PL231089B1 - Method for biofunctionalization of textile materials - Google Patents

Description

Description of the invention

The subject of the invention is a method of functionalisation of textiles leading to antibacterial and antifungal properties.

Providing textiles with antibacterial and antifungal properties is very important in the case of their special applications, especially for the production of hygienic and sanitary materials and elements of protective clothing.

It has been known for quite a long time that copper oxide has antibacterial, antiviral and antifungal properties [e.g. G. Borkow, J. Gabbay, FASEB J., Vol. 18, 1728-1737 (2004); Antimicrobial Agents and Chemotherapy, Vol. 51, 2605-2607 (2007); International Journal of Antimicrobial Agents, vol. 33, 587-590 (2009); Formatex, 197-209 (2011); The Open Biology Journal, vol. 6, 1-7 (2013); International Journal of Pharmaceutical Research and Developments, vol. 6, 72-78 (2014)]. Although low concentrations of copper are sufficient for most microorganisms, higher doses are usually used to inhibit the growth of some microorganisms and obtain bactericidal activity [New Journal of Chemistry, vol. 35, 1198 (2011)]. Permanent biocidal properties of fabrics containing 3-10% copper were described by Gabbay, Borkow et al. [Journal of Industrial Textiles, vol. 35 (2006) 323-335].

From the publication of C.C. Trapalis'a et al. [Journal of Sol-Gel Science and Technology, vol. 26, 1213-1218 (2003)] there is known a method of obtaining thin composite silicate coatings containing copper (Cu / SiO2) on glass plates. Using the sol-gel method, as a result of hydrolysis with a stoichiometric amount of water, and then condensation of Si (OC2Hs) 4 tetraethoxysilane with copper acetylacetonate Cu (acac) 2, in an acidic environment (pH = 3), a homogeneous green solution was obtained, which was heated in at 70 ° C for 2 hours, then cooled to room temperature and dip applied to microscopic glass plates. Thin copper silicate layers were annealed in an oxidizing and reducing atmosphere at temperatures up to 500 ° C in order to produce Cu nanoparticles. The structure of the coatings was examined using the XRD method and the UV-Vis and HIRBS spectroscopic methods. The obtained coatings showed high antibacterial activity against Escherichia Coli strains, increasing with increasing metal concentration and decreasing with increasing temperature of thermal treatment in the process of Cu nanoparticle formation. However, the most effective antibacterial properties were shown by coatings that were not subjected to thermal treatment in an oxidizing or reducing atmosphere.

The Journal of Physical Chemistry B, vol. 110, 24923-24928 (2006) describes the deposition of copper on the surface of spherical silica nanoparticles to obtain the hybrid structure of the Cu-SiO2 nanocomposite. SiO2 nanoparticles served as a substrate for continuous copper deposition. The chemical structure and morphology of the nanocomposite were investigated by spectroscopy (XPS), X-ray energy scattering scanning electron microscopy (SEM-EDX) and transmission electron microscopy (TEM). Copper nanoparticles, homogeneously produced on the surface of SiO2 nanoparticles, did not aggregate and showed excellent antibacterial activity against many microorganisms.

Xerogels mesoporous silicate, copper of high surface area (463 m ² / g) and pore size of 2 nm, exhibiting antibacterial properties depends on the concentration of copper were also obtained by the sol-gel [Biomedical Materials, Vol. 4, 045,008 (2009)].

Ren et al. [International Journal of Antimicrobial Agents, vol. 33 (2009) 587-590] found that the minimum bactericidal concentration of CuO nanoparticles in relation to the bacteria Pseudomonas aeruginosa is about 5000 gg / ml. At the same time, they suggested that the release of copper ions into the local environment is necessary to maintain microbial activity. However, using the AAS method, no simple correlation was found between the amount of copper released from the polymer matrix and the inhibition of bacterial growth. Most likely, this effect was caused by other factors, such as the smoothness of the surface. Another reason could be the release of organic polymer components. It has been shown that the highest activity towards bacteria is shown by CuO nanoparticles with dimensions of 1-10 nm [Nanotechnology, vol. 16 (2005) 2346-2353, Dyes and Pigments, vol. 73 (2007) 298-304].

Surface-modified nanosilica with copper particles was used to remove the smell of mercaptans and sulfur compounds from crude oil. According to the publication in the Langmuir journal, vol. 26, 15837-15844 (2010), the silica modified by the addition of copper also showed antibacterial activity.

PL 231 089 B1

In copper silicate CuO-SiO2, the antibacterial and antifungal properties of copper oxide and virucidal activity are combined with the biocompatibility, non-toxicity and diversity of the silica surface. Copper silicate is used in medicine and biology, e.g. for the controlled release of drugs and thermal cancer therapy. An additional advantage of copper silicate CuO-SiO2 is the possibility of modifying its surface and properties using hydrophobic substances, simple chemical processes and organofunctional compounds [Bioelectrochemistry, vol. 87, 50-57 (2012)].

It is known from the publication in the journal Nanoscale Research Letters, vol. 6, 594-602 (2011) that cotton textiles impregnated with silica sol containing 0.5-2% wt. After drying, copper nanoparticles showed excellent antibacterial properties against both gram-negative and gram-positive bacteria. In order to block the silica hydroxyl groups, some samples were modified by reaction with hexadecyl (trimethoxy) silane.

According to the article in the Journal of Biomedical Nanotechnology, vol. 8, 558-566 (2012), SiO2 nanoparticles with the "nucleus-shell" structure containing the addition of approx. 0.1 μg Cu (in the form of insoluble copper hydroxide) had much better antibacterial properties against Escherichia coli and Bacillus subtilis bacteria than was observed for Cu (OH) 2 alone. In the case of CuSiO3 with the "nucleus-shell" structure, the minimum concentration inhibiting the growth of these bacteria was 2.4 µg Cu / ml. On the other hand, the publication in the Journal of Agricultural and Food Chemistry (2014; dx.doi.org/10.1021/jf502350w) shows that silica nanocomposites with copper compounds of different valences, especially enriched by the addition of Cu (0) and Cu (l ) showed higher antimicrobial efficacy than Cu (II) compounds - against Xanthomonas alfalfae and Escherichia coli. Phytotoxicity studies in greenhouse conditions (with Vinca sp. And Hamlin orange) have shown that these nanocomposites are safe for plants and can be used as biocides in agriculture.

AMB Express, vol. 3, 53 (2013) describes the very good antibacterial properties of Cu-SiO2 nanocomposites obtained in the form of thin films by CVD method against numerous pathogens present in hospital conditions (Acinetobacter baumannii, Klebsiella pneumoniae, Stenotrophomonas maltophilia, Enterococcus faecium , Staphylococcus ureus and Pseudomonas aeruginosa). The nanostructure of Cu particles in a silica matrix was confirmed by the SEM method. The tested Cu-SiO2 nanocomposite coatings can also be used for the microbiological protection of metal and ceramic surfaces.

From an article in the Digest Journal of Nanomaterials and Biostructures, vol. 8, 869-876 (2013), it is known that copper and zinc alginates and their composites with silica have a stronger antibacterial effect than ordinary Cu and Zn salt solutions against Enterococcus faecalis bacteria, although they were used at a lower concentration. Moreover, these hybrid materials turned out to be biocompatible and did not cause cytotoxic effects on eukaryotic cells. They can therefore be useful for the gradual release of drugs and tissue engineering, while maintaining high microbial activity over time.

Information published in the journal Colloids and Surfaces B: Biointerfaces, vol. 108, 358-365 (2013) shows that copper nanoparticles deposited on the surface of sodium montmorillonite (MMT), or intercalated inside its layer structure, showed high persistence in the air atmosphere ( over 3 months) and excellent microbiological activity against various bacterial colonies: Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa, Enterococcus faecalis, resulting in the disappearance of> 90% of bacteria after 12 hours. Cytotoxicity tests showed a minimal adverse effect of this nanocomposite on human cells when the minimum the growth inhibitory concentration (MBC) of these microorganisms. Nevertheless, there are promising prospects for applications of the MMT-Cu nanocomposite for therapeutic purposes.

On the other hand, the Journal of Materials Science, vol. 41, 5208-5212 (2006) describes the strong antibacterial properties of monodisperse copper nanoparticles with dimensions of 2-5 nm, deposited on magnesium silicate [MgsSh2O3o (OH) 4 (H2O) 4 * 8H2O] ( sepiolite) against Staphylococcus aureus and Escherichia coli. Their effectiveness turned out to be comparable to the biological activity of Triclosan.

The information published in the Journal of Materials Chemistry B, vol. 2, 846-858 (2014) shows that also Cu ² + ions embedded in the structure of calcium silicate CaSiO3 layers deposited by electrophoresis on the titanium surface are gradually released from such a coating and show good antibacterial properties against Escherichia coli and Staphylococcus aureus bacteria strains, as well as increased anti-corrosion resistance in relation to pure titanium. However, CaSiO3 itself does not have antibacterial properties.

PL 231 089 B1

According to an article in the journal Biochimica et Biophysica Acta, vol. 1840, 3264-3276 (2014), both spherical copper and silver nanocomposites with mullite (3Al2O3'2SiO2) demonstrate strong antibacterial properties against Escherichia coli and Staphylococcus aureus. However, the microbial activity of the copper-mullite nanocomposite turned out to be higher than that of the silver-mullite nanocomposite, presumably due to the smaller particle size of this composite. Both nanocomposites showed good cytocompatibility at 1 mg / ml (M.B.C.) and therapeutic properties in the treatment of wounds in mice.

The essence of the invention is the method of biofunctionalization of textiles with the use of copper silicate, preferably in the form of a hydrate, which is premixed with the polymer component and plasticizer, the whole is heated to the polymer melt, and then the molten composition is subjected to the process of pneumothermic extrusion and blowing of the liquid polymer melt in hot air. Copper silicate is used in the form of a hydrate in an amount of 0.1-4% by weight.

In the process of the invention, polymers selected from the group consisting of polypropylene (PP) and its copolymers, polylactide (PLA), polyhydroxyalkanoates (PHA), polyethylene (PE) and / or mixtures thereof are used as polymer components. Alternatively, copper silicate is used in the form of a concentrate with a polymer, containing 1-25% by weight of copper silicate hydrate, which is mixed with the same or different polymer and other ingredients in such proportions by weight that the content of copper silicate hydrate in the fabric produced is 0. 1-4% by weight.

The plasticizers used are compounds of liquid consistency, selected from the group consisting of: ethylene glycol or propylene glycol oligomers, ethylene glycol and propylene glycol copolymers, monoalkyl ethers of ethylene glycol oligomers, glycerin esters, citric acid or tartaric acid esters, pentaerythritol acid esters, diesters of acid phthalic acid, paraffin oil, epoxy resins, hydroxyalkyl or hydroxyether polysiloxanes, oligoesters of silicic acid, oligodimethylsiloxanediol, polycarbonate diol, polycaprolactone or polycaprolactone diol. Plasticizers are used in an amount of 1.5-15% by weight relative to the weight of the polymer or the weight of the polymer mixture, preferably 2.5-5% by weight.

The following non-limiting examples illustrate the subject matter of the invention.

Example 1 (sample 5 in table 1).

To 100.0 g of HL 512 FB polypropylene (PP) pellets were added 5.0 g of ethylene glycol oligomer with a number average molecular weight of 600 g / mol (Polikol PEG 600), followed by 2% by weight of anhydrous copper silicate powder. The apparatus for the production of bioactive textiles includes: a screw extruder, a fiberising head, a compressed air heater and a receiving device in the form of a moving drum.

The processing parameters of PP were as follows:

temperature of the 1st zone of the extruder: 240 ° C, temperature of the 2nd zone of the extruder: 280 ° C, temperature of III zone of the extruder: 285 ° C, head temperature: 240 ° C, air heater temperature: 260-280 ° C, screw rotation speed: 50 rpm polymer performance: 3.4 g / min air flow: 8.8 m ³ / h.

After establishing the above-mentioned parameters for the processing of PP, all ingredients were thoroughly mixed and transferred to the hopper of the single-screw extruder. Next, the process of extruding the composite polypropylene non-woven fabric with the m elt-blown method was started. The obtained non-woven fabric was tested for microbiological activity against colonies of gram-negative (Escherichia coli) and gram-positive (Staphylococcus aureus) bacteria and Candida albicans.

Example 2 (sample 2 in table 1).

To 75.0 g of HL 512 FB (PP) polypropylene granulate was added 25.0 g of maleic anhydride grafted polypropylene (PP-g-MA) and 5.0 g of ethylene glycol oligomer with a number average molecular weight of 600 g / mol (Polikol PEG 600), and then 1% by weight of powdered copper silicate hydrate with the following chemical composition: 35.23% by weight. CuO, 62.16 wt. SiO2, 18.52 wt.% H2O, 0.02 wt.% Na2O and 0.01 wt.%. K2O.

PL 231 089 B1

The processing parameters of PP were as follows:

temperature of the 1st zone of the extruder: 240 ° C, temperature of the 2nd zone of the extruder: 280 ° C, temperature of III zone of the extruder: 285 ° C, head temperature: 240 ° C, air heater temperature: 260-280 ° C, screw rotation speed: 50 rpm polymer performance: 3.4 g / min air flow: 8.8 m ³ / h.

After establishing the above-mentioned parameters for the processing of PP, all ingredients were thoroughly mixed and transferred to the hopper of the single-screw extruder. Then the melt-blown method of extruding the composite polypropylene non-woven material was started. The obtained non-woven fabric was tested for microbiological activity against colonies of gram-negative (Escherichia coli) and gram-positive (Staphylococcus aureus) bacteria and Candida albicans.

Example 3 (sample 3 in table 1).

To 90.0 g of HL 512 FB (PP) polypropylene pellets were added 10.0 g of a polypropylene concentrate containing 10% by weight of powdered copper silicate hydrate (k-PP) and 5.0 g of ethylene glycol oligomer with a number average molecular weight of 600 g / mol (Polikol PEG 600).

The processing parameters of PP were as follows:

temperature of the 1st zone of the extruder: 240 ° C, temperature of the 2nd zone of the extruder: 280 ° C, temperature of III zone of the extruder: 285 ° C, head temperature: 240 ° C, air heater temperature: 260-280 ° C, screw rotation speed: 50 rpm polymer performance: 3.4 g / min air flow: 8.8 m ³ / h.

After establishing the above-mentioned parameters for the processing of PP, all ingredients were thoroughly mixed and transferred to the hopper of the single-screw extruder. Then the melt-blown method of extruding the composite polypropylene non-woven material was started. The obtained non-woven fabric was tested for microbiological activity against colonies of gram-negative (Escherichia coli) and gram-positive (Staphylococcus aureus) bacteria and Candida albicans.

Example 4 (sample 10 in table 1).

To 100.0 g of Ingeo 32510 polylactide (PLA) granulate, 5.0 g of ethylene glycol oligomer with a number average molecular weight of 600 g / mol (Polikol PEG 600) was added, followed by 1% by weight of powdered copper silicate hydrate with the following chemical composition: 35 , 23 wt.% CuO, 62.16 wt. SiO2, 18.52 wt.% H2O, 0.02 wt.% Na2O and 0.01 wt.%. K2O.

The processing parameters of PLA were as follows:

- temperature of the 1st zone of the extruder:

- temperature of the 2nd zone of the extruder:

- temperature of III zone of the extruder:

- air heater temperature

- screw rotation speed:

- polymer efficiency:

- air flow:

195 ° C, 245 ° C, 260 ° C, 270-290 ° C, 50 rpm., 5.4 g / min. To 6.7 m ³ / h.

After establishing the above-mentioned parameters for the processing of PP, all ingredients were thoroughly mixed and transferred to the hopper of the single-screw extruder. Then the melt-blown method of extruding the composite polypropylene non-woven material was started. The obtained non-woven fabric was tested for microbiological activity against colonies of gram-negative (Escherichia coli) and gram-positive (Staphylococcus aureus) bacteria and Candida albicans.

Example 5 (sample 13 in table 1).

To 100.0 g of Ingeo 32510 polylactide (PLA) granulate was added 5.0 g of PCL Capa ™ 2054 polycaprolactone diol (Perstorp) with a number average molecular weight of 550 g / mol (PCL-diol), and then

PL 231 089 B1

1% by weight of powdered copper silicate hydrate with the following chemical composition: 35.23% by weight CuO, 62.16 wt. SiO2, 18.52 wt.% H2O, 0.02 wt.% Na2O and 0.01 wt.%. K2O.

The processing parameters of PLA were as follows:

temperature of the 1st zone of the extruder: 195 ° C, temperature of the 2nd zone of the extruder: 245 ° C, temperature of III zone of the extruder: 260 ° C, head temperature: 260 ° C, air heater temperature: 270-290 ° C, screw rotation speed: 40 rpm polymer performance: 5.0 g / min air flow: 6.8 m ³ / h.

After establishing the above-mentioned parameters for the processing of PP, all ingredients were thoroughly mixed and transferred to the hopper of the single-screw extruder. Then the melt-blown method of extruding the composite polypropylene non-woven material was started. The obtained non-woven fabric was tested for microbiological activity against colonies of gram-negative (Escherichia coli) and gram-positive (Staphylococcus aureus) bacteria and Candida albicans.

Example 6 (sample 25 in Table 2).

To 100.0 g of Ingeo 32510 polylactide (PLA) granulate, 2.5 g of Desmophen C XP 2716 polycarbonate diol with a number average molecular weight of 650 g / mol was added, and then 0.5% by weight of powdered copper silicate hydrate with the following chemical composition: 35, 23 wt.% CuO, 62.16 wt. SiO2, 18.52 wt.% H2O, 0.02 wt.% Na2O 0.01 wt.% K2O.

The processing parameters of PLA were as follows:

temperature of the 1st zone of the extruder: 195 ° C, temperature of the 2nd zone of the extruder: 245 ° C, temperature of III zone of the extruder: 260 ° C, head temperature: 260 ° C, air heater temperature: 270-290 ° C, screw rotation speed: 72 rpm polymer performance: 6.8 g / min air flow: 4.7 m ³ / h.

After establishing the above-mentioned parameters for the processing of PP, all ingredients were thoroughly mixed and transferred to the hopper of the single-screw extruder. Then the melt-blown method of extruding the composite polypropylene non-woven material was started. The obtained non-woven fabric was tested for microbiological activity against colonies of gram-negative (Escherichia coli) and gram-positive (Staphylococcus aureus) bacteria and Candida albicans.

Example 7 (sample 24 in Table 1).

To 100.0 g of Ingeo 32510 polylactide (PLA) granulate, 2.5 g of ethylene glycol oligomer with a number average molecular weight of 600 g / mol (Polikol PEG 600) was added, followed by 0.5% by weight of powdered copper silicate hydrate with the following chemical composition %: 35.23 wt.% CuO, 62.16 wt. SiO2, 18.52 wt.% H2O, 0.02 wt.% Na2O and 0.01 wt.%. K2O.

The processing parameters of PLA were as follows:

temperature of the 1st zone of the extruder: 195 ° C, temperature of the 2nd zone of the extruder: 260 ° C, temperature of III zone of the extruder: 260 ° C, head temperature: 260 ° C, air heater temperature: 267-290 ° C, screw rotation speed: 72 rpm polymer performance: 6.8 g / min air flow: 5.0 m ³ / h.

After establishing the above-mentioned parameters for the processing of PP, all ingredients were thoroughly mixed and transferred to the hopper of the single-screw extruder. Then the melt-blown method of extruding the composite polypropylene non-woven material was started. The obtained non-woven fabric was tested for microbiological activity against colonies of gram-negative (Escherichia coli) and gram-positive (Staphylococcus aureus) bacteria and Candida albicans.

PL 231 089 B1

Example 8 (sample 26 in Table 1).

To 100.0 g of Ingeo 32510 polylactide (PLA) granulate, 1.5 g of ethylene glycol oligomer with a number average molecular weight of 600 g / mol (Polikol PEG 600) was added, and then 0.5% by weight of powdered copper silicate hydrate with the following chemical composition %: 35.23 wt.% CuO, 62.16 wt. SiO2, 18.52 wt.% H2O, 0.02 wt.% Na2O and 0.01 wt.%. K2O.

The processing parameters of PLA were as follows:

temperature of the 1st zone of the extruder: 195 ° C, temperature of the 2nd zone of the extruder: 245 ° C, temperature of III zone of the extruder: 260 ° C, head temperature: 260 ° C, air heater temperature: 270-290 ° C, screw rotation speed: 60 rpm polymer performance: 5.9 g / min air flow: 6.1 m ³ / h.

After establishing the above-mentioned parameters for the processing of PP, all ingredients were thoroughly mixed and transferred to the hopper of the single-screw extruder. Then the melt-blown method of extruding the composite polypropylene non-woven material was started. The obtained non-woven fabric was tested for microbiological activity against colonies of gram-negative (Escherichia coli) and gram-positive (Staphylococcus aureus) bacteria and Candida albicans.

Example 9 (sample 20 in table 1).

To 100.0 g of Ingeo 32510 polylactide (PLA) granulate, 5.0 g of ethylene glycol oligomer with a number average molecular weight of 600 g / mol (Polikol PEG 600) were added, and then 0.1% by weight of powdered copper silicate hydrate with the following chemical composition %: 35.23 wt.% CuO, 62.16 wt. SiO2, 18.52 wt.% H2O, 0.02 wt.% Na2O and 0.01 wt.%. K2O.

The processing parameters of PLA were as follows:

temperature of the 1st zone of the extruder: 195 ° C, Temperature of the 2nd zone of the extruder: 245 ° C, temperature of III zone of the extruder: 260 ° C, head temperature: 260 ° C, air heater temperature: 270-290 ° C, screw rotation speed: 72 rpm polymer performance: 6.8 g / min air flow: 4.0 m ³ / h.

After establishing the above-mentioned parameters for the processing of PP, all ingredients were thoroughly mixed and transferred to the hopper of the single-screw extruder. Then the melt-blown method of extruding the composite polypropylene non-woven material was started. The obtained non-woven fabric was tested for microbiological activity against colonies of gram-negative (Escherichia coli) and gram-positive (Staphylococcus aureus) bacteria and Candida albicans.

Example 10 (sample 7 in table 1).

To 100.0 g of HL 512 FB polypropylene granulate was added 5.0 g of ethylene glycol oligomer with a number average molecular weight of 600 g / mol (Polikol PEG 600), and then 4% by weight of powdered copper silicate hydrate with the following chemical composition: 35.23 wt.% CuO, 62.16 wt. SiO2, 18.52 wt.% H2O, 0.02 wt.% Na2O and 0.01 wt.%. K2O.

The processing parameters of PP were as follows:

temperature of the 1st zone of the extruder: 240 ° C, temperature of the 2nd zone of the extruder: 280 ° C, temperature of III zone of the extruder: 285 ° C, head temperature: 240 ° C, air heater temperature: 260-280 ° C, screw rotation speed: 59 RPM polymer performance: 3.6 g / min air flow: 8.5 m ³ / h.

After establishing the above-mentioned parameters for the processing of PP, all ingredients were thoroughly mixed and transferred to the hopper of the single-screw extruder. Then it started

PL 231 089 Β1 process of extruding polypropylene composite non-woven fabric with the melt-blown method. The obtained non-woven fabric was tested for microbiological activity against colonies of gram-negative (Escherichia coli) and gram-positive (Staphylococcus aureus) bacteria and Candida albicans.

The test results in Table 1 indicate the bactericidal and fungicidal properties of composite nonwovens modified with copper silicate hydrate.

Table 1.

Chemical compositions of composite nonwovens (made of PP or PLA) containing PEG Polikol 600 (or PCL-diol or other plasticizers) and hydrated copper silicate CuSiC> 3 xH2O and the results of their microbiological tests

No trials Polymer PEG (PCL- CuSi03 ^r xH 20 R [%] (L) Escherichia coli R [%] (L) Staphylococcu s aureus R [%] (L) Candida albicans ki dial *) (ATCC 25922) (ATCC 6538) (ATCC 10321) [phr] | phr] 1 PP / PLAa 5 2 96.90 (1.9) 97.39 (1.6) 99.63 (2.3) 2 PP / PP-g-MA b 5 1 74.12 (0.5) 82.53 (0.8) 96.06 (1.7) 3 PP / k-PPc 5 1 74.93 (0.5) 62.36 (0.8) 97.92 (1.7) 4 PP 5 1 73.76 (0.5) 82.24 (0.3) 97.80 (1.7) 5 PP 5 2 ' 98.70 (1.9) 97.16 (1.6) 99.54 (2.3) 6 15 PP PP 5 5 3 3 > 99.94 (> 3.2) > 99.70 (> 3.4) 98.20 (1.7) 80.40 (0.7) 7 PP 5 4 > 99.94 (> 3.2) 99.98 (3.7) 99.62 (2.7) 8 PP / PE d 15e 1 > 99.92 (> 3.2) 99.94 (3.6) 99.80 (2.6) 9 PHA ' 5 1 > 99.97 (> 3.7) 99.8 (2.6) > 99.79 (1,2) 10 PLA 5 1 > 99.94 (> 3.2) 99.97 (3.6) > 99.74 (AT) 11 PLA 5 2 > 99.94 (> 3.2) 99.98 (3.9) > 99.74 (13) 13 PLA (5) * > 99.96 (> 3.4) 99.6 (2.4) 84.7 (0.8) 16 PLA 5 0.50 > 99.96 (> 3.4) 93.0 (1.2) 51.0 (0.3) 17 PLA (5) 0.50 > 99.98 (> 3.7) 99.8 (2.6) 84.4 (0.8) 18 PLA 5 0.25 > 99.98 (> 3.7) 99.2 (2.6) 47 (0.3) twenty PLA 5 0.10 > 99.98 (> 3.6) 52.84 (0.3) 62.3 (0.4) 23 PLA 59 > 99.98 (> 3.7) 99.52 (2.3) 80 (0.7) 24 PLA 2.5 0.50 > 99.98 (> 3.7) 99.91 (3.0) 23.3 (0.1) 26 PLA 1.5 0.50 > 99.98 (> 3.7) 35.71 (0.2) 31.4 (0.2)

PL 231 089 B1 phr

R

L ** a

Explanations:

parts by weight per 100 parts wt. polymer, bacterial growth reduction factor R, bacterial growth reduction factor L, polycaprolactonediol PCL Capa ™ 2054 (Perstorp), anhydrous copper silicate, a mixture of PP (HL 512 FB) and PLA (Ingeo 32510), in the weight ratio 1: 1, was used, a mixture of PP (HL 512 FB) and maleic anhydride grafted polypropylene (PP-g-MA) in a weight ratio of 3: 1 was used, a mixture of PP (HL 512 FB) and a polypropylene concentrate containing 10 wt. CuSiO3-xH2O (k-PP), in a weight ratio of 9: 1, a mixture of PP and polyethylene (with a number average molecular weight of 35,000 g / mol) was used, in a weight ratio of 9: 1, paraffin oil was used, and the PHA was poly [( R) -3-Hydroxybutanoate] Biomer (r) P209F, PEG Polikol 400 was used.

T a b e l a 2.

Chemical compositions of other bioactive PLA composite nonwovens containing Polikol PEG 600 (or other plasticizers) and hydrated copper silicate CuSiO3-xH2O

Sample No. PEG (or other plasticizer) CuSiO3-xH2O [phr] [phr] 25 25 ^a 0.5 27 10 1 28 5 ^b 1 29 5 ^c 1 thirty 5 ^d 1 32 5 ^e 1 33 51 1 34 2.59 0.5 35 15 1.5 36 5 ^h 1 37 5 ⁱ 1 38 5 ⁱ 1 39 5 ^k 1

PL 231 089 B1 phr a

b c

d e

g h

Explanations:

parts by weight per 100 parts wt. polymer, Desmophen C XP 2716 polycarbonate diol (Bayer) was used, PEG Polikol 300 was used, ethylene oxide and propylene oxide Rokopol 30P10 copolymer was used, dioctyl phthalate (DOP) was used, PEG Polikol 200 was used, ROKAmer 2950 ethylene oxide and propylene oxide copolymer was used, ethyl silicate 40, oligodimethylsiloxanediol Polastosil M200 was used, hydroxyether polysiloxane grafted copolymer of poly [dimethylsiloxane-co- [3- [2 - [(2-hydroxyethoxy) propyl] methylsiloxane was used, epoxy resin Epidian 601 was used, paraffin oil was used.

Claims (8)

Patent claims 1. The method of biofunctionalization of textiles by means of extrusion, whereby the polymer component is pre-mixed with copper silicate and plasticizer, the whole is heated to melt the polymer, and then the molten composition is subjected to the process of pneumothermic extrusion and blowing of the liquid polymer melt in a stream of hot air characterized in that the copper silicate is used in the form of a hydrate. 2. The method according to p. The process of claim 1, wherein the amount of copper silicate is 0.1-4% by weight. 3. The method according to p. The process of claim 1 or 2, characterized in that the copper silicate is used in the form of a concentrate with a polymer containing 1-25% by weight of copper silicate hydrate. 4. The method according to p. A process as claimed in claim 1, characterized in that polymers selected from the group consisting of polypropylene and its copolymers, polylactide, polyhydroxyalkanoates, polyethylene and / or mixtures thereof are used as the polymer components. 5. The method according to p. The process of claim 1, wherein the plasticizers have a liquid consistency. 6. The method according to p. The method of claim 1 or 5, characterized in that the plasticizers are compounds selected from the group consisting of: ethylene glycol or propylene glycol oligomers, copolymers of ethylene glycol and propylene glycol, monoalkyl ethers of ethylene glycol oligomers, glycerol esters, esters of citric acid or tartaric acid, esters of pentaerythritol , phthalic acid alkyl diesters, paraffin oil, epoxy resin, silicic acid oligoesters, oligodimethylsiloxanediol, hydroxyalkyl or hydroxyether polysiloxane derivatives, polycaprolactone, polycaprolactone diol, or polycarbonate diol. 7. The method according to p. A process as claimed in claim 1 or 6, characterized in that an ethylene glycol oligomer is used as the plasticizer. 8. The method according to p. 1 or any of claims 5 to 7, characterized in that the plasticizers are used in an amount of 1.5-15% by weight based on the weight of the polymer or the weight of the polymer mixture, preferably 2.5-5% by weight.