Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
  • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
  • A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
  • A01N25/24—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing ingredients to enhance the sticking of the active ingredients
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3715—Polyesters or polycarbonates
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/507—Polyesters
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/507—Polyesters
  • D06M15/5075—Polyesters containing sulfonic groups
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/53—Polyethers
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic

Definitions

• BIOCIDAL COMPOSITIONS The invention relates to biocidal compositions and methods for controlling micro organisms using such compositions.
• Known biocidal compositions generally suffer from the disadvantage that they have no lasting effect. In other words, after they are applied to a surface their biocidal effect decreases rapidly, especially if the surface is washed.
• a composition suitable for application to a hard or textile surface which comprises an aqueous solution, suspension or dispersion of a biocide and a copolymer comprising chain units, Al, of the formula -OC n H 2n - where n is 2 or 3 and chain ester units, A2, of the formula
• R is a hydrophobic group; the mole ratio of units Al to A2 being from 1:10 to 3000:1 and the copolymer having a molecular weight from 1000 to 100,000.
• R is preferably an alkylene group, a cycloalkylene group, or an arylene group.
• the alkylene group preferably has six or more carbon atoms, the cycloalkylene group preferably ha ⁇ 4 to 10 carbon atoms, especially cyclohexylene and the arylene group is preferably a meta- or para- phenylene or naphthylene group.
• the groups represented by R may optionally be substituted. Suitable substituents include C x . 6 -alkyl, for example methyl, or hydrophilic groups such as sulphonic acid groups, optionally in alkali metal salt form, for example sodium sulpho-3,5-phenylene.
• the copolymer preferably has a molecular weight from 2000 to 30,000.
• the molar ratio of units Al to A2 is preferably from 1:1 to 100:1.
• copolymers possess a hydrophobic part which will give some adherence to the surface, resisting removal by water and weak surfactant solutions, and a hydrophilic part which will allow migration of the biocide through to the surface of the polymer, particularly when the surface is rinsed with water or an aqueous solution.
• the chain units Al are generally hydrophilic while the chain ester units A2 are hydrophobic.
• copolymers used preferably comprise chain units of the formula -(O-C n H2n)m-0-C-R-C- (A3)
• n and R are as defined above, especially polyoxyethylene terephthalate units, and chain units of formula:
• n and R are as defined above, especially polyethylene terephthalate units.
• Preferred polymers are those having an A3:A4 molar ratio of from 1:10 to 10:1, preferably from 1:2 to 1:6.
• the units A3 preferably contain (OC n H 2n ) ra groups having a molecular weight of from 500, preferably 1000, to 10,000, especially about 3400.
• the polymer preferably has a total molecular weight of from 1000 to 100,000, preferably from 15,000 to 35,000 especially about 20,000.
• m is an integer from 14 to 110, particularly about 75.
• the polymer in order to impart a slight ionic character, or increased hydrophilicity, to the polymer, the polymer is end-capped with a hydrophilic group.
• Suitable hydrophilic groups include those containing a sulpho group, for example those of formula (M0 3 S) (C 6 H 4 )C(0) - or (M0 3 S) (CH 2 ) x (CH 2 CH 2 0) (C n H 2n O) y - where M is a suitable cation, for example an alkali metal ion especially sodium, X is 0 or 1, y is from 0 to 4 and n is as defined above, monoesters of ethylene glycol or propylene glycol. They may be added during the preparation of the base polyester.
• the molar quantity of the hydrophilic group in the total molar quantity of units A2 used in such preparation is from 0 to 15%.
• Suitable polymers include those disclosed in US-A- 4,770,666 in groups B, C and D, US-A-4, 116, 885, US-A- 3,962,152, GB-A-2,196,013, US-A- ,702, 857, US-A-4, 711, 730, US-A-4,713,194, US-A-3,416, 952, US-A-4,427,557 and US-A- 4,201,824, which also describe methods for their preparation which are, of course, well known.
• the polymer is used as an aqueous solution, suspension or dispersion. It may optionally be solubilised or dispersed in water with the assistance of solubilising or dispersing agents such as non-ionic surfactants, in particular a fatty alcohol ethoxylate such as C 12 or C 14 alkyl ethoxylates.
• solubilising or dispersing agents such as non-ionic surfactants, in particular a fatty alcohol ethoxylate such as C 12 or C 14 alkyl ethoxylates.
• a dispersion or suspension is generally preferred since such formulation will adhere better to the surface than solutions.
• Biocides which may be used in the compositions of the present invention include: a) Quaternary ammonium and phosphonium biocides: Coco- alkyl benzyl dimethyl ammonium chloride; C 1214 -alkyl benzyl dimethyl ammonium chloride; Lauryl C 1214 -alkyl-benzyl dimethyl ammonium chloride; Coco-alkyl 2,4-dichlorobenzyl dimethyl ammonium chloride; Tetradecyl benzyl dimethyl ammonium chloride; diisobutyl phenoxy-ethoxy-ethyl dimethyl-benzyl ammonium chloride; Lauryl pyridinium chloride; C 12/14 -alkyl-benzyl imidazolinium chloride; Myristyl trimethyl ammonium bromide; Cetyl trimethyl ammonium bromide; Didecyl dimethyl ammonium chloride; Dioctyl dimethyl ammonium chloride; and Myristy
• N- (N' -C 8-18 -alkyl-3-aminopropyl) - glycine derivatives such as (dodecyl) (aminopropyl)glycine; N- (N' - (N"-C 8-18 -alkyl-2-aminoethyl) -2-aminoethyl) -glycine derivatives such as (dodecyl) (di-ethylene diamine)glycine; and N,N-bis (N' -C 8 _ 18 -alkyl-2-aminoethyl) -glycine derivatives.
• Phenolics Parachlorometaxylenol, dichlorometaxylenol, phenol, m-cresol, o-cresol, p-cresol, o-phenyl-phenol, 4-chloro-m-cresol, chloroxylenol, 6-n- amyl-m-cresol, resorcinol, resorcinol monoacetate, p-tert- butyl-phenol and o-benzyl-p-chlorophenol or biologically active, water soluble salts of these compounds, e.g.
• alkali metal salts Chlorhexidine and its salts for example chlorhexidine gluconate; f) Iodophors, hypochlorite salts and chlorine release agents, e.g. sodium dichloroisocyanurate; g) Polyquaternary ammonium biocides such as poly [hydroxyethylene (dimethylimino) ethylene (dimethylimino) methylene dichloride] , poly [oxyethylene (dimethylimino) ethylene (dimethylimino) ethylene dichloride] , poly[hydroxyethylene (dimethylimino) -2-hydroxypropyl (dimethylimino) methylene dichloride] and the polymer of IH-imidazole with (chloromethyl)oxirane.
• Polyquaternary ammonium biocides such as poly [hydroxyethylene (dimethylimino) ethylene (dimethylimino) methylene dichloride] , poly [oxyethylene (dimethylimino)
• the polymer is preferably used at a concentration of from 1 to 80% by weight, preferably from 5 to 50% more preferably from 10 to 30%, for example about 15%, by weight.
• the biocide is preferably used in a concentration range of from 0.1% to 20% by weight, preferably from 1 to 10%, more preferably from 1 to 5%, for example about 2.5%, by weight.
• the surface to be treated may be a hard surface or, for example, a textile fabric or a flexible polymer surface or a coating. Thus the compositions can be used to advantage during household or industrial laundry processes.
• the amount of solid active ingredient deposited on the hard surface per 2 m is typically 0.01 to lOg, preferably O.lg to lg of the biocide and O.lg to 20g, preferably 1 to 5g of the polymer.
• the amount deposited is typically 0.001% to 10%, preferably 0.01% to 5%, for example about 0.1%, of the biocide and 0.001% to 10%, preferably 0.01% to 5%, for example about 0.2%, of the polymer, by weight based on the weight of fabric.
• compositions according to the invention provide a sustained biocidal effect when applied to a hard surface. This sustained effect is resistant to washing of the surface.
• the polymer used in the composition has the advantage that it is biodegradable by virtue of the ester linkage present in the backbone of the polymer.
• Another advantage of the compositions is that they may easily be removed from the surface to which they have been applied by the application of an alkali .
• compositions are that there is no need for the polymer to contain cationic grouping to enhance hydrophilicity.
• grouping especially cationic nitrogen groupings, tends to give rise to effluent problems because polymers with such groupings are frequently toxic to fish.
• composition finds utility for general hospital laundry, including sheets, nurses' uniforms, surgeons' gowns, doctors' white coats, clothing aprons, used in some sensitive industries such as the food industry, cleaning cloths and towels, e.g. hand towels, at home or in industrial areas, clothing and uniforms worn during participation in energetic sporting activities and personal clothing, particularly worn next to the skin, e.g. socks and undergarments.
• composition towards the end of the laundry treatment thus avoiding any possible incompatability between the normal anionic detergent systems and the biocide, e.g. quaternary biocides.
• biocide e.g. quaternary biocides.
• biocide plus polymer may be incorporated into the fabric softener formulation itself.
• biocide plus polymer may be added with minimal water at a separate stage before drying. This ensures maximum transfer to the fabric or sheet.
• Fabrics include those of natural fibres such as cotton and wool, modified natural products such as cellulose acetates, synthetic polymers such as polyester, polyamide and acrylics, and coated fabrics, for example PVC coated polyester.
• Suitable fabric softeners include: 1. Simple Dialkyi quaternary ammonium compounds of general formula:
• R__ and R 2 which can be the same or different, each independently represents a long chain aliphatic group, e.g. C 16 - C 18 such as tallow, hydrogenated tallow, stearyl or oleyl.
• X is an anion such as halide, preferably chloride, or methosulphate (CH 3 S0 4 )
• A is hydroxyl (OH or amino (NH 2 )
• X is an anion such as halide, preferably chloride, or methosulphate (CH 3 S0 4 )
• A is hydroxyl (OH or amino (NH 2 )
• X is an anion such as halide, preferably chloride, or methosulphate (CH 3 S0 4 )
• A is hydroxyl (OH or amino (NH 2 )
• Such softeners are typically present in the composition in an amount of from 2 to 20%, preferably 3 to 15%, especially about 10% by weight.
• Such softener formulations can optionally contain other ingredients such as colouring agents, perfumes, optical brighteners and stabilising solvents such as isopropanol .
• a method of controlling microorganisms at a locus which comprises applying to the locus where such control is required a biocide and a copolymer as defined above, for example in the form of a composition according to the invention.
• a suitable locus is a hard surface, for example glazed and unglazed ceramic, glass, PVC, formica and other hard plastics, stainless steel or other painted or unpainted metals, and painted or unpainted wood, as well as a flexible polymer surface.
• compositions according to the present invention are preferably used in the method of the invention in diluted form at dilutions from 20 to 500 times, preferably 50 to 100 times. In laundry applications, the composition will normally be diluted by the washing/rinsing water.
• Gram positive bacteria Staphylococcus aureus; and Streptococcus faecium.
• Yeasts Saccharomyces cerevisiae; and Candida albicans.
• Fungi Aspergillus niger, • Fusarium solani; and Pencillium chrysogenum.
• Algae Chlorella saccharophilia; Chlorella emersonii; Chlorella vulgaris; and Chlamvdomonas eugametos.
• the microorganisms controlled by the method of the present invention are preferably Gram negative microorganisms, especially Pseudomonas aeruginosa, Gram positive microorganisms, especially Staphylococcus aureus, and fungi e.g. Aspergillus niger.
• Gram negative microorganisms especially Pseudomonas aeruginosa
• Gram positive microorganisms especially Staphylococcus aureus
• fungi e.g. Aspergillus niger.
• the positive results obtained using the compositions of the invention show that the compositions will be effective over a wide range of known microorganisms.
• biocide used was C 12 _ 14 -alkyl benzyl dimethyl ammonium chloride and the polymer was of the following formula:
• a hard surface having an area of 25cm 2 which had previously been sterilised by wiping with isopropyl alcohol was treated with 3ml of each of the disinfectant concentrates after appropriate dilution e.g. 100X and then dried at 45°C.
• the tile is then washed consecutively with a water spray or sponge and dried again at 45°C.
• 0.25ml of an aqueous medium containing about IO 8 cfu's/ml of the gram negative bacteria Pseudomonas Aeruginosa was then spread over the treated hard surface.
• the surface was then allowed to stand for the contact times shown in Table 2 below. This was to allow the biocide time to migrate through the polymer layer and kill the bacteria on the surface.
• the surfaces were then dried at 37°C.
• the surviving organisms were recovered using a sterile cotton wool swab, previously wetted with a neutralising medium. The whole surface was carefully swabbed by wiping it across back and forth several times. The swab was transferred to 9ml of neutralising medium comprising 3% Tween 80% and 2% soya lecithin which was then plated out using 10-fold serial dilutions onto nutrient agar. The plates were incubated at 37°C for 48 hours and the survivors were counted. Control tests were carried out using a clean hard surface of the same area and using the same method except that no polyester or biocide was applied.
• the sustained biocidal effect of the compositions of the invention was measured by washing the hard surface with a sponge before treating it with microorganisms using the method described above.
• the sponge treatment involved the use of a Gardener-Scrub washing machine, which pushes a sponge soaked in water across the surface, which is mounted horizontally, at a pressure of 5.6g/cm 2 .
• the sponge passed over the surface twice.
• Table 2 The results shown in Table 2 below were obtained:
• N represents the number of bacteria (cfu's/ml) recovered from the control and n represents the number of bacteria (cfu's/ml) recovered from the test sample.
• a Log 10 reduction of 5 shows an excellent result particularly for food contact areas and a Log 10 reduction of 3 shows a satisfactory result for general disinfection.
• Example 2 was carried out in a manner identical to that of Example 1 (with dilution 100X) except that instead of washing with a sponge the surfaces were subjected to non abrasive washing with a water spray. This involved mounting the surface vertically and spraying it with lg of water from a hand held trigger spray for each wash.
• Table 3 The results shown in Table 3 below were obtained:
• Disinfectant concentrates having the formulation shown in Table 4 below were prepared:
• the biocide used was Poly[hydroxyethylene(dimethyliminio) - 2-hydroxy propyl (dimethyliminio) ethylene dichloride] .
• the polymer used was the polymer of formula (I) as in Example 1. The percentages are percentages by weight.
• This Example was carried out in the same way as Example 2 except that disinfectant concentrates DC3 and DC4 were used. The results obtained are shown in Table 5 below: Table 5
• the polymer quaternary ammonium biocide is a relatively slow acting biocide and so testing was carried out after an 24 hour contact time. When the polymer is present, the biocide resists at least 2 water sprays before its effectiveness is greatly reduced.
• a control sample of fabric was treated as above with 5mls of water without the biocide present.
• Example 4 The same procedure was followed as in Example 4 but the treated fabric square was subsequently dipped for 10 seconds in a beaker of water before re-drying at 45°C followed by addition of bacteria and covering with nutrient agar as before. b) A similar control treatment was carried out using biocide without the polymer.
• the polymer helps to prolong the effect of the biocide to light rinsing with water.

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• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Textile Engineering (AREA)
• Wood Science & Technology (AREA)
• General Health & Medical Sciences (AREA)
• Health & Medical Sciences (AREA)
• Toxicology (AREA)
• Dentistry (AREA)
• Zoology (AREA)
• Environmental Sciences (AREA)
• Plant Pathology (AREA)
• Pest Control & Pesticides (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Organic Chemistry (AREA)
• Agronomy & Crop Science (AREA)
• Dispersion Chemistry (AREA)
• Biochemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Microbiology (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

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• 1995
  • 1995-08-18 GB GB9516966A patent/GB2304286B/en not_active Expired - Fee Related
• 1996
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  • 1996-08-19 JP JP9509074A patent/JPH11514342A/ja active Pending
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  • 1996-08-19 WO PCT/GB1996/002025 patent/WO1997006675A1/en not_active Application Discontinuation
  • 1996-08-19 CN CN96197047A patent/CN1196656A/zh active Pending
  • 1996-08-19 KR KR1019980701165A patent/KR19990037686A/ko not_active Application Discontinuation
  • 1996-08-19 AU AU68252/96A patent/AU711510B2/en not_active Ceased
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  • 1996-08-19 EP EP96928515A patent/EP0863701A1/en not_active Withdrawn
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• 1998
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