active ingredients for disinfecting surfaces. However, many of these compositions may be difficult to prepare or use due to toxicity considerations or difficulty of application. Further, and more particularly, after disinfection of the treated surfaces, the surfaces are susceptible to recontamination.

US-B-6,465,409 discloses an aqueous composition comprising a biocidal agent and a polyorganosiloxane containing water-soluble or water-dispersible polyether groups. The composition is used for disinfecting hard surfaces, such as floors, walls and work surfaces. However, after the composition has been applied to a surface the biocidal agent can only be released in a controlled manner when the surface is treated with an aqueous medium, typically water. This is a major disadvantage because bacteria or other micro organisms present on the surface can only be killed when the biocidal agent is released from the composition on the surface and this only occurs when the surface is made wet. Consequently, bacteria and germs can accumulate on surfaces treated with the composition over time and after the surface has been washed. This means that if the surface has not been washed for some time and it is used, for example, to prepare a food product or to conduct a medical operation in which it is important to have a disinfected surface, a substantial amount of bacteria or germs may be present on the surface leading to cross contamination.

Furthermore, the amount of biocidal agent that may be released from the composition is limited to the volume of the aqueous medium in contact with it. If a sufficient amount of water is not used to clean a surface, an insufficient amount of biocidal agent may be released meaning that all of the micro organisms present on the surface may not be killed. A further disadvantage is that the entire surface must be cleaned with water in order to release the biocidal agent to disinfect the overall surface.

GB-A-2,338,65 1 discloses a liquid polymer composition comprising polydimethylsiloxane and its use in treating surfaces, such as glass. The composition may be applied to a surface, where it bonds to the surface and may kill micro organisms present on the surface when the composition is dry.

However, this composition relies on acid-etching of the surface prior to bonding and therefore may be difficult to apply and damaging, if contacted, by the user.

Furthermore, the composition needs to be wet in order to be active.

There has now been developed an improved composition for use in disinfecting surfaces, implements or the like which has a substantially long lasting effect and addresses the above mentioned problems.

According to an aspect of the invention, there is provided a composition for use in treating a surface, comprising at least one polyorganosiloxane polymer having the formula A: T' R' R2SiO(R3R4SiO)(R5T2Sio)siR6R7T3 wherein, the symbols R', R2, R3, R4, R5, R6 and R7, which are identical or different, represent a phenyl or a C1 to C6 alkyl radical, and the symbols TI, T2 and T3, which are identical or different, represent a phenyl or a C, to C6 alkyl radical, or an alkyl radical of the formula: -R8-O-R9-.X wherein, the symbols R8 and R9, which are identical or different, represent a Ci to C6 alkyl radical, and the symbol X represents a primary alcohol, or a quatemary amine of the formula: -N(R' R' R'2)Z wherein, the symbols R' , R' , R'2, which are identical or different, represent a C, to C,9 alkyl or alkylene group, linear or branched chain, z represents an acetate anion; r is an average value ranging from I to 500; s is an average value ranging from 1 to 10; and an active agent.

Formula A may be further defined in that the C, to C6 alkyl radical of at least one of the R8 or R9 groups contains at least one secondary alcohol group.

Formula A may be further defined in that R8 comprises.(CH2)3-.

Formula A may be further defined in that R9 comprises -CH2CHOHCH2-.

Formula A may be further defined in that X represents at least one primary alcohol group.

Formula A may be further defined in that X represents at least one quatemary amine group.

Formula A may be further defined in that X represents a quaternary amine group of the formula: -N(Me2Y)Z * wherein, the symbol Y represents a C11 to C13 alkyl radical; the symbol Z represents an acetate anion.

Formula A may be further defined in that T2 comprises -(CH2)3N1-12.

Formula A may be further defined in that at least one of T' or T3 is a Methyl group.

Formula A may be further defined in that r has a value ranging from I to 300, preferably ranging from I to 200 and more preferably 1 to 80.

In one embodiment r represents a value of 80.

Formula A may be further defined in that s represents a value ranging from I to 10, preferably ranging from I to 5.

Formula A may be defined as: W-CH2CHOHCH2-O-(CH2)3-(SIMe2O-)r-(MeSiO-[CH2]3-O-CH2CHOHCH2W)sSiMe2(C112) yOCH2CHOHCH2W wherein, the symbol W occurs in the molecule at least four times, and is defined by at least two hydroxyl groups and at least two amine groups of the formula: -N(Me2Y)Z wherein, the symbol Y represents a C11 to C13 alkyl radical; the symbol Z represents an acetate anion, and r is an average value ranging from I to 200; s is an average value ranging from 2 to 5.

For example in one embodiment, hereinafter referred to as Polymer 1, Formula A can take the form: * Z(C1 CH2CHOHCH2OH)2-SiMe2(CH2)3-O-CH2CHOHCH2-N(Me2C13)Z The reason for having a large r value such as 80 (shown above) is to prevent steric hindrance which may be caused by the large quaternary amines. Accordingly, s has a small value such as 2 (shown above) which also prevents steric hindrance.

The terminal quaternary amine groups are attached to the siloxane backbone with the aid of linking ether groups, such as ROR (-CH2CHOHCH2-O-(CH2)3-) because the quaternary amine groups in themselves are too large to attach to the siloxane backbone directly. Once again this form of structure prevents steric hindrance, thereby providing stability to the overall structure.

Formula A may be defined as: Me3Si-O-(Me2Si-O-)r-(MeSIR-O-)s-SjMe3 wherein, the symbol R represents an alkyl amine of the formula: -(CH2)3-NI-12 and, r is an average value ranging from 1 to 500; s is an average value ranging from I to 10.

For example in this embodiment Formula A, hereinafter referred to as Polymer 2, may take the form: Me3Si-O-(Me2Si-O-)300-(MeSi[-(CH2)3NH2J-O-)6-SjMe3 In this form r has a value of 300 and s has a value of 6. This form of Formula A effectively defines a second polymer which may be used in combination with a first polymer described earlier.

The repeating units within the polymer chain may be partly, predominantly or completely defined by dimethylsiloxane.

The active agent may be selected from the group consisting of a biocidal, anti-microbial, bactericidal, flingicidal, germicidal, yeasticidal, moldicidal, algicidal and virucidal agent.

A composition formed in accordance with the present invention may be incorporated into a functional material or article.

According to a further aspect of the invention, there is provided a process for use in treating a surface, comprising applying an effective amount of a composition comprising one or more polyorganosiloxane polymers formed according to the present invention and an active agent to the surface.

According to another aspect of the invention, there is provided an article treated with a composition as described herein and an active agent.

According to another aspect of the invention there is provided a composition for use in treating a surface, comprising at least two different polyorganosiloxane polymers.

The polyorganosiloxane (which may comprise one polymer type or a blend of two or more polymer types) may be present in the composition in an amount of 5% to 95% by weight based on the weight of the composition. It is preferred that the polyorganosiloxane is present in an amount of from 10% to 50% and particularly preferred from 30% to 40% by weight based on the weight of the composition.

The composition may comprise a blend of between 5 to 95% of each polymer.

The active agent may be contained in a non-volatile carrier.

The active agent of the composition of the invention may be selected from the group consisting of a biocidal, anti-microbial, bactericidal, fungicidal, germicidal, yeasticidal, moldicidal, algicidal and virucidal agent. The active agent or combination of agents selected may depend on the polymer composition used and on the intended use of the composition, in particular may be based on the type of micro organism that is required to be killed by treatment of the surface or implement with the composition of the invention.

The active agent may comprise one or more biocidal agents.

The biocidal agent may be selected from cationic, amphoteric, amino, phenolic and halogen containing biocides. Examples of the biocides which may be used include: Cation.ic biocides such as quatemary monoammonium salts, for example Cocoalkylbenzyldimethylammortium, C12 - C14 alkylbenzyldimethylammonium, cocoalkyldichlorobenzyldimethylammonium, tetradecylbenzyldimethylammonium, didecyldimethylammonium and 1 5 dioctyldimethylammonium chlorides, Myristy1trimethy1amnonJuin and cetyltrimethylammonium bromides, Monoquatemary heterocyclic amine salts such as laurylpyridinium, cetylpyridinium and C12 -C14 alkylbenzyldimethylammonium chlorides, Triphenyiphosphonium fatty alkyl salts such as myristyltriphenylphosphonium bromide; Polymeric biocides such as those derived from the reactions Of epichiorohydrin and dimethylamine or diethylamine, Of epichiorohydrin and imidazole, Of I, 3-dichloro-2-propanol and dimethylamine, Of 1, 3-dichloro-2-propanol and 1, 3-bis (dimethylamino)-2-propanol, Of ethylene dichioride and I, 3-bis(dimethylamino)-2-propanol, Of bis (2-chioroethyl) ether and of N, N'-bis (dimethylaminopropyl)urea or -thiourea, Biguanidinc polymer hydrochiorides.

Amphoteric biocides such as derivatives of N-(N'-C8 -C13 alkyl-3-aminopropyl)glycine, of N-(N'-(N"-. C8 -C alkyl-2-aminoethyl)-2-aminoethyl) * glycine, of N,N-bis(N'-C8 -C18 alkyl-2-aminoethyl)glycine, such as (dodecyle) (aminopropyl) glycine and (dodecyl) (diethylenediamine) glycine; Amines such as N-(3-aminopropyl)-N-dodecyl-1,3-propanediamine; Phenolic biocides such as para-chloro-meta-xylenol, dichioro-meta-xylenol, phenol, cresols, resorcinoJ, resorcinol monoacetate, and their derivatives or watersoluble salts; Halogenated biocides such as iodophores and hypochiorite salts, for example sodium dichioroisocyanurate; S-chloro-2-methyl-4-isothiazolin.3-one; and 2-methyl-4-isothiazolin-3-one.

The active agent may be contained in a non volatile carrier. The non-volatile carrier may be water, a glycol, an ester derivative of a glycol or an ether derivative of a glycol. In particular, alkylene glycols and poly alkylene glycols such as diethylene glycol and polyethylene glycol may be used. Alternatively, the carrier may be an alcohol having from 3 to 30 carbon atoms, preferably at least 10 carbon atoms.

The active agent in the composition may be present in an amount of from 0.1% to 20% by weight based on the weight of the composition. It is particularly preferred that the active agent is present in an amount of from 0.2% to 11% by weight based on the weight of the composition.

The active agent may comprise one or a combination of Bac 50,DDQ 50, SPX and MBS.

The polyorganosiloxane and the active agent may represent the main ingredients of the composition of the invention. The composition may further comprise other ingredients, such as surfactants, chelating agents (such as aminocarboxylates, (ethylenediaminetetra-acetates, nitrilotriacetates, N,N-bis(carboxymethyl)-glutamates, citrates), alcohols (ethanol, isopropanol, glycols) detergency adjuvants (phosphates, silicates), dyes, and fragrances.

The composition may further comprise a surfactant. The surfactants which may be present in the composition of the invention may include: non-ionic surfactants such as ethylene oxide/propylene oxide block polymers, polyethoxylated sorbitan esters, fatty esters of sorbitan, ethoxylated fatty esters (containing from I to 25 units of ethylene oxide) polyethoxylated C8 -C22 alcohols (containing from 1 to 25 units of ethylene oxide), polyethoxylated C6 -C22 alkyiphenols (containing from 5 to 25 units of ethylene oxide), alkylpolyglycosides, amine oxides (such as C10 -C18 alkyldimethylamine oxides, C8 -C22 alkoxyethyldihydroxyethylamine oxides) amphoteric or zwitterionic surfactants such as C6 -C20 alkylamphoacetates or amphodiacetates (such as cocoamphoacetates), C10 C8 alkyldimethylbetaines, C10 -C alkylamidopropyldimethylbetaines, C10 -C18 alkyldimethylsuiphobetaines, C10 -C,8 alkylamidopropyldimethylsuiphobetaines.

The composition may be in the form of an aqueous composition.

Advantageously, the polyorganosiloxane acts as a carrier to introduce the active agent to the surface, implement or the like to be treated by the composition of the invention. The amino and/or polyether functions on the polyorganosiloxane allow adhesion to the treated surface by preferentially interacting with the biocidal agents and the surface.

The composition of the invention provides disinfection of surfaces for a considerable time after application and will remain active after washing and/or abrading (polishing). This is advantageous over conventional biocides which quickly lose their efficacy after application particularly when the treated surface is washed or abraded.

The composition may be applied to a surface or implement, for example a floor, wall or medical instrument, in the form of a coating and the polymer assists in adhering the active agent to the surface or the implement. The biocides in the composition of the invention are held to the treated surface by a polymer which is based on a polyorganosiloxane. This prevents the biocides from leaving the surface during washing or when abraded.

The composition of the invention may advantageously be incorporated into other materials. Such materials may include coatings such as paints and varnishes, which may be oil based or water soluble, The composition may also be incorporated into settable or curable compositions such as fillers, grouts, adhesives, mastics, putties and other materials which form a solid matrix over a period of time. Such prior art compositions are prone to the growth of mould and fungus, particularly in damp environments such as bathrooms and kitchens.

The composition of the invention may also be incorporated into plastics materials which may then be used to manufacture food processing implements, work surfaces, packaging materials, containers, and furniture for bathrooms, kitchens, hospitals and the like. Alternatively the composition may be impregnated or otherwise incorporated into a fabric or textile.

When the composition is applied to a surface or instrument, it may form a coating layer thereon which contains one or more active agents, preferably biocidal agents, so that any micro organisms present on or subsequently contacting the surface or instrument are killed. If the composition further comprises a surfactant, this may enhance the spreading ability of the composition over substantially the entire surface whilst imparting cleaning and detergent properties to the composition.

The composition is effective at killing micro organisms under dry or wet conditions.

The composition of the invention may be used to disinfect any suitable surface or implement, for example floors, walls, work surfaces, kitchen utensils, surgical instruments and the like. Advantageously, the composition may be used in different environments, that is in the medical or health care industry, for example in hospitals, in the food industry, for example in manufacturing plants and restaurants, in the commercial environment, for example in offices, and in the domestic environment, for example in kitchens and bathrooms.

The composition may be used to treat different surfaces, such as, for example, those made from ceramic, glass, pvc, formica or other polymeric materials, stainless steel, aluminium and wood.

The composition may be diluted before applying it to a surface or implement, such as by ito 100 fold or ito 1000 fold.

The composition may be effective at controlling the proliferation and/or elimination of many types of micro organisms, including gram-positive and gram-negative bacteria, such as: Bacillus cereus, Bacillus subtilis, Brevibacterium ammoniagenes, Brucella abortus, Klebsiella pneumonia, Lactobacillus casei, Proteus vulgaris, Listeria monocytogenes, Pseudomonas aeruginosa, Salmonella gallinarum, Salmonella typhosa, Staphylococcus aureus, Steptococcus faecalis, Flavobacterium species, Bacillus species, Escherichia species, Aeromonas species, Anchromobacter species and Alcaligenes species, fimgi such as: Cephalosporium species, Cladosporium species, Fusarium species, Paecilomyces species, Penicillium species, Streptomyces species, Trichophyton interdigitale, Chaetorarium globesom, Aspergillus niger, and Ceniphora puteana, Cornyebacterium species, Proteus penneri, Enterobacter aerogenes, Salmonella enteritidis; yeasts such as Monilia albicans and Saccharomyces cerevisiae, Candida albicans; algae such as Chlorella pyrenoidosa Chiorella vulgaris, Nostoc commune, Scenedesmus vacuolatus; and Anabaena cylindrical; and moulds such as Epidermophyton floccosum, Microsporum canis, Tricophyton mentagrophytes and Candida albicans.

Embodiments of the present invention will now be described by way of non-limiting example only: A. Biocidal activity of this solution was tested according to the standard suspension test prEN 13713 under the following conditions Diluent water Test strain Pseudomonas aeruginosa Staphylococcus aureus Enterococcus hirae Escherichia coli Temperature 20 degree C Contact time 5 minutes Interfering substance Dehydrated yeast and bovine serum albumin (10%) Neutralizing agent Lecithin 0.3%, polysorbate 80 (3%), sodium thiosuiphate (0.5%), L-histidine (0.1%) saponine (3%) in diluent Results Log 5 reduction in all bacteria at dilution of I in 20.

B. Demonstration of the residuality of the biocide.

The formulation was prepared by measuring the required volume of the biocides with a pipette and adding them to a lOOmI volumetric flask. The volume of polymer required was also measured and added.

The formulation was prepared according to the following recipe: Raw Material 1 8.0 % (1.5 % active 3:1 CIT:MIIT) Raw Material 2 20 % (50 % active Quaternary alkylbenzyl dimethylammonium chloride) Raw Material 3 30 % (Approx. 20 % active polymer) Water 42 % [CIT -choromethylisothia.zolone, MIT -methylisothiazolone] The solution was mixed on a shaker and the volume adjusted to I OOml with water.

Three dilutions of the formulation were tested, concentrated, I in 10 and 1 in 20.

The diluent used was water.

I. Using each of the dilutions (concentrated, I in 10 and 1 in 20), the inside of three small petri dishes (total of 9 petri dishes) were coated and left to dry.

2. At the same time, innoculate bacterial culture from frozen stock were placed into universals containing 1 OmI Mueller Hinton Broth and incubated for 24 hours at 37 Deg C in a shaking incubator set at 100rpm.

3. The culture was diluted in PBS such that there are 108 bacteria ml'.

550j.tl is added to each plate and I O0tl immediately removed for sampling.

4. The plates were incubated at room temperature.

5. A further lOOmI was removed for sampling at I and minutes and 3 x 20t1 removed for plating of neat solution where required.

6. Steps 3 and 4 were repeated at 72 hours and 7 days.

Sampling 1. 1 00.tl of sampled culture was added to 900iI of sterile PBS pre-prepared eppindorfs.

2. Serial dilutions were made in PBS 3. 3x20.tl of each dilution was added to nutrient agar plates 4. Drops were allowed to dry and then the plates incubated for 24 hours for S. enteritidis, E. co/i 0157.

Results The number of CFU (colony forming units) formed in each 20p.l drop was counted and the average of three calculated. This was multiplied by the dilution factor to give the number of cfu per millilites of culture (cfu mI-I) Escherichja coil 0157 Iday 2day 7day Blank Tlmin 4. 5 x lO 4.1 x 1O 9.1 x iO T=5min 5.5 x i0 4.1 x 10 9.0 x Biocides only Tlmin BLD BLD 3.2 x i04 TSmjn BLD BLD BLD Concentrated formulation Tlmin BLD BLD BLD T5min BLD BLD BLD Diluted formulation 1 in 10 Tlmin BLD BLD BLD TSmin BLD BLD BLD Diluted formulation 1 in 20 Tlmin BLD BLD BLD TSmin BLD BLD BLD BLD= <50 cfu ml' Salmonella enteriridis iday 2day 7day Blank 1=1mm 1.31 x 1O 9.75 x i07 1.21 x IO7 1=5mm 1.36x108 l.38x1O L43x107 Biocides only T=lmin BLD BLD 1.2 x i T=5min BLD BLD BLD Concentrated formulation T=lmin BLD BLD BLD T5min BLD BLD BLO Diluted formulation 1 in 10 T=lmin BLD BLD BLD T=5min BLD BLD BLD Diluted formulation I in 20 Tlmin BLD BLD BLD T5min BLD BLD BLD BLD= <50 cfu mF' C. Durability of residual biocide to washing and wiping The following experiment was carried out to test the resistance of the biocide to being washed or wiped after drying and to compare this to biocides alone.

* Method 1. Formulation was prepared as above and diluted to a I in 10 dilution with water (Solution 1) A second solution was prepared using the same quantities of biocides as in A but without the polymer (Solution 2), 2. 9 glass beakers were sprayed with Solution 1, 2 or water (3 beakers of each).

3. The beakers were either left to dry (7 hours), left to dry then rinsed with 25m1 of water, or left to dry and wiped with a soft cloth (see Table of treatments shown below) Treatment Left to dry (7 hours) Solution I Solution 2 Left to dry and rinsed Solution 1 Solution 2 with 25 ml water Left to dry and wiped Solution I Solution 2 soft cloth Left to dry Water Water 24 hours later 108 cfu of E. coli 0157 are pipetted onto the surface of the beakers and 1 OOiil aliquots removed at 0, and 15 minutes. The number of viable bacteria will be counted and reported as cfu ml'.

Results Solution I Solution 2 Treatment 0 mm 15 mm 0 mm 15 mm Left to dry (7 hours) 1x102 BLD 2.1x103 BLD Left to dry and rinsed 7x108 8x102 1x109 Ix with 25 ml water Left to thy and wiped 4x108 BLD 5x102 BLD soft cloth Treatment 0 mm 15 mm Control (sprayed with > lx I 0 > Ix I water and left to dry) BLD<lOOcfu Accordingly, solution I demonstrates a greater durability to washing and wiping then solution 2.

D. Further Comparative Formulations The following formulations were prepared. The difference between the formulations residing in the type and quantity of isothiazolone content: Components. CAS No. 5-Chloro-2-methyl-2H-isothiazol-3-one 26172-55-4 2-Methyl -2H-i sothiazol-3-one 2682-20-4 1,2-benzisothiazol-3(2H)-one 2634-33-5 Cocoalkyldimethylbenzylammonium chloride 61789-71-7 * Di-n-decyl dimethylammonium chloride 7173-51-5 Propan-2-ol 67-63-0 Di-quaternary terminated polydimethylsiloxane Polymer Aliphatic alcohol ethoxylate Water Formulations A B C Raw Material 1 8.0% Zero Zero Raw Material 2 Zero 8.0% Zero Raw Material 3 5.0% 5.0% 6.0% Raw Material 4 11.0% 11.0% 12.0% Raw Material 5 30.0% 3 0.0% 3 0.0% Water 46.0% 46.0% 52.0% Raw Material I is a mixture of benzisothia.zolone and methylisothiazolone at 5% total activity.

CAS Nos. 2634-33-5 and 2682-20-4 Raw Material 2 is a mixture of chioromethylisotbiazolone and methylisothiazolone at 1.5% total activity.

CAS Nos. 26172-55-4 and 2682-20-4 Raw Material 3 is a solution of cocoalkyl dimethylbenzyl animonium chloride at 50% activity.

CASN0.61789-71-7 Raw Material 4 is a solution of 50% di-n-decyl dimethyl ammonium chloride stablised with 20% propan-2-ol.

CAS Nos. 7173-51-5 and 67-63-0 Raw Material 5 is an appoximate 20 % solution of a di-quaternary terminated polydimethylsiloxane polymer stabilised with an aliphatic alcohol ethoxylate at * <5% (CAS Nos. not available).

Polymer 1 FormuLation -Table 1 Component Amount Polymer 1 30% of a 20% microemulsion added to give 6% Active Ingredient Surfactant Variable Methylisothiazolone and 8% of a 5% solution added to give 0.2% Benzisothjazolone Active Ingredient of each Isothiazolone Dialkyldimethylammonium Chloride 11% of a 50% solution added to give 5.5% Active Ingredient, together with 2.2% propan-2-ol Alkyl Benzyldimethylammonium 5% of a 50% solution added to give Chloride 2.5% Active Ingredient Water 46% It will be understood that the components in the above table are provided as an example only. Variants of the components may be used, as well as varying amounts of active ingredient.

Versions may also be formulated without the isothiazolones, where a quick contact kill rate is not necessarily required, for example fabric treatment where preventing of organism growth is required.

An alternative formulation may comprise Polymer 2. This formulation is the same as described in Table I except that polymer 2 may be added to polymer 1 (pre-mixed) before adding to the remaining components. The combination of polymers I and 2 may amount to at least 10% Active Ingredient. Accordingly, the amount of water in the formulation would be reduced to compensate for the addition of the second polymer. The ratio of different polymers in the polymer component in formulations where multiple polymers are used may be any suitable level, usually * between 5% and 95%.

Polymer 2 may, of course also be used independently of Polymer 1.

E. Shelf-Life The isothiazolone type and content of each formulation influences in particular, the shelf life of the formulation. For example, the shelf life of formulation C is greater than that of formulation B, which in turn is greater than that of formulation B, as exemplified below: Accelerated ageing tests carried out over 48 hours: Formulation C has an indefinite shelf life, as shown from accelerated ageing tests at up to 60 C for 48 hours, where no visible changes were observed.

Formulation B has a shelf-life of at least 3 months. However, a colour change is observed after 40 hours during accelerated ageing tests carried out at 60 C. The concentration of CIT in the formulation dropped to about 60 % of its original value after 3 months natural storage, whilst the MIT concentration remained at over 90 Formulation A demonstrated a shelf-life of at least six months in corresponding accelerated ageing tests. Accelerated aging tests carried out over 65 hours: At 60 C for 65

hours, formulation C remained unchanged, whilst formulation A demonstrated only marginal changes. The observed changes affected only the isothiazolones in the formulation and do not compromise the remainder of the formulation.

F. Kill Rates The kill rate per minute was measured for each formulation against E.coli (0157), S.enteritidis, K.pneumoniae, C. albicans and MRSA by applying a 7 day * application of a 1:20 dilution. This 7 day application of a 1:20 dilution involves challenging treated surfaces with bacteria after increasing lengths of time to see if the bactericide was still working, as follows: A batch of clean plates were sprayed with the appropriately diluted formulation and leaving to dry. After various time intervals, the plates were then challenged with bacterial cultures and incubated for testing. The resulting plates were then compared with plates sprayed with the same bactericide in the absence of polymer.

Result A 100 % kill rate in 1 minute was achieved against all the above-mentioned bacteria by a 1:20 dilution of the formulation.

The speed of kill for each formulation appears to corresponds to the stability of the formulation in that the lower the stability of the formulation, the greater the speed of kill, such that formulation B demonstrates a greater speed of kill that formulation A, which in turn demonstrates a greater speed of kill than formulation C. However, for the application to which a residual biocide may be put, speed of kill is less important since, by definition, residual biocides have long contact times.

Hence, under the expected conditions of use, all three formulations performed to a similar level.

The formulations exemplified above exhibit antibacterial activity, as evidenced by the biocidal properties of the formulations. The kill spectrum is very similar for all of formulations A, B and C. In addition, these particular formulations also have proven flmgicidal properties.

This ability to effectively disinfect surfaces of bacteria, fungi (including yeast) as well as remain useable over a significant period of time allows the use of the formulations as disinfecting agents for the treatment of surfaces in, for example, the food and beverage industry, hospitals and the veterinary industry, where the formulations may be used, for example, to treat working surfaces and equipment, all industries in which high regulatory standards are applied and strict controls are maintained in respect of hygiene.

Efficacy against Mycobacterium The formulations A, B and C demonstrate a low speed of kill for Mycobacterium.

In order to guarantee an efficient kill speed, the pH needs to be carefully controlled. As an example, formulation D (detailed below) demonstrates excellent results against Mycobacterium.

Formulation D: Raw Material4 14.0% Raw Material 5 30.0 % Raw Material 6 8.0 % Raw Material 7 8.0 % RawMaterial8 5.0% Water 35.0% Raw Materials 4 and 5 are as for formulations A, B and C Raw material 6 is 2-aminoethanol, CAS No. 14 1-43-5.

Raw Material 7 is a 30% solution of trisodium ethylenediamine disuccinate, CAS No. 178949-82-1.

Raw Material 8 is a 90% solution of an alcohol ethoxylate, CAS No. 68439-45-2.

[N.B. Raw Material 7 can be replaced by 6% of Raw Material 9, a 40% solution of tetrasodium ethylenediamine tetra-acetate, CAS No. 64-02-8, increasing the water to 37.0% to make Formulation E.J The proved efficacy of formulations D and E against Mycobacterium makes the formulations of exceptional value in medical applications and food preparation environments where regulatory standards relating to the specified efficacies of utilised formulations are high and stringent controls are in place to ensure that the standards are being met by any formulation approved for such application.

Claims

CLAIMS

1. A composition for use in treating a surface, comprising at least one polyorganosiloxane polymer having the formula A: T' R' R2SiO(R3R4SiO)r(R5T2SjO)sSjR6R7T3 wherein, the symbols R', R2, R3, R4, R5, R6 and R7, which are identical or different, represent a phenyl or a C1 to C6 alkyl radical, and the symbols T', T2 and T3, which are identical or different, represent a phenyl or a C1 to C6 alkyl radical, or an alkyl radical of the formula: -R8-O-R9-X wherein, the symbols R8 and R9, which are identical or different, represent a C1 to C6 alkyl radical, and the symbol X represents a primary alcohol, or a quaternary amine of the formula: -N(R' R' R'2)Z wherein, the symbols R' , R and R'2, which are identical or different, represent a C1 to C19 alkyl or alkylene group, linear or branched chain, z represents an acetate anion; r is an average value ranging from 1 to 500; s is an average value ranging from 1 to 10; and an active agent.

2. A composition as claimed in Claim I, wherein Formula A is further defined in that the C1 to C6 alkyl radical of at least one of the R8 or R9 groups contains at least one secondary alcohol group.

3. A composition as claimed in any of Claims 1 or 2, wherein Formula A is further defined in that R8 is of the formula: 4. A composition as claimed in any preceding claim, wherein Formula A is further defined in that R9 is of the formula: -CH2CHOHCH2- 5. A composition as claimed in any preceding claim, wherein Formula A is further defined in that X represents at least one primary alcohol group.

6. A composition as claimed in any preceding claim, wherein Formula A is further defined in that X represents at least one quaternary amine group.

7. A composition as claimed in Claim 6, wherein Formula A is further defined in that X represents a quaternary amine group of the formula: -N(Me2Y)Z wherein, the symbol Y represents a C11 to C13 alkyl radical; the symbol Z represents an acetate anion.

8. A composition as claimed in a.ny preceding claim, wherein Formula A is further defined in that T2 is of the formula: -(CH2)3NH2 9. A composition as claimed in any preceding claim, wherein Formula A is further defined in that at least one ofT' or i is a Methyl group.

10. A composition as claimed in any preceding claim, wherein Formula A is further defined in that r has a value ranging from 1 to 300.

11. A composition as claimed in any preceding claim, wherein Formula A is further defined in that r represents a value ranging from I to 200.

12. A composition as claimed in any preceding claim, wherein Formula A is further defined in that r represents a value of 80.

13. A composition as claimed in any preceding claim, wherein Formula A is further defined in that s represents a value ranging from 1 to 5.

14. A composition as claimed in Claim 1, wherein Formula A is defined as: W-CH2CHOHCH2-O-(CH2)3-(SjMe2O-)r-(MeSiQ-[CH2}3-O-CH2CHOHCH2W)sSiMe2(CH2) 3OCH2CHOHCH2W wherein, the symbol W occurs in the molecule at least four times, and is defined by at least two hydroxyl groups and at least two amine groups of the formula: -N(Me2Y)Z wherein, the symbol Y represents a C11 to C13 alkyl radical; the symbol Z represents an acetate anion, and r is an average value ranging from 1 to 200; s is an average value ranging from 2 to 5.

15. A composition as claimed in Claim 1, wherein Formula A is defined as: Me3Si-O-(Me2Si-O-)r-(MeSiR-O-)s-SiMe3 wherein, the symbol R represents an alkyl amine of the formula: -(CH2)3-NH2 and, r is an average value ranging from 1 to 500; s is an average value ranging from I to 10.

16. A composition as claimed in any preceding claim, wherein the active agent is selected from the group consisting of a biocidal, anti-microbial, bactericidal, fungicidal, germicidal, yeasticiclal, moldicidal, algicidal and virucidal agent.

17. A composition as claimed in any preceding claim, wherein the active agent comprises one or more biocidal agents.

18. A composition as claimed in any preceding claim, further comprising a surfactant.

19. A composition as claimed in any preceding claim, wherein the active agent is contained in a non-volatile carrier.

20. A composition as claimed in any preceding claim, which is incorporated into a functional material or article.

21. An article which has been treated by the composition according to any of Claims ltol9.

22. A composition for use in treating a surface, comprising at least two different polyorganosiloxane polymers formed according to any of Claims 1 to 20.

23. A composition as claimed in Claim 22, wherein the composition comprises a blend of between 5 to 95% of each polymer.

24. A process for use in treating a surface, comprising applying an effective amount of a composition comprising one or more polyorganosiloxane polymers formed according to any of Claims ito 20 and 22 to 23.