WO2014196881A1 - Method of wet washing to produce biocide textiles - Google Patents

Method of wet washing to produce biocide textiles Download PDF

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Publication number
WO2014196881A1
WO2014196881A1 PCT/PL2013/000113 PL2013000113W WO2014196881A1 WO 2014196881 A1 WO2014196881 A1 WO 2014196881A1 PL 2013000113 W PL2013000113 W PL 2013000113W WO 2014196881 A1 WO2014196881 A1 WO 2014196881A1
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WIPO (PCT)
Prior art keywords
copper
silver
nanoparticles
fabric
oxide
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PCT/PL2013/000113
Other languages
French (fr)
Inventor
Marian ŁOŚ
Original Assignee
Eko-Styl Sp. Z O. O.
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Publication date
Application filed by Eko-Styl Sp. Z O. O. filed Critical Eko-Styl Sp. Z O. O.
Priority to DE112013007131.2T priority Critical patent/DE112013007131T5/en
Priority to SK50078-2015A priority patent/SK288551B6/en
Publication of WO2014196881A1 publication Critical patent/WO2014196881A1/en

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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L1/00—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods
    • D06L1/12—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using aqueous solvents
    • D06L1/16—Multi-step processes
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • 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
    • A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/001—Softening compositions
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/1213—Oxides or hydroxides, e.g. Al2O3, TiO2, CaO or Ca(OH)2
    • 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
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L1/00—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods
    • D06L1/12—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using aqueous solvents
    • D06L1/20—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using aqueous solvents combined with mechanical means
    • 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
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
    • 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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/144—Alcohols; Metal alcoholates
    • D06M13/148—Polyalcohols, e.g. glycerol or glucose
    • 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
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03—Polysaccharides or derivatives thereof
    • D06M15/11—Starch or derivatives thereof
    • 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
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/327—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof
    • D06M15/333—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof of vinyl acetate; Polyvinylalcohol
    • 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
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
    • D06M15/3562—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing nitrogen
    • 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
    • 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
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/08—Processes in which the treating agent is applied in powder or granular form
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/12—Soft surfaces, e.g. textile

Definitions

  • the matter of invention is the method of furnishing textile during wet washing, especially applicable in large scale laundries providing bedding wash services for hospitals, hotels and related places, as well as work clothes.
  • fleece, cotton, and synthetic fiber surfaces are known, including impregnation to make them, for instance antiseptic, waterproof, or flame resistant. It has been also recognized that silver and copper reveal antimicrobial properties.
  • Ciofi et al (2005) [Ciofi N. et al. Copper Nanoparticle /Polymer Composites with Antifungal and Bacteriostatic Properties, Chem. Mater., 17 (2005), 5255-5262] have described polymer nanocomposite containing nanomolecules of copper as antimicrobial and antifungal agent. It was proven experimentally that nanoparticles were released from nanocomposite surface and resulted in growth inhibition of fungi and other pathogenic microorganisms. The biological activity corroborated with metal nanoparticle content.
  • liquid composition possesing antimicrobial and antifungal properties, dedicated to cleaning of interiors, like floors and walls, and sanitary area and equipment, containing among others, at least one nanosilver(O) colloid up to 500 ppm concentration at 1% to 99% weight and/or at least one nanocopper(O) colloid up to 500 ppm concentration at 1% to 99% weight was described in Polish patent application no P.390497.
  • the nanoparticles of silver and/or copper as well as their oxides are obtained by Turkevich method (i.e. by readuction of metal cations with citrate or ascorbic acid) to get colloidal mixture with polymer, from which the granules of polymer-nanoparticles composite are formed by extrusion. Then the granules of nanocomposite are mixed with base polymer and synthetic fibers are formed by spinning.
  • Such obtained fabric showed antibacterial, antifungal, and fungal cytostatic properties even after many washing cycles.
  • liquid mixture was dosclosed, containing peroxide bleacher and chelating agent for copper and/or iron and/or manganese, at the preliminary washing step and compositions applicable in this process.
  • the method of furnishing fibers with antibacterial silver particles in entire washing was also described.
  • the fibers are treated with mixture of specimen containing colloidal silver and/or ionic silver and softener agent composed of surfactants in such proportion that mixture contains 100 to 5000 mg Ag/dm 3 and/or fibers are sprayed after centrifuging step with mixture containing colloidal silver, surfactants, and/or glycerol, and/or plant starch, and/or polyvinylpyrrolidone, and/or polyvinyl alcohol; the mixture containing 100 to 5000 mg Ag/dm 3 as silver nanoparticles of size no higher then 100 nm, followed by drying.
  • the nanoparticles of silver on fiber surface are stabilized at further step of wet pressing (mangling) or dry pressing (ironing) upon heating.
  • the last step of water washing is mangling/ironing of textile, usually performed at 180 - 230 °C, depending on kind of textile. In that process the elimination of most of bacteria take place. However, the gained status is not permanent; during the use of textile the number of bacteria and fungi increases. This remains a fundamental problem in case of bedclothes and work clothes used in hospitals and other health care places, health care for the elderly places, hotels, prisons, and so on. In such areas the increase of bacteria population, especially of causal microorganisms, may lead to developing of infections and infectious disseases in human populations of lowered dissease resistance.
  • Furnishing of textile during washing process in which textiles undergo preliminary washing, essential washing, water rinsing and water removal, neutralization and/or starching, and/or softening, final centrifuging, drying, mangling (wet pressing) or ironing (dry pressing) steps, according to this invention, consists of that:
  • the textile are treated with specimen containing nanoparticles of copper and copper(II) oxide and/or other compounds of copper(II) of 20- 50 nm diameter average size, or with specimen containing nanoparticles of copper and copper(II) oxide and/or other compounds of copper(II) of 20- 50 nm diameter average size as well as nanoparticles of silver and silver(I) oxide and /or other compounds of silver(I) 20- 50 nm diameter average size, the weigh ratio of metals being between 10.T and 1 : 10, the metal nanoparticles are introduced in a way that ensures the final amount of 10 - 1000 mg of copper or copper and silver per 1 kg of dry textile; furthermore at the softening step the known softener is introduced into washing bathwater and after the centrifuging step the known refiner is introduced, followed by water removal and drying and afterwards the nanoparticles of copper or copper and silver and their oxides are stabilized on textile surface by exposing the textile to high temperature
  • copper and silver are introduced as specimen containing bimetalic nanoparticles of alloy type composed of metallic copper and metallic silver, of average 20-50 diameter size, with weigh ratio of metals from 10: 1 to 1 :10 and/or mixture of specimen composed of Cu/CuO and Ag/Ag 2 0 nanocomposite of core-sheath (metal core and metal oxide sheath) of the size below 20 nm diameter, with weigh ratio of metal to metal oxide being between 1 : 1 and 1 :5.
  • the textile is treated with specimen A containing nanoparticles of copper and/or copper(II) oxide and/or other compounds of copper(II) as well as softener, and then is treated with specimen B, containing nanoparticles of silver and/or silver(II) oxide and/or other compounds of silver(I) as well as softener.
  • the textile is treated, preferably splashed, with specimen A, containing nanoparticles of copper and/or copper(II) oxide and/or other compounds of copper(II), as well as refiner, and then is treated with specimen B containing nanoparticles of silver and/or silver(II) oxide and/or other compounds of silver(I) as well as refiner.
  • softener contains anionic and/or cationic and/or non-ionic surfactants
  • refiner contains anionic and/or cationic and/or non-ionic surfactant and/or glycerol and/or plant starch and/or polyvinylpyrrolidone and/or polyvinyl alcohol.
  • the residual water content is 45%, which further decreases upon mangling.
  • the textiles after washing and water removal are subjected to mechanical and thermal work -up in mangling or ironing step accompanied by immobilization of nanoparticles of copper and/or silver and/or oxides of these metals on textile.
  • Textile mangling or ironing is performed at 180 - 230°C temperature, depending on kind of textile.
  • Upon heating the water evaporates, while nanoparticles of copper and/or silver and/or CuO and/or Ag 2 0 are mechanically pressed into fabric. Also upon heating the reduction of copper(II) and silver(I) into metallic copper and silver occur, respectively.
  • Metal nanoparticles are formed in situ.
  • the fabrics gain antibacterial, bacteriostatic, and antifungal properties, which are adjusted at every washing/mangling cycle.
  • Example 1 In order to obtain nanoparticles of copper and CuO dispersed uniformly on the surface of cotton fabric, 5 kg of dry cotton fabric were processed as follows: a) preliminary washing at 15 L solution containing 80 g of washing specimen Tenalan at 70°C b) essential washing in ⁇ 5 L solution of 20g of disinfecting-bleaching agent PENTA- ACTIV c) twice rinsing with 15 L water d) rinsing with 15 L solution of 4 g Tenapre Exquist agent and 20 000 mg copper as nanoparticles obtained by mixing 14 L water, 4 g Tenapre Exquist agent and 1 L 5: 1 water-glycerol mixture, containing Cu nanoparticles of average 50 nm diameter size. e) drying f) mangling at 200°C.
  • the content of copper nanoparticles immobilized on textile surface was 200 mg Cu/kg textile.
  • Biological activity of resulted textile was tested on Candida albicans ATCC 10231, Candida glabrata, DSM 1 1226, Candida tropicalis KKP 334, Saccharomyces cerevisiae JG, Saccharomyces cerevisiae JG CDR1 and Staphylococcus aureus ATCC 9763.
  • the suspension of 24 hour microorganism culture containing 10 6 cfu/ml was 10 times diluted with nourishment.
  • the 7 cm 2 sample of fabric was sterilized by UV irradiation and placed in 2.5 ml of the cell culture prepared as described above. This mixture was shaken for 1 hour and 1 ml suspension aliquots were then diluted with sterile physiological salt.
  • Example 2 In order to obtain cotton fiber with antibacterial and antifungal properties, with the surface modified with mixture of nanocomposites Cu/CuO and Ag/Ag 2 0 type, 5 kg of dry cotton fabric was processed as follows: a) preliminary washing at 15 L solution containing 80 g of washing specimen Tenalan at 70°C b) essential washing at 15 L solution with 20 g of disinfecting-bleaching agent PENTA-ACTIV c) twice rinsing with 15 L water d) rinsing with 15 L solution of 4 g Tenapre Exquist agent and 3 000 mg copper as nanoparticles and 7 500 mg silver as nanocomposite of Ag/Ag 2 0 obtained by mixing 14 L water, 4 g Tenapre Exquist agent and 1 L 5: 1 water-glycerol mixture, containing Cu/CuO nanoparticles of average 30-60 nm diameter size and Ag/AgO nanoparticles of average 50-70 nm diameter size. e) drying f) mangling at 200°C
  • the content of copper and silver immobilized on the fabric surface was about 30 mg of Cu nanoparticles per kg of fabric and about 75 mg of Ag nanoparticles (as Ag/Ag 2 0 nanocomposite) per kg of fabric.
  • Biological activity of resulted textile was tested on Candida albicans ATCC 10231 , Candida glabrata, DSM 1 1226, Candida tropicalis KKP 334, Saccharomyces cerevisiae JG, Saccharomyces cerevisiae JG CDR1 and Staphylococcus aureus ATCC 9763.
  • the suspension of 24 hour microorganism culture containing 10 6 cfu/ml was 10 times diluted with nourishment.
  • the 7 cm 2 sample of fabric was sterilized by UV irradiation and placed in 2.5 ml of the cell culture prepared as described above. This mixture was shaken for 1 hour and 1 ml suspension aliquots were then diluted in sterile physiological salt.
  • Example 3 In order to obtain cotton fabric covered with alloy-type bimetallic Cu/Ag nanocomposite, 10 kg of dry cotton fabric was processed as follows: a) preliminary washing in 30 L of 80 g washing specimen Tenalan at 70 °C temperature b) essential washing in 30 L solution containing 80 g of Tenalan at 70 °C temperature c) washing with disinfection at 30 L solution of 40 g of disinfecting-bleaching agent PENTA-ACTIV d) twice 30 L water rinsing e) rinsing with 30 L of solution containing 8 g Tenapre Exquist specimen f) drying g) impregnation with nanoparticles by spraying fiber surface with the solution containing 500 mg Cu/dm and 250 mg Ag/dm as bimetallic alloy-type nanoparticles of the 10 to 25 nm size, plant starch and polyvinylpyrrolidone at the proportion 2 liters of solution per 10 kg of cotton fiber h) mangling at 180 °C temperature.
  • Resulting amount of copper and silver immobilized on fabric surface was 100 mg Cu/kg of fabric and 50 mg Ag/kg of fabric as bimetallic alloy-type Cu/Ag nanoparticles.
  • Biological activity of resulted fabric was tested on Candida albicans ATCC 10231 , Candida glabrata, DSM 1 1226, Candida tropicalis KKP 334, Saccharomyces cerevisiae JG, Saccharomyces cerevisiae JG CDRl and Staphylococcus aureus ATCC 9763.
  • Example 4 In order to obtain cotton fabric covered with mixture of nanoparticles of copper, nanoparticles of silver, nanoparticles of copper(II) oxide, and nanoparticles of silver(I) oxide, 10 kg of dry cotton fabric was processed as follows: a) preliminary washing in 30 L of 80 g washing specimen Tenalan at 70 °C temperature b) essential washing in 30 L solution containing 80 g of Tenalan at 70 °C temperature c) washing with disinfection at 30 L solution of 40 g of disinfecting-bleaching agent PENTA-ACTIV d) twice rinsing with 30 L water e) rinsing with 30 L of solution containing 8 g Tenapre Exquist specimen f) drying g) impregnation with nanoparticles by spraying fabric surface with the solution containing 2000 mg Cu/dm as copper citrate and 1000 mg Ag/dm as silver citrate, plant starch and polyvinylpyrrolidone at the proportion 1 liter of solution per 10 kg of cotton fabric h
  • the Cu, CuO, Ag, and Ag 2 0 nanoparticles are formed at the fabric surface in situ during mangling upon high temperature.
  • Resulting amount of copper and silver immobilized on fabric surface was 200 mg Cu/kg of fabric and 100 mg Ag/kg of fabric as a mixture of nanoparticles of copper, nanoparticles of silver, nanoparticles of copper(II) oxide, and nanoparticles of silver(I) oxide.
  • the fabric modified with mixture of nanoparticles of copper, nanoparticles of silver, nanoparticles of copper(II) oxide, and nanoparticles of silver(I) oxide inhibited the bacteria and fungi growth up to 95%, depending on type of microorganism.
  • Example 5 In order to obtain cotton fabric covered with nanoparticles of copper and copper(II) ions, 5 kg of dry cotton fabric was processed as follows: a) preliminary washing in 15 L solution of 80 g washing specimen Tenalan at 70 °C temperature b) washing with disinfection in 15 L solution of 20 g of disinfecting-bleaching agent PENTA-ACTIV at 75 °C c) twice rinsing with 15 L water d) rinsing with 15 L water solution containing 6 g Tenapre Exquist specimen and 8 g of copper citrate e) drying f) impregnation with nanoparticles by spraying the fiber surface with solution containing 500 mg Cu/dm as Cu nanoparticles, preferably of the size below 20 nm and 500 mg of copper(II) citrate, plant starch, and polyvinyl alcohol at the proportion 0.5 liter of solution per 5 kg of cotton fabric g) mangling at 180°C.
  • Resulting amount of copper immobilized on fabric surface was 50 mg Cu/kg of fabric as a nanoparticles of copper and 50 mg Cu/kg of fabric as copper(II) ions.
  • Example 6 In order to obtain nanoparticles of Cu@CuO composed of metallic copper as core and copper(II) oxide as sheath deposited on the cotton fabric surface, 10 kg of dry cotton fabric was processed as follows: a) preliminary washing in 30 L of 80 g washing specimen Tenalan at 70 °C temperature b) essential washing in 30 L solution containing 80 g of Tenalan at 70 °C temperature c) washing with disinfection at 30 L solution of 40 g of disinfecting-bleaching agent PENTA-ACTIV d) twice rinsing with 30 L water e) rinsing with 30 L of solution containing 8 g Tenapre Exquist specimen f) drying_ g) impregnation with nanoparticles by spraying the fabric surface with solution containing 1500 mg Cu/dm as Cu@CuO nanoparticles of core-sheath structure, in which the Cu : CuO weight ratio is 2: 1 and particle size is 10 to 25 ran, plant starch and polyvinylpyrrolidone
  • Resulting amount of copper immobilized on fabric surface was 300 mg Cu/kg of fabric as Cu@CuO nanoparticles of of core-sheath structure.
  • Resulting amount of copper and silver immobilized on fabric surface was 150 mg Cu/kg of fabric as Cu@CuO nanoparticles of core-sheath structure and 150 mg Ag/kg of fabric as Ag@Ag 2 0 nanoparticles of core-sheath structure.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Textile Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • General Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Toxicology (AREA)
  • Agronomy & Crop Science (AREA)
  • Zoology (AREA)
  • Dentistry (AREA)
  • Plant Pathology (AREA)
  • Pest Control & Pesticides (AREA)
  • Environmental Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Emergency Medicine (AREA)
  • Mechanical Engineering (AREA)
  • Biochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Microbiology (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Artificial Filaments (AREA)

Abstract

The method of furnishing fabric during washing, which comprise of preliminary washing, essential washing, water rinsing with further water removal, and then neutralization and/or starching, and/or softening, final centrifugation and drying, wet or dry pressing, characteristic of that during softening step and/or after centrifuging step the fabric is treated with specimen containing nanoparicles of copper and copper(II) oxide and/or other compounds of copper(II) of 20- 50 nm diameter average size, or with specimen containing nanoparicles of copper and copper(II) oxide and/or other compounds of copper(II) of 20- 50 nm diameter average size as well as nanoparticles of silver and silver(I) oxide and/or other compounds of silver(I) of 20- 50 nm diameter average size, the weight ratio of metals being between 10: 1 and 1 : 10, the copper nanoparticles or silver and copper nanoparticles are introduced in such a way which ensures the final amount of 10 - 1000 mg of copper or copper and silver per 1 kg of dry fabric; furthermore at the softening step the known softener is introduced into washing bathwater and after the centrifuging step the refiner is introduced, followed by water removal and afterwards the nanoparticles of copper or copper and silver and their oxides are stabilized on fabric surface by exposing the fabric to high temperature during dry or wet pressing (ironing or mangling).

Description

METHOD OF WET WASHING TO PRODUCE BIOCIDE TEXTILES
The matter of invention is the method of furnishing textile during wet washing, especially applicable in large scale laundries providing bedding wash services for hospitals, hotels and related places, as well as work clothes. Plenty of modifications of textile, cotton, and synthetic fiber surfaces are known, including impregnation to make them, for instance antiseptic, waterproof, or flame resistant. It has been also recognized that silver and copper reveal antimicrobial properties.
Copper had been used already in ancient times for some diseases treatment and hygiene purposes. According to Zhang et al (2007) [Zhang, W., Zhang, Y. Yan, J-Ji, Q., Huang, A., and Chu, P.K., Antimicrobial polyethylene with controlled copper release, J. Biomed. Mater. Res. A, 83 (2007) 838-844] addition of copper to nanocomposites resulted in inhibition of E. coli and Listeria growth; the copper was reported as antimicrobial agent when attached to polyvinylpyrrolidone coating, which has medical application.
Perelshtein et al. (2009) [Perelshtein I, Applerot G, Perkas N, Wehrschetz-Sigl E, Hasmann A, Guebitz, G, Gedanken A (2009) CuO-cotton nanoparticles: formation, morphology and antibacterial activity. Surf Coat Technol 204:54] reported that thin layer of metal oxides, among them copper oxide, layered on cotton fiber surface showed antibacterial activity against Staphylococcus aureus.
Borkow and Gabbay (2004) [Borkow G, Gabbay J (2004) Putting copper into action: copper impregnates, products with potent biocidal activities. FASEB J 18(14): 1728-1730] have shown that copper oxide deposited on synthetic fibers indicated broad spectrum of biological activity, i.e. antimicrobial, antifungal, antiviral, antimites activity. Antimicrobial and antifungal properties of copper were also described by Grace et al (2009) Grace M., Bajpai S.K., Chand N. Copper (II) ions and copper nanoparticles- loaded chemically modified cotton cellulose fibers with fair antibacterial properties, Journal of Applied Polymer Science 1 13 (2009) 757-766], which reported on release of copper(II) from cellulose fibres, which were modified by oxidation with periodate and then average 29 nm diameter nanoparticles of copper(O) were deposited on chitosane by reduction with sodium borohydride. Thus modified fibres had very high antimicrobial activity against E. coli.
Ciofi et al (2005) [Ciofi N. et al. Copper Nanoparticle /Polymer Composites with Antifungal and Bacteriostatic Properties, Chem. Mater., 17 (2005), 5255-5262] have described polymer nanocomposite containing nanomolecules of copper as antimicrobial and antifungal agent. It was proven experimentally that nanoparticles were released from nanocomposite surface and resulted in growth inhibition of fungi and other pathogenic microorganisms. The biological activity corroborated with metal nanoparticle content.
Described properties of silver and copper resulted in their practical applications.
Thus liquid composition possesing antimicrobial and antifungal properties, dedicated to cleaning of interiors, like floors and walls, and sanitary area and equipment, containing among others, at least one nanosilver(O) colloid up to 500 ppm concentration at 1% to 99% weight and/or at least one nanocopper(O) colloid up to 500 ppm concentration at 1% to 99% weight was described in Polish patent application no P.390497.
In case of fabrics there were described the ways of introduction and deposition of mentioned metals on fabric surface. This aim was realized on various chemical and physical methods.
The way of impregnation of fabrics with nanoparticles of silver is described in polish patent application P.387686. In that procedure fabrics are modified with chemicals like: acetic acid and/or solution of sodium hydroxide and benzoil chloride and/or solutions of polymers like: polyacrylamide, polyvinylpyrrolidone, polyvinyl alkohol, polyacrylic acid in order to replace surface hydroxyl group (-OH) with other functional groups, depending on kind of modifier or to diminish the number of -OH groups on surface. Modified fabrics are then impregnated with colloidal solution containing from 100 to 2000 mg of Ag/dm3 obtained by reduction of silver(I) salt with sodium borohydride or citric acid. Then the water is removed from fibers, preferably by. drying with neutral gas.
The method of obtaining fabrics possessing antibacterial properties with help of ultrasonographic treatment is described by Beddow et al. (2012) [Beddow et al. Sonochemical coating of textile fabrics with antibacterial nanoparticles. autorstwa .International Congress on Ultrasonics,: Gdansk 2011. AIP Conference Proceedings, Vol. 1433, 400-403 (2012)]. In that method the nanoparticles of metal oxides like ZnO and CuO were deposited upon ultrasonochemical treatment. Both metal oxides showed high antibacterial activity against all tested bacteria. Similarly the ultrasonographic treatment of fibers in order to provide layers of metal oxides (ZnO, MgO, and CuO) was described in patent US 201 1/0097957 Al .
Another procedure was described in patent US 8,183,167 Bl, in which the fabrics were covered with well-dispersed metal nanoparticles of antimicrobial properties like silver and/or copper, which were well-bonded covalently. Powdered nanoparticles of metals (silver and/or copper) are mixed with the solution containing a component compatible to reactive block copolymer, then their suspension with polymer is transferred to extruder in which the granules of polymer-nanoparticles composite is formed. The obtained nanocomposite is mixed with base polymer to obtain fibers in spinning process.
In modified procedure the nanoparticles of silver and/or copper as well as their oxides are obtained by Turkevich method (i.e. by readuction of metal cations with citrate or ascorbic acid) to get colloidal mixture with polymer, from which the granules of polymer-nanoparticles composite are formed by extrusion. Then the granules of nanocomposite are mixed with base polymer and synthetic fibers are formed by spinning. Such obtained fabric showed antibacterial, antifungal, and fungal cytostatic properties even after many washing cycles.
Chattopadhyay and Patel (2010) [Chattopadhyay D.P. and Patel B.H." Effect of nanosized colloidal copper on cotton fabric", Journal of Engineered Fibers and Fabrics 5 (2010) 1-6] have described the method of obtaining colloidal copper and its application to cotton fibers. Colloidal copper particles of averaged 60 to 100 ran size were obtained by reduction of copper(II) with sodium borohydride in presence of sodium citrate. Fabric impregnation was performed by dipping in colloidal copper solution (the solution : textile ratio was 50: 1) at 40°C for 60 min., and then at 80°C for 30 min. Finally the textile was rinsed with water and air-dried. The copper impregnated "textile~sh"owed antibacterial activity.
Methods of introducing metals on fiber surface while washing were also described.
In polish patent application P.322021 the liquid mixture was dosclosed, containing peroxide bleacher and chelating agent for copper and/or iron and/or manganese, at the preliminary washing step and compositions applicable in this process.
In another patent application P.397964 the method of furnishing fibers with antibacterial silver particles in entire washing was also described. In particular at the softening step the fibers are treated with mixture of specimen containing colloidal silver and/or ionic silver and softener agent composed of surfactants in such proportion that mixture contains 100 to 5000 mg Ag/dm3 and/or fibers are sprayed after centrifuging step with mixture containing colloidal silver, surfactants, and/or glycerol, and/or plant starch, and/or polyvinylpyrrolidone, and/or polyvinyl alcohol; the mixture containing 100 to 5000 mg Ag/dm3 as silver nanoparticles of size no higher then 100 nm, followed by drying. The nanoparticles of silver on fiber surface are stabilized at further step of wet pressing (mangling) or dry pressing (ironing) upon heating.
The adjustment of content of biologically active metals in textile during their use cannot be performed which causes decrease of antimicrobial activity and is a disadvantage of known furnishing methods.
The last step of water washing is mangling/ironing of textile, usually performed at 180 - 230 °C, depending on kind of textile. In that process the elimination of most of bacteria take place. However, the gained status is not permanent; during the use of textile the number of bacteria and fungi increases. This remains a fundamental problem in case of bedclothes and work clothes used in hospitals and other health care places, health care for the elderly places, hotels, prisons, and so on. In such areas the increase of bacteria population, especially of causal microorganisms, may lead to developing of infections and infectious disseases in human populations of lowered dissease resistance.
Although the adjustment of nanosilver amount in textile during washing process is known from patent application P.397964, we have found that introducing both silver and copper nanoparticles is advantageous and more effective solution in this matter. The aim of this invention is improvement of antibacterial, antifungal properties and inhibition of mites proliferation in textiles during ^shing r^oc^ss, _especi_ally_. performed at large scale in comparison with known and described protocols.
Furnishing of textile during washing process, in which textiles undergo preliminary washing, essential washing, water rinsing and water removal, neutralization and/or starching, and/or softening, final centrifuging, drying, mangling (wet pressing) or ironing (dry pressing) steps, according to this invention, consists of that:
during softening step and/or after centrifuging step the textile are treated with specimen containing nanoparticles of copper and copper(II) oxide and/or other compounds of copper(II) of 20- 50 nm diameter average size, or with specimen containing nanoparticles of copper and copper(II) oxide and/or other compounds of copper(II) of 20- 50 nm diameter average size as well as nanoparticles of silver and silver(I) oxide and /or other compounds of silver(I) 20- 50 nm diameter average size, the weigh ratio of metals being between 10.T and 1 : 10, the metal nanoparticles are introduced in a way that ensures the final amount of 10 - 1000 mg of copper or copper and silver per 1 kg of dry textile; furthermore at the softening step the known softener is introduced into washing bathwater and after the centrifuging step the known refiner is introduced, followed by water removal and drying and afterwards the nanoparticles of copper or copper and silver and their oxides are stabilized on textile surface by exposing the textile to high temperature during dry or wet pressing (ironing or mangling).
Preferably, copper and silver are introduced as specimen containing bimetalic nanoparticles of alloy type composed of metallic copper and metallic silver, of average 20-50 diameter size, with weigh ratio of metals from 10: 1 to 1 :10 and/or mixture of specimen composed of Cu/CuO and Ag/Ag20 nanocomposite of core-sheath (metal core and metal oxide sheath) of the size below 20 nm diameter, with weigh ratio of metal to metal oxide being between 1 : 1 and 1 :5.
Preferably, during softening step the textile is treated with specimen A containing nanoparticles of copper and/or copper(II) oxide and/or other compounds of copper(II) as well as softener, and then is treated with specimen B, containing nanoparticles of silver and/or silver(II) oxide and/or other compounds of silver(I) as well as softener.
Preferably, after centrifuging step, the textile is treated, preferably splashed, with specimen A, containing nanoparticles of copper and/or copper(II) oxide and/or other compounds of copper(II), as well as refiner, and then is treated with specimen B containing nanoparticles of silver and/or silver(II) oxide and/or other compounds of silver(I) as well as refiner.
Preferably, softener contains anionic and/or cationic and/or non-ionic surfactants, while refiner contains anionic and/or cationic and/or non-ionic surfactant and/or glycerol and/or plant starch and/or polyvinylpyrrolidone and/or polyvinyl alcohol.
Generally the technology of washing providing antibacterial properties of textile comprise following steps: a) Preliminary washing b) Essential washing with disinfection c) Water rinsing followed by water removal d) Neutralization / starching / softening / impregnation with copper and/or silver specimen e) Final centrifuging f) Drying, mangling or ironing with concomitant immobilization and stabilization of nanoparticles of copper and/or silver and/or metal oxides
In the proposed process, after washing the clothes the residual water content is 45%, which further decreases upon mangling. The textiles after washing and water removal are subjected to mechanical and thermal work -up in mangling or ironing step accompanied by immobilization of nanoparticles of copper and/or silver and/or oxides of these metals on textile. Textile mangling or ironing is performed at 180 - 230°C temperature, depending on kind of textile. Upon heating the water evaporates, while nanoparticles of copper and/or silver and/or CuO and/or Ag20 are mechanically pressed into fabric. Also upon heating the reduction of copper(II) and silver(I) into metallic copper and silver occur, respectively. Metal nanoparticles are formed in situ.
Due to this invention the fabrics gain antibacterial, bacteriostatic, and antifungal properties, which are adjusted at every washing/mangling cycle.
The invention will be exemplified as follows:
Example 1. In order to obtain nanoparticles of copper and CuO dispersed uniformly on the surface of cotton fabric, 5 kg of dry cotton fabric were processed as follows: a) preliminary washing at 15 L solution containing 80 g of washing specimen Tenalan at 70°C b) essential washing in ί 5 L solution of 20g of disinfecting-bleaching agent PENTA- ACTIV c) twice rinsing with 15 L water d) rinsing with 15 L solution of 4 g Tenapre Exquist agent and 20 000 mg copper as nanoparticles obtained by mixing 14 L water, 4 g Tenapre Exquist agent and 1 L 5: 1 water-glycerol mixture, containing Cu nanoparticles of average 50 nm diameter size. e) drying f) mangling at 200°C.
According to this protocol the content of copper nanoparticles immobilized on textile surface was 200 mg Cu/kg textile.
Biological activity of resulted textile was tested on Candida albicans ATCC 10231, Candida glabrata, DSM 1 1226, Candida tropicalis KKP 334, Saccharomyces cerevisiae JG, Saccharomyces cerevisiae JG CDR1 and Staphylococcus aureus ATCC 9763. The suspension of 24 hour microorganism culture containing 106 cfu/ml was 10 times diluted with nourishment. The 7 cm2 sample of fabric was sterilized by UV irradiation and placed in 2.5 ml of the cell culture prepared as described above. This mixture was shaken for 1 hour and 1 ml suspension aliquots were then diluted with sterile physiological salt. From these diluted samples 0.1 ml samples were used to surface inoculation on plates with YEPG (for fungi) or TSA (for bacteria). After 24 hour incubation of plates at 30 °C (in case of fungi) or 37 °C (in case of bacteria) the colonies of microorganisms were counted.
It has been found that fabric modified v/ith Cu and CuO nanoparticles resulted in inhibition of bacteria and fungi growth from 40% to 95%.
Example 2. In order to obtain cotton fiber with antibacterial and antifungal properties, with the surface modified with mixture of nanocomposites Cu/CuO and Ag/Ag20 type, 5 kg of dry cotton fabric was processed as follows: a) preliminary washing at 15 L solution containing 80 g of washing specimen Tenalan at 70°C b) essential washing at 15 L solution with 20 g of disinfecting-bleaching agent PENTA-ACTIV c) twice rinsing with 15 L water d) rinsing with 15 L solution of 4 g Tenapre Exquist agent and 3 000 mg copper as nanoparticles and 7 500 mg silver as nanocomposite of Ag/Ag20 obtained by mixing 14 L water, 4 g Tenapre Exquist agent and 1 L 5: 1 water-glycerol mixture, containing Cu/CuO nanoparticles of average 30-60 nm diameter size and Ag/AgO nanoparticles of average 50-70 nm diameter size. e) drying f) mangling at 200°C.
In this way the content of copper and silver immobilized on the fabric surface was about 30 mg of Cu nanoparticles per kg of fabric and about 75 mg of Ag nanoparticles (as Ag/Ag20 nanocomposite) per kg of fabric.
Biological activity of resulted textile was tested on Candida albicans ATCC 10231 , Candida glabrata, DSM 1 1226, Candida tropicalis KKP 334, Saccharomyces cerevisiae JG, Saccharomyces cerevisiae JG CDR1 and Staphylococcus aureus ATCC 9763. The suspension of 24 hour microorganism culture containing 106 cfu/ml was 10 times diluted with nourishment. The 7 cm2 sample of fabric was sterilized by UV irradiation and placed in 2.5 ml of the cell culture prepared as described above. This mixture was shaken for 1 hour and 1 ml suspension aliquots were then diluted in sterile physiological salt. From these diluted samples 0.1 ml samples were used to surface inoculation on plates with YEPG (for fungi) or TSA (for bacteria). After 24 hour incubation of plates at 30 °C (in case of fungi) or 37 °C (in case of bacteria) the colonies of microorganisms were counted.
It has been found that fabric modified with Cu/CuO and Ag/Ag20 nanoparticles resulted in inhibition of bacteria and fungi growth from 90% to 95%.
Example 3. In order to obtain cotton fabric covered with alloy-type bimetallic Cu/Ag nanocomposite, 10 kg of dry cotton fabric was processed as follows: a) preliminary washing in 30 L of 80 g washing specimen Tenalan at 70 °C temperature b) essential washing in 30 L solution containing 80 g of Tenalan at 70 °C temperature c) washing with disinfection at 30 L solution of 40 g of disinfecting-bleaching agent PENTA-ACTIV d) twice 30 L water rinsing e) rinsing with 30 L of solution containing 8 g Tenapre Exquist specimen f) drying g) impregnation with nanoparticles by spraying fiber surface with the solution containing 500 mg Cu/dm and 250 mg Ag/dm as bimetallic alloy-type nanoparticles of the 10 to 25 nm size, plant starch and polyvinylpyrrolidone at the proportion 2 liters of solution per 10 kg of cotton fiber h) mangling at 180 °C temperature.
Resulting amount of copper and silver immobilized on fabric surface was 100 mg Cu/kg of fabric and 50 mg Ag/kg of fabric as bimetallic alloy-type Cu/Ag nanoparticles. Biological activity of resulted fabric was tested on Candida albicans ATCC 10231 , Candida glabrata, DSM 1 1226, Candida tropicalis KKP 334, Saccharomyces cerevisiae JG, Saccharomyces cerevisiae JG CDRl and Staphylococcus aureus ATCC 9763.
It has been found that the fabric modified with bimetallic Cu/Ag nanoparticles inhibited the bacteria and fungi growth up to 98%, depending on type of microorganism.
Example 4. In order to obtain cotton fabric covered with mixture of nanoparticles of copper, nanoparticles of silver, nanoparticles of copper(II) oxide, and nanoparticles of silver(I) oxide, 10 kg of dry cotton fabric was processed as follows: a) preliminary washing in 30 L of 80 g washing specimen Tenalan at 70 °C temperature b) essential washing in 30 L solution containing 80 g of Tenalan at 70 °C temperature c) washing with disinfection at 30 L solution of 40 g of disinfecting-bleaching agent PENTA-ACTIV d) twice rinsing with 30 L water e) rinsing with 30 L of solution containing 8 g Tenapre Exquist specimen f) drying g) impregnation with nanoparticles by spraying fabric surface with the solution containing 2000 mg Cu/dm as copper citrate and 1000 mg Ag/dm as silver citrate, plant starch and polyvinylpyrrolidone at the proportion 1 liter of solution per 10 kg of cotton fabric h) mangling t at 180 °C temperature.
The Cu, CuO, Ag, and Ag20 nanoparticles are formed at the fabric surface in situ during mangling upon high temperature.
Resulting amount of copper and silver immobilized on fabric surface was 200 mg Cu/kg of fabric and 100 mg Ag/kg of fabric as a mixture of nanoparticles of copper, nanoparticles of silver, nanoparticles of copper(II) oxide, and nanoparticles of silver(I) oxide.
Biological activity of resulted fabric was tested on Candida albicans ATCC 10231, Candida glabrata, DSM 1 1226, Candida tropicalis KKP 334, Saccharomyces cerevisiae JG, Saccharomyces cerevisiae JG CDRl and Staphylococcus aureus ATCC 9763.
It has been found that the fabric modified with mixture of nanoparticles of copper, nanoparticles of silver, nanoparticles of copper(II) oxide, and nanoparticles of silver(I) oxide inhibited the bacteria and fungi growth up to 95%, depending on type of microorganism.
Example 5. In order to obtain cotton fabric covered with nanoparticles of copper and copper(II) ions, 5 kg of dry cotton fabric was processed as follows: a) preliminary washing in 15 L solution of 80 g washing specimen Tenalan at 70 °C temperature b) washing with disinfection in 15 L solution of 20 g of disinfecting-bleaching agent PENTA-ACTIV at 75 °C c) twice rinsing with 15 L water d) rinsing with 15 L water solution containing 6 g Tenapre Exquist specimen and 8 g of copper citrate e) drying f) impregnation with nanoparticles by spraying the fiber surface with solution containing 500 mg Cu/dm as Cu nanoparticles, preferably of the size below 20 nm and 500 mg of copper(II) citrate, plant starch, and polyvinyl alcohol at the proportion 0.5 liter of solution per 5 kg of cotton fabric g) mangling at 180°C.
Resulting amount of copper immobilized on fabric surface was 50 mg Cu/kg of fabric as a nanoparticles of copper and 50 mg Cu/kg of fabric as copper(II) ions.
Biological activity of resulted fabric was tested on Candida albicans ATCC 10231, Candida glabrata, DSM 1 1226, Candida tropicalis KKP 334, Saccharomyces cerevisiae JG, Saccharomyces cerevisiae JG CDR1 and Staphylococcus aureus ATCC 9763.
It has been found that the fabric modified with nanoparticles of copper and copper(II) ions inhibited the bacteria and fungi growth up to 90%, depending on type of microorganism.
Example 6. In order to obtain nanoparticles of Cu@CuO composed of metallic copper as core and copper(II) oxide as sheath deposited on the cotton fabric surface, 10 kg of dry cotton fabric was processed as follows: a) preliminary washing in 30 L of 80 g washing specimen Tenalan at 70 °C temperature b) essential washing in 30 L solution containing 80 g of Tenalan at 70 °C temperature c) washing with disinfection at 30 L solution of 40 g of disinfecting-bleaching agent PENTA-ACTIV d) twice rinsing with 30 L water e) rinsing with 30 L of solution containing 8 g Tenapre Exquist specimen f) drying_ g) impregnation with nanoparticles by spraying the fabric surface with solution containing 1500 mg Cu/dm as Cu@CuO nanoparticles of core-sheath structure, in which the Cu : CuO weight ratio is 2: 1 and particle size is 10 to 25 ran, plant starch and polyvinylpyrrolidone at the proportion 2 liters of solution per 10 kg of cotton fabric h) mangling at 180°C temperature.
Resulting amount of copper immobilized on fabric surface was 300 mg Cu/kg of fabric as Cu@CuO nanoparticles of of core-sheath structure.
Biological activity of resulted fabric was tested on Candida albicans ATCC 10231 , Candida glabrata, DSM 1 1226, Candida tropicalis KKP 334, Saccharomyces cerevisiae JG, Saccharomyces cerevisiae JG CDR1 and Staphylococcus aureus ATCC 9763.
It has been found that the fabric modified with Cu@CuO nanoparticles of metallic copper core and copper(II) oxide sheath inhibited the bacteria and fungi growth up to 99%, depending on type of microorganism.
Exampie 7. In order to obtain cotton fabric possessing antimicrobial and antifungal properties, with surface covered with mixture of Cu@CuO nanoparticles (possessing structure metallic copper core and copper(II) oxide sheath) and Ag@Ag20 nanoparticles (possessing structure metallic silver core and silver(I) oxide sheath), 10 kg of dry cotton fabric was processed as follows: a) preliminary washing in 30 L of 80 g washing specimen Tenalan at 70 °C temperature b) essential washing in 30 L solution containing 80 g of Tenalan at 70 °C temperature c) washing with disinfection at 30 L solution of 40 g of disinfecting-bleaching agent PENTA-ACTIV d) twice rinsing with 30 L water e) rinsing with 30 L of solution containing 8 g Tenapre Exquist specimen f) drying
Figure imgf000014_0001
solution- containing: 750 mg Cu/dm as Cu@CuO nanoparticles of core-sheath structure, with Cu to CuO weight ratio 5: 1 and preferable particle size 10 to 25 nm, 750 mg Ag/dm3 as Ag@Ag20 nanoparticles of core-sheath structure, with Ag to Ag20 5: 1 and particle size 40 to 60 nm, and plant starch and polyvinylpyrrolidone, at the proportion 2 liters of solution per 10 kg of cotton fabric h) mangling at 180 °C.
Resulting amount of copper and silver immobilized on fabric surface was 150 mg Cu/kg of fabric as Cu@CuO nanoparticles of core-sheath structure and 150 mg Ag/kg of fabric as Ag@Ag20 nanoparticles of core-sheath structure.
Biological activity of resulted fabric was tested on Candida albicans ATCC 10231 , Candida glabrata, DSM 1 1226, Candida tropicalis KKP 334, Saccharomyces cerevisiae JG, Saccharomyces cerevisiae JG CDRl and Staphylococcus aureus ATCC 9763.
It has been found that the fabric modified with Cu@CuO nanoparticles and Ag@Ag20 nanoparticles inhibited the bacteria and fungi growth up to 95% to 99%, depending on type of microorganism.

Claims

Patent claims
1. We claim the method of furnishing fabric during washing, which comprise of preliminary washing, essential washing, water rinsing with further water removal, and then neutralization and/or starching, and/or softening, final centrifugation and drying, wet or dry pressing, characteristic of that during softening step and/or after centrifuging step the fabric is treated with specimen containing nanoparicles of copper and copper(II) oxide and/or other compounds of copper(II) of 20- 50 nm diameter average size, or with specimen containing nanoparicles of copper and copper(II) oxide and/or other compounds of copper(II) of 20- 50 nm diameter average size as well as nanoparticles of silver and silver(I) oxide and /or other compounds of silver(I) of 20- 50 nm diameter average size, the weight ratio of metals being between 10: 1 and 1 : 10, the copper nanoparticles or silver and copper nanoparticles are introduced in such a way which ensures the final amount of 10 - 1000 mg of copper or copper and silver per 1 kg of dry fabric; furthermore at the softening step the known softener is introduced into washing bathwater and after the centrifuging step the refiner is introduced, followed by water removal and afterwards the nanoparticles of copper or copper and silver and their oxides are stabilized on fabric surface by exposing the fabric to high temperature during dry or wet pressing (ironing or mangling).
2. The method claimed at point 1 is characteristic of that copper and silver are introduced as specimen containing bimetalic nanoparticles of alloy type composed of metallic copper and metallic silver, of average 20-50 diameter size, with weigh ratio of metals from 10: 1 to 1 : 10 and/or mixture of specimen composed of Cu/CuO and Ag/Ag20 nanocomposite of core-sheath (metal core and metal oxide sheath) of the size below 20 nm diameter, with weigh ratio of metal to metal oxide being between 1 : 1 and 1 :5.
3. The method claimed at point 1 is characteristic of that during softening step the textile is treated with specimen A contaning nanoparticles of copper and/or copper(II) oxide and/or other compounds of copper(II) as well as softener, and then is treated with specimen B, contaning nanoparticles of silver and/or silver(II) oxide and/or other compounds of silver(I) as well as softener.
4. The method claimed at point 1 is characteristic of that after centrifuging step, the textile is treated, preferably splashed with specimen A, containing nanoparticles of copper and/or copper(II) oxide and/or other compounds of copper(II), as well as refiner, and then is treated with specimen B contaning nanoparticles of silver and/or silver(II) oxide and/or other compounds of silver(I) as well as refiner.
5. The method claimed at point 1 is characteristic of that softener contains anionic and/or cationic and/or non-ionic surfactants, while refiner contains anionic and/or cationic and/or non-ionic surfactant and/or glycerol and/or plant starch and/or polyvinylpyrrolidone and/or polyvinyl alcohol.
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