Articles possessing antibacterial and antifungal activity

FIELD: medicine.

SUBSTANCE: invention relates to using zinc sulfide in articles possessing N antibacterial and antifungal activity. In particular, it can be used in preparing any product able to interact with microorganisms and/or fungi, such as dress, carpets, curtains, bed affiliations and textile materials used for medicinal aims.

EFFECT: valuable properties of articles.

6 cl, 8 tbl, 7 ex

 

The present invention relates to products having antibacterial and antifungal activity, containing the zinc sulfide. Yarns, fibers, filaments and articles of the present invention may, in particular, be used to manufacture any product that can interact with bacteria and/or fungi, such as clothing, carpets, curtains, bedding and textile materials for medical purposes. The present invention also relates to the application of zinc sulfide for the manufacture of threads, fibers, filaments and/or products that have antibacterial and antifungal activity.

In various applications, such as textile industry, seek to limit the spread of bacteria and fungi to prevent diseases and to prevent unpleasant smells. In medicine, for example, it is also important to limit the growth of bacteria and fungi on the surface of the working tools, building materials and clothing.

Long been known and are widely used by various agents, which are able to destroy living organisms. Among these agents, the most well-known element-based metals such as silver, copper or zinc, Quaternary ammonium, or organic compounds, such as triclosan.

Were the development of the NY various impregnation, contains bioactive compounds, with the goal of making the textile surfaces ability to destroy living organisms. However, the impregnation always have limited durability, and their effect disappears after one or more washings. Thus, in many cases, it is important to introduce the active ingredient directly into the product in order to exhibit its biological activity.

There are various antibacterial and antifungal agents, which are produced on an industrial scale. However, these agents can be introduced into the polymer matrix, because they have no resistance to the temperatures of the molding said matrices and can be transformed at specified temperatures or interact with the matrix.

Continue the search for new cheap antibacterial and antifungal agents, which can be easily applied in products based on polymer matrix.

The authors of the present invention have found that the threads, fibers, filaments and/or products, such as film containing zinc sulfide (ZnS) in their polymer matrix, have excellent antibacterial and antifungal properties.

These antimicrobial properties ensure that the addition of zinc sulfide in the form of mineral filler in the polymer matrix.

The zinc sulfide Le is to dispersed in the polymeric matrix, that ensures a uniform distribution of the compounds in the threads, fibres, filaments and/or products. The zinc sulfide does not accumulate in the polymer matrix, in contrast to different particles on the basis of metals, known from the field of technology as an antimicrobial agent.

By diffusion and migration of the active ingredient in the form of zinc sulfide and/or zinc is moved on the surface of the yarns, fibres, filaments and/or products and interacts with the medium containing the bacteria and fungi that allows you to achieve a more lasting antibacterial and antifungal activity. During washing of the threads, fibres and/or filaments is small, the removal of the active component from the surface. However, diffusion of the active ingredient in a polymer matrix from the center to the surface of the yarns, fibres, filaments and/or products to maintain antibacterial and antifungal activity. Thus, the activity persists for a long time despite washing yarns, fibres, filaments and/or products.

Zinc sulphide also has the advantage that it is resistant to temperatures of molding a thermoplastic matrix. Thus, properties of zinc sulfide does not change and is not particularly limited in the above mentioned temperatures.

In addition, su is hid zinc inert and does not react with the polymer matrix, without causing the problems associated with degradation, staining, yellowing of threads, fibers, filaments and/or products in contrast to antimicrobial agents known from the technical field, such as, for example, zinc oxide (ZnO) or silver (Ag). In addition, threads, fibers, filaments and/or products containing zinc sulfide, are not abrasive.

The zinc sulfide meets also the requirements from the standpoint of cost, ease of use and introduction into the polymer matrix, such as a thermoplastic matrix. Zinc sulphide also has the advantage that it is a good matting agent.

Under antibacterial understand the action, the purpose of which is to limit, reduce, or remove bacteria present in the medium. Under the bacterium understand eubacteria and archeobacteria. Eubacteria include firmicute, gracility and turnicate. Gracilicutes include gram-negative bacteria, such as Enterobacteriaceae, such as Klebsiella (such asKlebsiella pneumoniae) and Escherichia (such asEscherichia coli). Firmicute include gram-positive bacteria, such as Micrococcaceae, such as, for example, Staphylococcus (such asStaphylococcus aureusand sticks that form endospores, including Bacillus (Bacillaceae), such as, for example,Bacillus circulans. All of these references are listed in Bergey''s Manual of Systematic Bacteriology, Williams &Wilkens, 1st ed. Vol. 1-4, (1984).

Under prot is Pogrebkov understand the action the purpose of which is to limit, reduce, or remove mushrooms (mycetes), available in the environment. The term Myceteae includes Amastigomycota, as, for example, Deuteromycotina, which includes Deuteromycetes. Deuteromycetes include Aspergillis (Aspergillus niger) and Candida (Candida albicans).

Under the environment understand any environment containing at least bacteria and/or fungi. The medium can be a liquid or a gas, preferably air. The term limitation understand the decrease in the number of bacteria and/or fungi present in the medium, compared with the number present in the medium before the introduction of threads containing zinc sulfide. Also, the term restriction see also reducing the spread of new bacteria and/or fungi in time and environment. Also, the term limitation understand the decrease of the coefficient of bacteria and/or fungi. The term delete understand the destruction of the environment of most bacteria and/or fungi, i.e. the destruction of bacteria and/or fungi present in the environment, or translate them into their inactive state. The term destruction see also preventing the growth of new bacteria and/or fungi.

The present invention also relates to the use of zinc sulfide in the polymeric matrix for the manufacture of threads, fibers, filaments and/or products that have antibacterial and antifungal properties of zinc Sulfide plays a role in antibacterial and antifungal agent.

The first object of the present invention are yarns, fibers and/or filaments that have antibacterial and antifungal properties, containing a polymer matrix and zinc sulphide.

The presence of zinc sulfide in the polymeric matrix can be determined using various methods well-known to the specialist, such as a direct quantitative elemental analysis of zinc and sulfur by x-ray fluorescence spectrometry; possibly in combination with the quantitative elemental analysis of zinc by atomic spectrometry after mineralization by the action of a mixture of sulfuric and nitric acids, with the aim to reduce the amount of zinc sulfide. It is also possible to quantify sulfur by microanalysis and/or dissolving a polymer matrix in the solvent, filter, additive and analyzed by x-ray diraction processes.

The mass ratio of zinc sulfide to the total weight of the composition intended to form the threads, fibres and/or filaments may be in the range from 0.01 to 10%, preferably from 0.1 to 7%, and even more preferably from 0.2 to 5%, in particular from 0.3 to 3%. The amount of zinc sulfide in the threads, fibres and/or filaments can vary depending on various criteria, such as matte, composition, type of polymer, the method of administration, method of application, type of harmful org the isms and the environment.

As examples of polymers containing a polymer matrix can lead to: polylactones, such as poly(pivalate), poly(caprolactone) and polymers of the same class; polyurethanes obtained by the reaction between diisocyanates such as 1,5-naphthalenedisulfonate; p-delete the entry, the m-delete the entry, 2,4-colorvision, 4,4'-diphenylmethanediisocyanate, 3,3'-dimethyl-4,4'-diphenylmethanediisocyanate, 3,3'-dimethyl-4,4'-biphenyldiol, 4,4'-diphenylmethanediisocyanate, 3,3'-dimethyl-4,4'-diphenyldiisocyanate, 3,3'-dimethyl-4,4'-diphenylmethanediisocyanate, 3,3'-dimethoxy-4,4'-biphenyldiol, dianisidines, toluylenediisocyanate, hexamethylenediisocyanate, 4,4'-diisocyanatobutane and compounds of the same class and diols with long linear chains, such as poly(tetramethylthiuram), poly(atlandia), poly(1,4-bucilandia), poly(etranscript), poly(2,3-Butyrskiy), simple polyetherdiol and compounds of the same class; polycarbonates such as poly[methane bis(4-phenyl)carbonate], poly[1,1-simple ether bis(4-phenyl)carbonate], poly[difenilmetana-bis(4-phenyl)carbonate], poly[1,1-cyclohexane bis(4-phenyl)carbonate] and polymers of the same class; polysulfones; polyethers; polyketone; polyamides, such as poly(4-aminobutanoic acid), poly(hexamethylenediamine), poly(ε-caprolactam), poly(6-aminohexanoic acid), poly(m-xylylenediamine), poly(p-xylylenediamine), poly(2,2,2-trimethylhexamethylenediamine), poly(metaphenylenediamine), poly(p-phenyleneterephthalamide) and polymers of the same class; polyesters, such as poly(utilisateur), poly(ethylene-1,5-naftalin), poly(1,4-cyclohexanedimethanol), poly(utilizationof), poly(para-hydroxybenzoate), poly(1,4-cyclohexanedimethanol), poly(1,4-cyclohexanedimethanol), polyethylene terephthalate, polybutylene terephthalate and polymers of the same class; poly(aristocracy), such as poly(2,6-dimethyl-1,4-phenyleneoxy), poly(2,6-diphenyl-1,4-phenyleneoxy) and polymers of the same class; poly(allensolly), such as poly(phenylindole) and polymers of the same class; simple polyetherimides; vinyl polymers and their copolymers such as polyvinyl acetate, polyvinyl alcohol, polyvinyl chloride, polyvinyl butyral, grades, copolymers of ethylene and vinyl acetate and polymers of the same class; acrylic polymers, polyacrylates and their copolymers, such as politicalit, poly(n-butyl acrylate), polymethyl methacrylate, polimetilmetakrilat, poly(n-butylmethacrylate), poly(n-propylbetaine), polyacrylamide, polyacrylonitrile, poly(acrylic acid), copolymers of ethylene and acrylic acid, copolymers of ethylene and vinyl alcohol, copolymers of Acrylonitrile, copolymers of methyl methacrylate and is of Tirol, copolymers of ethylene and ethyl acrylate, copolymers of methacrylate, butadiene and styrene, a copolymer of Acrylonitrile, butadiene and styrene (ABS) and polymers of the same class; polyolefins such as low density polyethylene, polypropylene, chlorinated low density polyethylene, poly(4-methyl-1-penten), polyethylene, polystyrene and polymers of the same class; ionomers; polyepichlorohydrins; polyurethanes, such as polymerization products of diols such as glycerin, trimethylol-propane, 1,2,6-hexanetriol, sorbitol, pentaerythrit, polyether polyols, polyesters, polyols and compounds that the same class with polyisocyanates, such as 2,4-colorvision, 2,6-colorvision, 4,4'-diphenylmethanediisocyanate, 1,6-hexamethylenediisocyanate, 4,4'-decimalequivilentchart and compounds of the same class; and polysulfones such as the reaction products between the sodium salt of 2,2-bis(4-hydroxyphenyl)propane and 4,4'-dichlorodiphenylmethane; furan resins such as polyfuran; plastics based on cellulose ethers, such as cellulose acetate, acetate-butyrate cellulose propionate, cellulose and polymers of the same class; silicone polymers such as polydimethylsiloxane, a copolymer of dimethylsiloxane and phenylmethyl of siloxane and polymers of the same class; a mixture of at least two of these polymers.

As another p the polymer matrix can also lead, for example, viscose, cellulose and cellulose acetate; polyamidimide or polyimides; latexes such as acrylic and urethane latexes.

The polymer matrix of the present invention may also be a polymer, used in adhesives, such as, for example, copolymers of acetates vinylplasts, acrylic latex, urethane latexes and plastisol polyvinylidenechloride (PVC).

The polymeric matrix preferably is a thermoplastic matrix.

Preferably the threads, fibres and/or filaments of the present invention contains a thermoplastic matrix comprising a thermoplastic polymer chosen from the group consisting of polyamides; polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (RHT), polytrimethylene (PTT); polyolefins, such as polypropylene, polyethylene, polyvinylidene chloride (PVC), their copolymers and mixtures.

Thermoplastic matrix preferably contains at least one polyamide chosen from the group consisting of: polyamide 6, polyamide 6.6, polyamide 11, polyamide 12, polyamide 4, polyamide 4-6, 6-10, 6-12, 6-36, 12-12, their copolymers and mixtures such as a mixture of polyamide 6 and 6.6. You can also use different types of aromatic polyamides.

In accordance with a preferred embodiment of the present invention thermoplastic Matri who she is polymer, containing macromolecular chains of star-shaped or H-shaped form and, if necessary, linear macromolecular chains. Polymers containing macromolecular chains of star-shaped or H-shaped, as described, for example, in patents FR 2743077, 2779730, USA 5959069, EP 0632703, 0682057 and 0832149.

thermoplastic matrix of the present invention may also be a polymer statistical tree type, preferably copolyamide with a statistical tree-like structure. These copolyamids with a statistical tree-like structure, and the method of their derivation are described in particular in document WO 99/03909. thermoplastic matrix of the present invention may also be a composition comprising a linear thermoplastic polymer and a thermoplastic polymer, star-shaped, H-shaped and/or tree-like form, such as described previously. thermoplastic matrix of the present invention may also contain hyperbranched copolyamide type copolyamids that disclosed in document WO 00/68298. thermoplastic matrix of the present invention may also contain any combination of thermoplastic polymer, star-shaped, H-shaped, tree-shaped and hyperbranched copolyamid described earlier.

The zinc sulfide may be in the form of particles. Particles su is hide zinc can have a diameter of less than or equal to 5 μm, preferably less than or equal to 1 μm, even more preferably a diameter in the range from 0.1 to 0.5 μm, preferably a diameter of about 0.3 microns.

Yarns, fibers and/or filaments of the present invention as an antibacterial and antifungal agent preferably contain only zinc sulphide. However, the zinc sulfide can be used in combination at least one other antimicrobial agent, such as, for example, silver, silver oxide, silver halide, oxide copper (I)oxide copper (II), copper sulfide, zinc oxide and silicate of zinc, the expert can choose the type and amount of antimicrobial agent depending on the destination, method of application, type of harmful organisms, type of fibers, threads, filaments and/or products and the environment.

The zinc sulfide introduced into the polymer matrix may be in the form of particles that are not coated with a special coating and are not enclosed in capsules. However, these particles can also be coated with a special envelope and enclosed in capsules. Particles of zinc sulfide can be covered with a special membrane and/or enclosed in the capsule, at least one mineral and/or organic compounds. You can use particles of zinc sulfide containing no mineral shell.

Yarns, fibers, filaments and/or product p. the present invention may also contain any other additives, which can be used, for example fillers for hardening, flame retardant agents, UV stabilizers, heat, pigments and matting compounds such as titanium dioxide.

The present invention also relates to a method for yarns, fibers and/or filaments that have antibacterial and antifungal properties, which consists in molding compositions containing a polymeric matrix, preferably a thermoplastic matrix, and zinc sulfide.

Mixing zinc sulfide and the polymer matrix can be made in various ways well known to the specialist. Compositions containing a polymer matrix and the zinc sulfide according to the present invention, preferably receive the introduction of zinc sulfide in the polymer melted in the mixing, for example, in the upper part of the device for molding. They can also get the introduction of zinc sulfide in the polymer solution, for example, in the upper part of the device for forming the wet way. The composition can also be obtained by the introduction of zinc sulfide before polymerization (together with the raw material) and/or during polymerization of the polymer matrix, preferably a thermoplastic polymer matrix. To the polymer matrix, you can add ready uterine mixture (masterbatch) based on a polymeric matrix containing zinc sulphide.

You can, in h is particularly apply the following process comprising at least steps:

a) interaction of the polymer matrix may, in the melt, with zinc sulfide and/or concentrated composition based on a polymeric matrix containing zinc sulfide; and

b) molding the mixture obtained in stage a), with the aim of obtaining yarns, fibers and/or filaments.

The compositions can take the form of yarns, fibers and/or filaments directly after polymerization, without intermediate stages of solidification and re-melting. The composition may also take the form of granules, intended for re-melting, in order to give them further specific form, for example, to obtain molded products or for the manufacture of threads, fibers or filaments.

Can be used all methods of forming in the melt.

To obtain mnogoelementnykh threads known integrated or reintegrirovat methods of forming the thread or forming filament - stretching or forming filament - drawing - texturing, whatever the speed of the forming yarn. You can get thread by high molding speed molding above 3500 m/min Such methods are commonly referred to by the following terms: POY (Partially Oriented Yarn is partially oriented yarn), FOY (Fully Oriented Yarn is fully oriented yarn), FEI (FilageEtirage Inté gré integrated molding filament-stretching).

To obtain fiber filaments immediately after molding or re, for example, to combine in the form of strands or layers, pulling, texture, or twist and cut. The resulting fibers can be used for the manufacture of non-woven fibers or yarn. The composition can also be used to obtain short fibers for flocking.

You can also get the threads, fibres and/or decomposition filaments, some of which contain zinc sulphide.

Yarns, fibers and/or filaments of the present invention can be subjected to various treatments, such as, for example, continuous pulling or portions of the extrusion, deposition of sizing, impregnating, weaving, texturing, twisting, stretching, heat treatment for fixing or relaxation, section, torsion and/or staining. For staining of lead, in particular, methods of staining by the method of dipping or spraying. The preferred types of staining are acid staining, metallsoderjasimi or nemateleotris staining.

The present invention also relates to an article having antibacterial and antifungal properties obtained at least from the threads, fibres and/or filaments, which the op is Sana'a earlier.

These products can be fabrics or textile surfaces, such as woven, knitted, non-woven surfaces or carpets. Indeed, threads, fibers, filaments, products and/or composite products can be used for any product that can interact with bacteria and/or fungi, such as, for example, carpets, rugs, upholstery, floor surface, sofas, curtains, bedding, mattresses and pillows, clothing and textile materials for medical purposes.

Similar products can be obtained, in particular, from one type of yarns, fibers and/or filaments; or, on the contrary, from a mixture of yarns, fibers and/or filaments of various types. The product contains, at least partially, threads, fibres and/or filaments of the present invention. For this type of threads, fibers, filaments, such as filaments, fibers, filaments, not containing zinc sulfide, the product of the present invention can be used yarns, fibers or filaments of various types. The present invention also relates to composite articles having antibacterial and antifungal properties, and includes at least one product according to the present invention. Composite products are products with multiple components. These components can be, for example,short fibers, the basics of the product obtained from filaments, fibers, filaments, such as non-woven products. In the framework of the present invention, at least one of the components of the composite textile product contains zinc sulphide.

The present invention relates also to the products obtained by molding composition based on a polymeric matrix containing at least zinc sulphide. These products can in particular be obtained by the method, which is chosen from the group comprising extrusion method, such as extrusion of sheets and films, the method of molding such as compression molding and injection method, such as injection molding. The film can also be obtained by the methods mentioned earlier, using a flat die plate. Preferably thermoplastic matrix is a polyamide, a complex polyester or polyolefin. The films obtained can be subjected to one or more stages of different kinds of processing, such as unilateral or bilateral stretching, stabilization heat treatment, antistatic treatment or impregnation.

Example 1: Obtaining samples

Standard polyamide 66 having a relative viscosity of 2.6 (measured in the form of a solution at 1 /100 ml in 96%sulfuric acid at a temperature of 25°C), then dried in the usual manner to obtain a residual moisture content of 0.09%. C is the fact it is crushed into powder and mixed with 2%ZnS powder (Sachtolith HD-S de Sachtleben - Germany). The resulting mixture is melted in the extruder and poured a trickle in the die plate, having 10 holes, thus obtaining 10 filaments which are cooled by blowing air (20°C, a relative humidity of 66%. Next, the filaments are combined and grease 8,6%standard emulsion, and then wound on the tube with a speed of 4200 rpm Obtained partially oriented yarn (POY), a common title 42 decitex, then knit on a conventional machine to obtain the product (stocking). Then, the specified product is subjected to one cycle of staining in the following conditions:

- Removal of the binder at a temperature of 60°C for 20 min with 1 g/l of anionic surfactants (Invatex CRA de CIBA) and 1 g/l of sodium carbonate.

- Painting in the open-air bath (volume 7 l) with heating at a temperature of 1.6°C/min, then incubated 45 min at a temperature of 98°C. Receiving tank contains 1% Nylosan Bleu NBLN (Clariant), 1% Sandogen NH (controller, Clariant), 1 g/l Sandacid VA (donor, acid Clariant) and 0.5 g/l sodium acetate.

A similar product without the addition of ZnS was manufactured in the same conditions as the control sample for carrying out antibacterial and antifungal tests.

Example 2: Antibacterial test

Antibacterial activity measured in accordance with JIS L 1902: 1998, depending on the particular practically the way the Laboratory of Hygiene and Biotechnology Institute Hoenstine (Germany):

- use bacteriaStaphylococcus aureusADS R and Klebsiella pneumoniae DSM 789, which initially supported in a dry and frozen. Culture, grafted on a nutrient basis (LAB8, LabM) and incubated in an incubator at a temperature of 37°C for 48 hours. Next, the bacteria move into the Erlenmeyer flask with a capacity of 250 ml per nutrient basis(LAB14, LabM) and incubated in an incubator at a temperature of 37°C for 18 hours. The culture is diluted in the ratio of 1/200 isotonic saline solution (NaCl 0.85 wt.%+0,05% Tween 80) so that the suspension contained about 105bacteria/ml.

Tests carried out on the surfaces jerseys 18 mm 18 mm Using a sample with such a surface area as is necessary for the absorption of exactly 0.2 ml of suspension.

The test samples are control sample and the sample of the present invention.

The surface of the jerseys placed in jars with a capacity of 30 ml Prepare six jars containing control samples, and three jars of the test specimen according to the present invention. Jars and cover with foil and sterilized at a temperature of 121°C for 15 minutes

Bacteria impart to the samples that are in the jars, using 0.2 ml suspension of bacteria, ensuring that the suspension does not interact with the walls of the jars. Immediately after a when is ivci 20 ml of isotonic solution of Tween 80 (0.2 wt.%) add the three cans, containing control sample, cover them with a sterile lid and stirred for 30 seconds. Then count the number of bacteria.

Other jars are placed in the desiccator and leave bacteria in the incubator for 18 hours at a temperature of 37°C. After incubation, count the number of bacteria in the same way that the number of bacteria at time 0.

Determine, in particular, the following amounts:

A=average number of active bacteria directly after vaccination in the control sample

In=the average number of active bacteria after incubation for 18 h in the control sample

C=the average number of active bacteria after incubation for 18 h in the sample according to the present invention (ZnS)

F=growth regulator=Log ()-Log(A). The test is considered reliable if F>0±0,5

S=specific activity=Log ()-Log(C)

Cfu (colony forming unit): colony-forming unit (KOI).

The results are shown in tables 1 and 2 for gram-positive and gram-negative bacteria.

Table 1< / br>
Staphylococcus aureus(Gram+): Strain ADS R
Sample 1 (cfu)Sample 2 (cfu)Sample 3 (cfu)The average value (cfu)The average value is the (Log cfu)
Monitoring via 0 h4,50×1053,60×1054,50×1054,20×1055,62
Control through 18 hwith 4.64×1058,39×1058,70×1057,25×1055,86F=0,24
Test after 18 h<204,07×102<201,36×1022,13S=a 3.87

Test after 18 h
Table 2< / br>
Klebsiella pneumoniae (Gram-): Strain DSM 789
Sample 1 (cfu)Sample 2 (cfu)Sample 3 (cfu)The average value (cfu)The average (Log cfu)
Monitoring via 0 h2,15×1056,70×1057,40×1055,42X1055,73
Control through 18 hto 3.58×1074,00×1074,28×1073,95X1077,60F=1,86
2,28×1072,71×107was 2.76×1072,58X1077,41S=0,18

Thus, it is seen that the products obtained from yarns containing ZnS, possess strong antibacterial activity against gram-positive and gram-negative bacteria.

Example 3:The persistence of antibacterial activity after washing

Two samples (control and according to the present invention)obtained previously, washed 30 times in accordance with standard EN 26330 Protocol 5A: temperature wash 40°With, use a detergent without optical Brightener" and use the standard home washing machine. The samples dried at room temperature.

Next antibacterial activity of the newly measured according to previously described methodology. The results are presented in tables 3 and 4.

Table 3< / br>
Staphylococcus aureus(Gram+): Strain ADS R
Sample 1 (cfu)Sample 2 (cfu)Sample 3 (cfu)The average value (cfu)The average (Log cfu)
Monitoring via 0 h the 3,40×1053,10×1053,80×1053,43×1055,54
Control through 18 h8,10×102<20<202,71×1022,43F=-3,1
Test after 18 h<20<20<20<200,01S=2,42

S=1,07
Table 4< / br>
Klebsiella pneumoniae (Gram-): Strain DSM 789
Sample 1 (cfu)Sample 2 (cfu)Sample 3 (cfu)The average value (cfu)The average (Log cfu)
Monitoring via 0 h-----
Control through 18 h3,00×1062,70×1072,30×1071,77×1077,25-
Test after 18 h1,10×1061,10×1062,30×1061,50×1066,18

Thus, it is shown that the products obtained from yarns containing ZnS, possess strong antibacterial activity against gram-positive and gram-negative bacteria even after 30 washes.

Example 4:Antifungal test

Evaluation of antifungal (antimiani) activity carried out in accordance with ASTM E 2149-01 (Shake flask test) depending on the practical method used by the Laboratory of Hygiene and Biotechnology Institute Hohenstein (Germany) for fungi. 1 g of the test product interacts with 70 l of a solution of mineral salts and 5 ml suspensionAspergillus nigerat 1-3,105CFU/ml Erlenmeyer flask with a capacity of 250 ml of a Solution of mineral salts previously obtained using the following exact composition:

NaNO32.0 g
KH2PO40.7 g
K2HPO40.3 g
KCl0.5 g
MgSO4x7 H2O0.5 g
FeSO4x7 H2O0.01 g
H201000 ml
TWEEN 800.1 g

Repeat the procedure in a similar way in the Erlenmeyer flask using 1 g of the checkpoints for important locations the th sample. The Erlenmeyer flask shaken at a speed of 300 movements per minute at room temperature. Counting fungi carried out after 0 and 3 days of incubation.

The reduction coefficient R is determined as follows:

R=100(B-A)/B

A=the number of colony forming units per milliliter for the Erlenmeyer flask containing the sample after interaction in 3 days

In=number of colony forming units per milliliter for Erlenmeyer flask to interaction with the sample (time 0)

The results are shown in table 5:

Table 5< / br>
Aspergillus niger"von Thieghem: Strain ADS 6275 (DSM 1957)
Time 0 (KOI/ml)Time 3 days (KOI/ml)R
The control experiment>1,00x1061,90x106R=-90% (increase)
Test8,00x1051,00x104R=99% (decrease)

Thus, it is shown that the products obtained from yarns containing ZnS, possess strong antifungal activity.

Example 5:Receiving spools of thread and distinctive properties

Index yellowing and degradation of the polymer matrix compared to threads containing ZnS and threads, provided the ZnO.

Used polyamide 66 (RA) is a polyamide containing no titanium dioxide, with a relative viscosity of 2.5 (measured at a concentration of 1 g/100 ml in 96%sulfuric acid at a temperature of 25°).

Introduction ZnS or ZnO in RA carry out the mixing. The mixture is dried for 20 hours at a temperature of 100°in vacuum at a pressure of about 50 mbar, then placed in a device for the extrusion with dual screw, which ensures mixing in the molten phase. The ratio of introduction of ZnS or ZnO, shown in the following table, calculated relative to the total weight of the composition. Then carry out molding the molten mixture at the appropriate temperature in the head part of the die, allowing you to get the thread (the temperature of the molding shown in the following table), and speed at the first point of measurement, equal to 4200 m/min, in order to obtain continuous mnogoelementnyi thread with a size of 42 decitex 10 filaments. Mnogomillionnoe fiber or thread consist of 10 single yarn (filler consists of 10 holes the thickness of 0.38 mm, and the diameter of the single yarn is about 20 microns.

The obtained filaments differ in the magnitude of the molecular weight of a polyamide matrix, measured by the GPC method (gel permeation chromatography) in dichloromethane after derivatization with triperoxonane anhydride compared to the control is a solution of polystyrene (PS). For detection use refractometry. The molecular weight matrix is estimated as the maximum peak of refraction.

Threads are also different dimension index yellowing in accordance with standard YI DIN 6167 (light source D65).

The results are presented in table 6:

Table 6
TrackThe molding temperature (°)The yellowing indexGPC (g/mol EQ. PS)
Control RA 662838,765000
RA 66+0,24% ZnS2839,465000
RA 66+0,5% ZnS2839,267000
RA 66+0,2% ZnO28013,556000
RA 66+0,5% ZnO27114,852000

Thus, ZnS gives the thread more substantial properties than ZnO, when it comes to resistance to yellowing and preservation of the polyamide matrix. Therefore, ZnS is more suitable for introduction into the matrix to obtain filaments compared to ZnO, which is known for its antimicrobial properties.

Example 6:antifungal test compared with the ZnS powder

Used mushroom is what I Eurotium amstelodami(strain CBS 11248). It is cultivated in a medium containing 20 g/l of malt extract, 200 g/l sucrose and 15 g/l agar. The tested samples contain the following basic products:

powder of polyamide 6 with a relative viscosity of 2.6 (measured in the form of a solution of 1 g/100 ml in 96%sulfuric acid, at a temperature of 25° (C) and particle size less than 500 microns;

- ready uterine mixture with 40 wt.% ZnS in polyamide 6 (link to Sachtolen PA ZS 40 de Sachtleben containing Sachtolith HD-S de Sachtleben), particle size less than 500 microns; and

powder ZnS (Sachtolith HD-S de Sachtleben).

Get 4 different environment culture:

- Wednesday 1: 20 g/l of malt extract, 200 g/l sucrose and 15 g/l agar;

- Wednesday 2: medium 1 containing 7.5 wt.% powder RA 6;

- Wednesday 3: Wednesday 1 containing 12.5 wt.% powder 40%ready masterbatches; namely, 5 EQ.% ZnS and 7.5 equiv.% RA 6; and

- Tuesday 4: Wednesday 1 containing a mixture of powder: 5 wt.% of ZnS powder and 7.5% powder RA 6 (polyamide, not containing ZnS).

The four medium is sterilized before pour into Petri dishes with a diameter of 85 mm

DisputesE. amstelodamicollect on a three-week culture, placed in suspension in a medium containing 1/1000 peptone and 1 / 1000th of Tween 80, then diluted to obtain 106spores/ml.

30 CL suspension is placed in the center of each test environment. For each environment are carried out on 3 of the experiment.

Then the Petri dishes placed is up in the incubator at a temperature of 25° With under constant white light source.

On the 12th and 16th day of incubation, measure the diameter of the colony in each environment. The results are mean values of three experiments are presented in the following table:

Table 7
The diameter of colony (mm)
The number of days of incubationWednesday 1Wednesday 2Wednesday 3Wednesday 4
01111
1278805561
1685856069

The difference between the different experiments is ±1 mm

Thus, it is shown that ZnS contained in RA 6, leads to a strong decrease in the growth of fungi.

Example 7:antifungal test compared with the ZnS powder

The tested samples contain the following basic products:

powder of polyamide 6 (hereinafter denote the powder (A) with a relative viscosity of 2.6 (measured in the form of a solution of 1 g/100 ml in 96%sulfuric acid, at a temperature of 25°), and

powder ZnS (Sachtolith HD-S de Sachtleben).

Antibacterial activity measured in accordance with that the same methodology, as in example 2, except that is injected into the interaction of the powder with a bacterial suspension.

Control experiment: (A) extr:

The powder is produced by extrusion of powder A. the Extrusion carried out as follows: the powder is dried for 16 hours at a temperature of 80°under vacuum at a pressure of about 50 mbar, then placed in the device for the extrusion with dual auger. The operating parameters of the extruder, double screw as follows: melting point: approximately 240°; time-keeping in the melt: 3 min Fiber obtained at the output of the device for the extrusion, dipping in water at a temperature of about 20°C, then crushed and pulverized after cooling with dry ice using ultracentrifuging grinder Retsch ZM 1000. Granulometric composition of the obtained powder is less than 500 microns.

Test 1: (A+ZnS)extr.:

The powder is produced by mixing 2 wt.% ZnS in the form of powder with powder and extrusion of the mixture powder, as described previously.

Thus, the resulting powder contains pellets of polyamide 6, comprising ZnS.

Test 2: (A)extr+ZnS

The powder obtained by mixing 2 wt.% ZnS in the form of a powder with the control powder (A)extr. Thus, the resulting powder contains pellets of polyamide 6 and ZnS.

The results are shown in the following table.

Table 8< / br>
Staphylococcus aureus(Gram+): Strain ADS R
Sample 1 (cfu)Sample 2 (cfu)Sample 3 (cfu)The average value (cfu)The average (Log cfu)
Monitoring via 0 h1,20×1051,20×1051,50×1051,3×1055,11
Control through 18 h2,90×1052,70×1053,00×1051,87×1055,46
Test 1 18 h1,50×1042,50×1043,70×1042.57 m×104to 4.41S=1,05
Test 2 18 h3,10×1056,30×105the ceiling of 5.60×1055,00×1055,70S=-0,24

The specified test unexpectedly shows that the antibacterial activity of ZnS get when ZnS is mixed within the polymer matrix.

1. The use of zinc sulfide in a thermoplastic matrix for the manufacture of threads, fibers, filaments or articles about ladyship antibacterial and antifungal activity.

2. The use according to claim 1, characterized in that the mass ratio of zinc sulfide to the total weight of the composition, intended for forming of threads, fibers, filaments or products, is in the range from 0.01 to 10%.

3. The use according to claim 1 or 2, characterized in that the mass ratio of zinc sulfide to the total weight of the composition, intended for forming of threads, fibers, filaments or products, is in the range from 0.2 to 5%,

4. The use according to claim 1 or 2, characterized in that thermoplastic matrix contains at least one thermoplastic polymer selected from the group consisting of polyamides, polyesters, such as polyethylene terephthalate, polybutylene terephthalate, polytrimethylene; polyolefins, such as polypropylene, polyethylene; polyvinyl chloride and their copolymers and mixtures.

5. The use according to claim 1 or 2, characterized in that thermoplastic matrix contains at least one polyamide selected from the group consisting of polyamide 6, polyamide 6.6, polyamide 11, polyamide 12, polyamide 4, polyamide 4-6, 6-10, 6-12, 6-36, 12-12; their copolymers and mixtures.

6. The use according to claim 1 or 2, characterized in that the zinc sulfide is in the form of particles that are coated and/or enclosed in the capsule, at least one mineral and/or organic compounds.



 

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