SK288551B6 - The method of finishing textiles during the washing cycle - Google Patents

Abstract

Disclosed is the method of finishing textiles during the washing cycle, whereby during softening and/or after centrifugation, the textile is treated with a composition containing copper nanoparticles or copper and silver nanoparticles in the form of Cu/CuO and Ag/Ag2O nanocomposites with a core-shell structure, where the core is a metal and the shell is a metal oxide, in an amount ensuring application from 10 to 1000 mg of copper or copper and silver per 1 kg of dry textile. The weight ratio of the metals in the nanoparticle composition consisting of copper and silver is from 10:1 to 1:10, while the weight ratio of the metal and the metal oxide nanocomposites in the form of core-shell is from 1:1 to 5:1. The nanoparticles of copper or copper and silver are then stabilized on the textile surface during ironing or mandling at a teperature form 180 to 230øC. The preferred size of the copper and silver nanoparticles is 20 to 50 nm.

Description

Technical field

It is an object of the present invention to provide a method of finishing textiles during laundering, particularly useful in large laundry laundries for hospitals, hotels and the like, as well as work clothes.

BACKGROUND OF THE INVENTION

Many surface finishes of textiles, cotton and synthetic fibers are known, including impregnation, to make these fibers, for example, antiseptic, waterproof or fireproof. It is also known that silver and copper have antibacterial properties.

Copper has been used in the treatment of certain diseases and for hygienic purposes since ancient times.

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] the addition of copper to nanocomposites results in inhibition of the growth of E. coli and Listeriv, copper has been described as an antimicrobial agent when added to polyvinylpyrrolidone coatings used in medicine.

Perelshtein et al. (2009) [Perelshtein I, Applerot G, Perkasa 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 a thin layer of metal oxides, among other copper oxides, deposited on the surface of the cotton fiber, has antibacterial activity against Staphylococcus aureus.

Borkowo and Gabbay (2004) [Borkowo 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 has a broad spectrum of biological activity, e.g. antibacterial, antifungal, antiviral, anti-mite.

The antibacterial and antifungal properties of copper have also been described by Grace et al (2009) Grace M., Bajpai SK, Chand N. Copper (II) ions and copper nanoparticles-loaded chemically modified cotton cellulose fibers with fair antibacterial properties, Journal of Applied Polymer Science 113 (2009) 757-766], which discloses the release of copper (II) from cellulose fibers that has been treated with periodate oxidation and subsequently copper (0) nanoparticles of 29 nm mean diameter were coupled to chitosan by reduction with sodium borohydride. The treated fibers had a very high antibacterial 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] described a polymer nanocomposite comprising copper nanoparticles as an antibacterial and antifungal agent. It has been experimentally demonstrated that nanoparticles have been released from the surface of the nanocomposite, thereby inhibiting the growth of fungi and other pathogenic microorganisms. The biological activity was correlated with the content of metal nanoparticles.

The described properties of silver and copper resulted in their use in practice.

A liquid composition having antibacterial and antifungal properties, for cleaning interiors such as floors and walls, also sanitary facilities and equipment, containing inter alia at least one nanosilver colloid (0) in a concentration of up to 500 ppm in an amount of 1-99% by weight and / or at least one nanomedi (0) colloid having a concentration of up to 500 ppm in an amount of 1-99 weight percent was described in Polish patent application no. P.390497.

In the case of fabrics, methods have been described for depositing and placing said metals on their surface. This was accomplished by various chemical and physical methods.

A method for impregnating fabrics with silver nanoparticles is described in Polish patent application P. 387686. In this process, fabrics are treated with chemical compounds such as: acetic acid and / or sodium hydroxide solution and benzoyl chloride and / or polymer solutions such as: polyacrylamide, polyvinylpyrrolidone, polyvinyl alcohol; polyacrylic acid, in order to replace the hydroxyl group (-OH) with functional groups corresponding to the type of modifying agent, or to reduce the number of -OH groups on the surface. The treated fabrics are then impregnated with a colloidal solution containing 100 to 2000 mg Ag / dm ³ , obtained by reduction of the silver salt (I) with sodium borohydride or citric acid. Water is then removed from the fibers, preferably by neutral gas drying.

Another method is described in US Patent No. 8,183,167 B1, in which fabrics are coated with well dispersed metal nanoparticles of antibacterial properties, such as silver and / or copper, which are bound by a covalent bond. Metal powder nanoparticles (silver and / or copper) are mixed with a solution containing a component compatible with the reactive block copolymer, then their polymer suspension is transferred to an extruder in which the polymer-nanoparticle composite granules are formed. The resulting nanocomposite is mixed with the base polymer to obtain fibers in the weaving process.

In the modified process, silver and / or copper nanoparticles, as well as their oxides, are obtained by the Turkevich method (i.e., reducing metal cations with citrate or ascorbic acid) to form a colloidal polymer solution from which granules of the polymer-nanoparticle composite are extruded. Then, the zeros of the nanocomposite are mixed with the base polymer, and synthetic fibers are formed by weaving. The fabrics thus obtained have antibacterial, antifungal and fungistatic 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] described a method for obtaining colloidal copper and applying it to cotton fibers. Colloidal copper particles of average size 60-100 nm were obtained by reduction of copper (II) with sodium borohydride in the presence of sodium citrate. The fabric was impregnated by immersion in a solution of colloidal copper (solution: fabric ratio was 50: 1) at 40 ° C for 60 min. and then at 80 ° C for 30 min. Finally, the fabric was rinsed with water and air dried. The copper-impregnated fabric had antibacterial activity.

Methods for placing metals on the fiber surface during washing have also been described.

Polish patent application P.322021 discloses a liquid composition comprising a peroxide bleaching agent and a chelating agent for copper and / or iron, and / or manganese for prewash, and compositions useful in the process.

Another patent application P.397964 has disclosed a method of finishing fibers with antibacterial silver particles during the washing process. Particularly during fabric softening, the fibers are exposed to a mixture of colloidal silver and / or ionic silver and a softening agent containing surfactants in a ratio such that the mixture contains 100-5000 mg Ag / dm ³ and / or the fibers are spun by a mixture containing colloidal silver, surfactants and / or glycerol, and / or vegetable starch, and / or polyvinylpyrrolidone, and / or polyvinyl alcohol; the mixture contains 100-5000 mg Ag / dm ³ as silver nanoparticles not greater than 100 nm. This is followed by drying. Silver nanoparticles are stabilized on the fiber surface by heating in the mangling or ironing phase.

A softening composition with excellent antibacterial and anti-odor properties is known from the patent specification JP.20043006660. The softening composition contains 0.01-10% by weight of microcapsules containing a silver diameter below 500 nm. This not only limits the growth and proliferation of microorganisms, but also suppresses unpleasant odors in garments worn or dried in humid conditions, such as in summer or rainy days.

JP 2007046184 discloses a method of antimicrobial treatment of natural fibers. This treatment was achieved by washing the fibers of animal or vegetable origin with a basic detergent pH 12-13 in hot water, followed by spraying and impregnating with ionic water containing an antimicrobial agent as silver, copper or titanium dioxide nanoparticle particles with a diameter of 1-20 nm. reached a final concentration of 150-5 ppm in or on the fiber, then washing with a detergent to allow the antimicrobial agent to enter the fiber, and finally drying the fiber at 60 - 120 ° C to immobilize the antimicrobial agent in the fiber structure.

Another patent EP 1947167 discloses a fiber softening composition comprising 5-60 weight percent antistatic agent, 0.5-5 weight percent quencher, 1-5 weight percent armatures, 0.01-0.1 weight percent dyes and water containing 1 - 10,000 ppm of metal nanoparticles such as silver, gold, copper, zinc and their biologically active compounds.

A disadvantage of the known finishing methods is the impossibility of adjusting the content of biologically active metals in the textiles during their use, which causes a decrease in their antimicrobial activity.

The last step of water washing is textile mangling / ironing, usually carried out at a temperature of 180-230 ° C, depending on the type of fabric. This eliminates most bacteria. But the achieved state is not permanent, the number of bacteria and fungi increases during the use of textiles. This is a fundamental problem in the case of bed linen and work clothes used in hospitals and other medical facilities, nursing homes for seniors, hotels, prisons, etc. In these areas, an increase in the population of bacteria, particularly pathogenic, can lead to the development of infections and infectious diseases in immunocompromised persons.

Although adjusting the amount of nanosilver in textile during the washing process is known from patent application P.397964, it has unexpectedly been found that applying nanoparticles of silver and copper together as a composition comprising Cu / CuO and Ag / Ag2O nanocomposites with a core-shell structure is more advantageous. and a more efficient solution.

It is an object of the invention to improve the antibacterial, antifungal properties and limit the spread of mites in textiles during a washing process, especially on a large scale, as compared to known and described processes.

SUMMARY OF THE INVENTION

A method of finishing fabrics during a washing process in which the fabrics undergo prewashing, washing, rinsing and suction, neutralization and / or starching, and / or softening, final spinning, drying, mangling or ironing, provided that:

during the softening bath and / or after the spin bath, the fabrics are treated with a composition comprising copper nanoparticles having a mean diameter of 20-50 nm and copper oxide (II) and / or other copper compounds (II) or composition containing copper nanoparticles and copper oxide (II) and / or other copper compounds (II) and silver nanoparticles with a mean diameter of 20-50 nm and silver oxide (I) and / or other silver compounds (I) according to the invention are based on the introduction of copper or copper nanoparticles and silver as a preparation containing Cu / nanocomposites. CuO and Ag / Ag2O core-shell in amounts providing 10-1000 mg of copper nanoparticles or copper and silver nanoparticles per kg dry matter, with a metal-to-metal weight ratio of 10: 1 to 1: 10, and a metal-oxide ratio the metal makes from 1: 1 to 5: 1, and the nanoparticles of copper or copper and silver are stabilized in the fabric surface by exposing the fabric to a high temperature during ironing or mangling at 180-230 C.

The preferred size of copper and silver nanoparticles is 20-50 nm.

In general, the washing technology providing textiles with antibacterial properties comprises the following steps:

(a) prewash;

b) own washing with disinfection,

c) rinsing followed by suction of water,

(d) neutralization / starch / softening / impregnation of the copper and / or silver preparation;

(e) final centrifugation,

f) drying, mangling or ironing with concomitant immobilization and stabilization of copper and / or silver nanoparticles and / or metal oxides.

In the proposed process, the residual water content after washing clothes is 45%, which further decreases by mangling. The fabrics are subjected to mechanical and thermal treatment after washing and removal of water during the mangling or ironing process accompanied by the immobilization of copper or copper nanoparticles and silver and oxides of these metals to the fabric. Mangling or ironing of fabrics takes place at a temperature of 180 - 230 ° C, depending on the type of fabric. On heating, water evaporates, while copper and CuO or copper and silver nanoparticles and CuO and Ag2O and / or Cu (II) ions or Cu (II) and Ag (I) ions and / or bimetallic Cu / Ag nanoparticles are mechanically " ironed 'into the fabric. Also, during heating, copper (II) and silver (I) are reduced to metallic copper and silver. In this way, metal nanoparticles are formed in situ.

Thanks to the present invention, the substances acquire bactericidal, bacteriostatic and antifungal properties which are modified in each wash / mange cycle.

DETAILED DESCRIPTION OF THE INVENTION

The invention will be illustrated by the following examples.

Example 1

For the purpose of obtaining a core / shell Cu / CuO nanoparticle, wherein the core is copper and the shell is copper oxide dispersed evenly on the surface of the cotton fabric, 10 kg of dry cotton fabric was treated as follows:

(a) prewash in 30 l of a solution containing 80 g of Tenalan detergent at 70 ° C;

(b) self-washing in 30 l of a solution containing 80 g of Tenalan detergent at 70 ° C;

(c) washing with disinfection in 30 l of a solution containing 40 g of disinfectant-bleach PENTA-ACTIV,

d) double rinsing in 30 l of water,

(e) rinse in 30 l of solution with 8 g of Tenapre Exquist;

f) drying,

g) impregnation with nanoparticles by spraying the surface of a 2 L solution per 10 kg of a substance containing 1500 mg Cu / dm ³ as Cu / CuO core-shell nanoparticles, wherein the Cu: CuO weight ratio is 2: 1, nanoparticle diameter is 10-25 nm , starch and polyvinylpyrrolidone,

(h) Manganese at 200 ° C.

According to this procedure, the copper content immobilized on the fabric surface was 300 mg Cu / kg of fabric, as Cu / CuO core-shell nanoparticles.

The biological activity of the obtained substance was tested on Candida albicans ATCC 10231, Candida glabrata, DSM 11226, Candida tropicalis KKP 334, Saccharomyces cerevisiae JG, Saccharomyces cerevisiae JG CDR1, and Staphylococcus aurens ATCC 9763. It was found that Cu / O the coating inhibits the growth of bacteria and fungi by up to 99%.

Example 2

For the purpose of obtaining cotton fibers with antibacterial and antifungal properties, with a surface treated mixture of Cu / CuO and Ag / Ag2O nanocomposites where copper is the core and copper oxide (II) as the coating and also silver as the core and silver oxide (I) as packaging, 10 kg of dry cotton fabric was processed as follows:

(a) prewash in 30 l of a solution containing 80 g of Tenalan detergent at 70 ° C;

(b) self-washing in 30 l of a solution containing 80 g of Tenalan detergent at 70 ° C;

(c) washing with disinfection in 30 l of a solution containing 40 g of disinfectant-bleach PENTA-ACTIV,

d) double rinsing in 30 l of water,

(e) rinsing in 30 l of a solution containing 8 g of Tenapre Exquist;

f) drying,

g) impregnating with nanoparticles by spraying the surface of a 1 liter solution per 5 kg of fabric when the solution contains 750 mg Cu / dm ³ as Cu / CuO core-shell nanoparticles where the Cu: CuO weight ratio is 5: 1, the nanoparticle diameter is 10 - 25 nm, 750 mg Ag / dm ³ in the form of Ag / AgO core-shell nanoparticles, where the weight ratio of Ag to Ag ₂ O is 5: 1, the nanoparticle diameter is 40-60 nm, starch and polyvinylpyrrolidone, 200 ° C.

In this way, the content of copper and silver immobilized on the surface of the fabric was about 150 mg of Cu nanoparticles per kg of fabric, applied as a Cu / CuO nanoparticles of core-shell, and about 150 mg of Ag nanoparticles per kg of fabric, applied as an Ag / Ag ₂ 0 nanoparticles core-shell.

The resulting biological activity of the fabric was tested on Candida albicans ATCC 10231, Candida glabrata, DSM 11226, Candida tropicalis KKP 334, Saccharomyces cerevisiae JG, Saccharomyces cerevisiae JG

CDR1 and Staphylococcus aureus ATCC 9763.

It has been found that the fabric is treated with nanoparticles of Cu / CuO and Ag / Ag ₂ O inhibits the growth of bacteria and fungi from 95% to 99% (depending on the microorganism).

Claims (1)

PATENT CLAIMS 1. A method of finishing fabrics during a wash, during which the fabrics undergo prewashing, self-washing, water-suction rinsing followed by neutralization and / or starching, and / or softening, finally spinning5 and drying, mangling or ironing within which the fabrics are during softening and / or after centrifugation, treated with a composition comprising nanoparticles of average size less than 500 nm, characterized in that the nanoparticles are copper nanoparticles or copper and silver nanoparticles, wherein the nanoparticles of the treatment agent are applied to the Ag / Ag2 type nanocomposite and nanocomposite fabric / or Cu / CuO with a core-shell structure, wherein the core consists of a metal which is copper or silver and a shell 10 is composed of a metal oxide, CuO or Ag2O, in an amount providing a final content of 10 to 1000 mg of copper or copper and silver per kg of dry fabric, the metal to metal ratio in the nanoparticle composition being between 10 and 1000; 1 to 1: 10, while the weight ratio of metal to metal oxide in core-shell nanocomposites is from 1: 1 to 5: 1, and the copper or copper and silver nanoparticles are stabilized on the fabric surface during ironing or mangling at temperature 180 15 DEG-230 DEG.