WO2006087460A1

WO2006087460A1 - Composite thread and obtained textile

Info

Publication number: WO2006087460A1
Application number: PCT/FR2006/000334
Authority: WO
Inventors: Olivier Lefebvre; Alain Cotte; Bruno Thevenet; Lionel Benant
Original assignee: Actif Wear
Priority date: 2005-02-15
Filing date: 2006-02-14
Publication date: 2006-08-24
Also published as: JP2008531858A; CA2599027A1; FR2882067B1; EP1856315A1; US20090124152A1; FR2882067A1

Abstract

The invention relates to a composite thread (18), comprising a core (16) and a shell (17). The core (16) is produced from at least one thread of one or more metallic materials with biocidal properties. The shell (17) is made from one or more textile fibres directly covering all or part of the core (16).

Description

COMPOSITE YARN AND TEXTILE OBTAINED

The invention relates to a composite yarn. The invention also relates to a textile obtained with the composite yarn, used alone or in combination with other textile materials. The invention also relates to an article of clothing or packaging made from this composite yarn.

In general, a textile has a protective coating function for packaging, covering and protecting living or inert materials against the main factors detrimental to their safety. Textiles provide protection against biological aggressions, such as bacteria, fungi, yeasts, viruses, allergens, algae, against chemical attacks, such as gases, fumes, dust, against physical aggression , such as radiation, hot or cold air, moisture and against mechanical aggression, such as friction, shock, punctures and cuts. A yarn is a basic constituent of a textile and has characteristics of flexibility, fineness, great length relative to its diameter.

For a long time, the therapeutic properties of certain metals have been widely recognized. Copper, zinc and silver in metallic form are strongly biocidal or germicidal, by action against germs such as bacteria, yeasts and fungi, and algicides by action against algae, according to a particular mechanism called "oligodynamic effect". These metals are almost insoluble in water. The few ions produced penetrate the cells of microorganisms or algae and act by complexing the formed metal ions (Cu ²⁺ for copper, Zn ²⁺ for zinc, Ag ⁺ for silver) on the thiol groups ( -SH), carboxylic acids (-COOH), phosphates (-PO ₄ H ₂ ), hydroxyls (-OH), amines (-NH ₂ ), imidazoles or indoles of the proteins and on the bases of the nucleic acids of the RNAs of the nucleus of the cells . The growth of these microorganisms or algae is inhibited by biocidal action. The bacterial cells are bacteriostatic because they are rendered sterile and can no longer divide. As a result, the bacterial population does not multiply anymore. State of the art

According to the literature, the antibacterial activity of copper is limited to Staphylococcus and Streptococcus (Gram +). Copper-based compounds and in particular copper sulfate are especially endowed with antifungal properties. Copper is active on fungi such as Trichophyton interdigital or Trichophyton gypseum. Copper is inactive against other filamentous fungi such as Aspergillus niger. Antibacterial activity is more important on Gram-positive bacteria than Gram + bacteria.

To combat micro-biological risks, one technique consists of enriching textiles with active agents. These agents are added to the fibers, yarns and / or textile. To date, there are various antimicrobial, antibacterial and antifungal agents widely used in this field.

First, minerals or zeolites, for example tectosilicates, aluminosilicates, calcium or alkali, are combined with metals, such as mainly copper, silver and zinc. They are incorporated in fibers obtained by molten route. As an example, the ceramic based on zirconium phosphate and silver, marketed under the name of AlphaSan® RC 5000.

These agents are also added to the surface of several fibers. These are for example a filament of Polyamide 6-6, known under the name X-static ™, marketed by the company Noble Fiber Technology. These mineral treatments are suitable for textiles having high melting temperatures above 250 ° C, such as polyamides, polyesters.

Next, chemical molecules, such as triclosan (Irgasan® from Ciba Specialty Chemicals), are agents with a broad spectrum of antibacterial and antimicrobial activity. Triclosan can only be used in materials with a melting point below 215 ° C.

Finally, chitosan is a natural polymer derived from chitin used in health applications, agriculture, as well as as a dyeing aid for fabrics. It also cleans and whitens pool water, eliminating algae and other impurities.

However, these methods have the problem of the rate of antimicrobial agents to be incorporated in order to obtain convincing results, without modifying the characteristics of the fiber. Indeed, zeolites are minerals that make the wire brittle. In addition, thermal stresses can also modify or even destroy the characteristics antimicrobial agents, such as triclosan. Then, these antimicrobial agents can also be incorporated after extrusion, during the sizing of son or in coating processes and or dyeing son. But, the permanence of the metal and metal ions in time is only very random. The size will undergo friction and its resistance in aqueous medium remains limited. These treatments with zeolites, coating or gaseous metal deposits, impregnation of triclosan or chitosan, are labile, and extractable to solvents, laundry, sweat or other chemical dyes or bleaching agents, at temperature. This makes the effectiveness of antimicrobial agents will decrease and disappear as and when textile uses.

To be active on the existing seeds on the surface of the fibers, part of the active ingredient incorporated in the polymer must be on the surface. Depletion of the active ingredient due to dyeing, abrasion, extraction by sweat or cleaning products must be compensated for by slow migration through the filament or fiber to the surface. The mass concentration of the active ingredient, its distribution, mobility in the polymer and the diameter of the filament or fiber are therefore important parameters.

While keeping a high efficiency, the textiles obtained by finishing have a better resistance to maintenance than textiles having undergone a simple deposition without binder. However, the presence of binder will modify the surface properties of the fibers, the binding of the fibers together and therefore the properties of the fabrics (flexibility, feel and appearance) and will partially mask the effectiveness of the biocide molecules. The durability of these treatments depends on many factors, the main one being the strength of the attachment of the active ingredient to the surface of the fibers with respect to dyeing conditions, abrasion and washes.

Presentation of the invention

The main problem to be solved by the invention is to make a wire preventing the development of bacteria, fungi, algae or other living elements. A second problem is that of keeping the "textile" touch for a thread with bacteriostatic properties. A third problem is to make bacteriostatic properties of a yarn durable, without altering over time and regardless of the conditions of use of the textile. A fourth problem is to avoid the formation of bad odors, as well as allergies, by developing a new type of yarn for a textile. A fifth problem is to make a wire that can be ennobled without special precautions, dyeing, printing, and others. A sixth problem is that of preventing the formation of static electricity in a textile by the addition of a specific wire. A last problem is finally to make a textile article or an article of clothing, comprising at least one wire with biocidal properties.

According to the present invention, a composite yarn comprising a core and a sheath, characterized in that the core is made from at least one continuous yarn in one or more metal materials with biocidal properties and in that the sheath is made from one or more textile fibers directly covering all or part of the core.

In other words, the core provides the biocidal properties and the sheath brings the characteristics of the yarns traditionally used in the textile field. By "biocide" is meant properties referring to the European Biocide Directive 98-8. By wire into one or more metallic materials is also meant sections of continuous wire, which can be calibrated or isotropic and spinned with a fiber ribbon. By one or more textile fibers is also meant son or a continuous filament. The yarn will thus have bacteriostatic, fungistatic and / or algicidal properties, slow diffusion and controlled. It is therefore a thread, which by its composition, prevents the development of potentially pathogenic elements for living beings. The wire and the achievements that implement it, is no longer a source of contamination for the materials with which it comes into contact. The metal ions released by the core of the wire penetrate and complex with the ribonucleic acids and the proteins of the microorganisms, thus blocking any multiplication. The presence and low solubility of this metal core in liquid medium, gives it an extreme longevity, linked to the permanence of its presence in the wire. The sheath will provide the properties usually known for textile yarns of the state of the art. Due to its characteristics, this type of yarn is used in the field of human and animal hygiene, food safety, the medical and agricultural environment, and the filtration of aqueous and gaseous media. The yarn is adapted to be implemented according to all the techniques used in the textile field, winding, sewing, weaving, knitting, braiding, embroidery, topping, and others. In a particular embodiment, the son or son of the core can be plated (covered by electrolysis) with one or more metal materials with biocidal properties. This embodiment makes it possible to obtain a composite yarn, of which only the metal surface has the desired biocidal properties. In another variant, this same embodiment relates to a composite yarn made of a first metallic material with the desired biocidal properties which is plated with a second metal material with other desired biocidal properties. The presence of two materials, copper and silver, prevents any oxidation of the two metals. On the wire, there are no black (for silver) or bluish (for copper) traces. Very preferably, in order to promote the holding of the son or textile fibers on the core of the wire, the core may have an apparent surface with a structure forming attachment points for the textile fiber or fibers of the sheath. All the structures of a wire are possible. Thus, the soul has a geometric structure, as for example a line, a blade, a star, a flake, filamentous or all other forms, which facilitate the catch, the flu of the textile. Depending on the type of fibers used for the sheath, the metal core may be streaked, blasted, undergo any type of treatment, to facilitate the attachment of the sheath. Similarly, a non-planar, porous structure can be made to trap micro-air bubbles, with the aim of increasing the exchange surfaces and improve the thermoregulatory characteristics of the wire.

If one wants to influence the microbial and antistatic characteristics of the soul, one will be able to play on its geometrical structure. Indeed, depending on the type of migration desired, we can by the geometric structure used for the soul, affect either the level of solubility or the oligodynamic effect. This effect lies in the mass / surface ratio of the core and the mass / surface of the wire. If you want a greater effect on a given thread, with a mass identical for the soul, then we prefer a blade instead of a line. An equivalent mass will thus be obtained with a larger chemical exchange surface. This phenomenon can be further increased by producing a non-planar surface, granular, striated, shell. These different factors make it possible to regulate the levels of migration in order to be in conformity with the rules of individual and global migration necessary for the approval for the food contact.

Depending on the desired biocidal activity, the metal material (s) with biocidal properties may be favorably selected, alone or in alloy, in the group including zinc, silver, tin, copper, gold and nickel. With this choice of metallic materials, the targeting of bacteria and other pathogenic elements to be destroyed leads to broad spectrum efficiency or the opposite with a particular action precision. For a food application whose objective will be the control of pathogenic colonies, such as Listeria, Salmonella, Escherichia coli, Staphylococcus aureus, etc., the mixtures will be mainly composed of zinc and silver, the presence of copper being less important. On the other hand, if the yarn has a smell prevention destination in a shoe sole, the fungistatic function will be put forward and, in this case, the proportion of copper will be greater. The presence of the metal core, electrically conductive material, in the wire of the present invention will therefore be sufficient to dissipate the static electricity charges. The presence of a metal core, in the heart of a composite wire, provides the latter with a function of resistance to cutting.

Depending on the final desired textile, the textile fiber or fibers of the sheath may be chosen, alone or in a mixture, from the group comprising fibers of natural, artificial and synthetic origin. In a first case, the fibers of natural origin can be advantageously chosen, alone or as a mixture, from the group comprising animal and / or vegetable fibers, for example cotton, wool, silk, linen, cellulose and still others. For example, depending on the textile fiber used in sheath, good heat resistance is obtained. If the sheath is wool, a good resistance to heat is obtained.

In a second case and advantageously, the synthetic fibers may be chosen, alone or as a mixture, from the group comprising acrylics, polyamides, polypropylenes and others. The yarn according to the present invention can withstand dyeing, printing, heat setting, under the same processing conditions as conventional textiles. Thus, if the yarn in a particular embodiment is composed of a cotton top layer, the latter may be bleached, dyed or printed under the same conditions of chemistry as a pure cotton yarn.

The sheath can be favorably achieved by a method of assembly, wrapping, guimping, twisting, milling, friction spinning Dref ™ (from FEHRER AG) and others. The mechanical implementation of the textile sheath by textile fibers, short or long, by a fiber yarn, by a cardboard tape, by a combed tape, mono or multifilament, continuous or discontinuous, allows to maintain the "textile touch " some thread. In another embodiment, all or part of the core may be covered by a porous coating, so as to facilitate the attachment of the or textile fibers of the sheath.

In a second aspect of the present invention, a textile is characterized in that it comprises at least one composite yarn as described above. The textile can be made by a process of weaving, knitting, braiding, embroidery, topping, nonwoven (by needling), and others. The fineness of section of the strand (s) composing the core allows the composite yarn to retain its flexibility. The fineness of section limits the so-called shape memory phenomenon related to the upper section wire (spring effect). The yarn of the present invention will withstand the stresses of shaping, specific to the implementations of textiles, such as the embossing, the needle passage, the tension of the sewing machines, etc. Pleasant to wear, the textile will not provide any inconvenience of contact for the wearer or in the case of packaging for the transported or conditioned material. According to a third aspect of the invention, an article of clothing is characterized in that it is assembled using at least one composite yarn as described above.

Brief description of the figures

The invention will be better understood and its various advantages and different characteristics will become more apparent in the following description, of the nonlimiting exemplary embodiment, with reference to the appended diagrammatic drawings, in which:

- Figure 1 shows a round core (line) of a composite wire according to a first embodiment;

- Figure 2 shows, in side view, a first processing method of the core of Figure 1 for obtaining a flat core (blade) and a composite wire according to a second embodiment;

- Figure 3 shows, in side view, a second method of processing the core of Figure 1 for obtaining a core and a composite wire according to a third embodiment; FIG. 4 represents, in a view from above, a third process for treating the core of FIG. 2 to obtain a core and a composite yarn according to a fourth embodiment; - Figure 5 shows, in top view, a fourth core processing method of Figure 2 for obtaining a core and a composite wire according to a fourth embodiment;

- Figure 6 shows a side view of a composite wire according to a first embodiment; and

- Figure 7 shows a cross sectional view of a composite wire according to a second embodiment.

DETAILED DESCRIPTION OF THE INVENTION As shown in FIGS. 1 and 2, and in a preferred embodiment, the core (1) of a composite yarn is constituted by a line or monofilament, that is to say by a continuous round copper wire (2) covered with a thin layer of silver or tin (3). The copper wire (2) has a diameter of about 67 μm. The silver layer (3) has a thickness of about 5 thousandths of copper. As shown in Figure 2, the core (1) is laminated by passage between two rollers (4 and 6) of a smooth cold rolling mill. A new continuous laminated core (7) of silver-plated or tin-plated copper, approximately 5 μm thick and with a width of approximately 0.20 mm, is obtained.

Figure 3 shows a method of treating the surface of the core (1) of Figure 1 by two knurling cylinders (8 and 9). The resulting silver-copper wire core (11) is marked to improve the grip of yarns and / or textile fibers, and to optimize the mass-to-surface ratio of the metals.

Figure 4 shows a method of treating the surface of the core (7) of Figure 2 by two simple knurling rolls (12). The blade (13), forming the core, has transverse striations parallel to each other.

Figure 5 shows a method of treating the surface of the core (7) of Figure 2 by two cross-knurling cylinders (14). The blade (16) forming the core has staggered ridges by cross knurling.

In a first exemplary embodiment (see FIG. 6), the blade-shaped core (16), for example that obtained and shown according to the method of FIG. 5, is covered with a continuous textile fiber (17) by grinding. or wrapping. The composite yarn obtained (18) is thus guiped. For example, the core (16) is gimped with a cotton of metric number 28. The covering consists of covering a core wire with one or more sheaths made of different wires. The monofilament blade (16) is energized to be guiped in mono or double sheath. In the particular embodiment, the cotton, first winding, brings its strength and softness. It can in case of double wrapping there is an outer winding. The covering fiber (17) is chosen according to its characteristics, so that it provides its own qualities (thermoregulation, textured fiber, etc.).

In a second exemplary embodiment (see FIG. 7), the blade-shaped core (16), for example that obtained and shown according to the method of FIG. 5, is covered with discontinuous fibers (19). The composite yarn (21) is thus obtained by the Dref ™ friction spinning technique.

Tests carried out with the composite yarns according to the invention

The antibacterial and antifungal properties of different yarns (see Table 1 below), composed of metal monofilaments (silver and copper) gimped by cotton fiber, were evaluated. The yarns are transformed into knits for testing according to standardized microbiological tests, according to: Swiss Standard SNV 195 920, a qualitative test which determines the antibacterial activity by diffusion on agar; this standard shows the antibacterial activity of a textile support having undergone a finishing treatment or containing a fiber treated in the mass and giving rise to a diffusion of the active ingredient in the nutrient medium; Swiss standard SNV 195 921, a qualitative test which determines antifungal activity by agar diffusion; this standard demonstrates the antifungal activity of a textile support having undergone a finishing treatment or containing a fiber treated in the mass and giving rise to a diffusion of the active ingredient in the nutrient medium; the French standard XP G 39-010, a quantitative test that measures bacteriostatic properties by agar contact; this standard makes it possible to determine the bacteriostatic activity on the surface of the fabrics and the polymeric surfaces acting by contact or by diffusion of the antibacterial active agent, whether the fabrics are hydrophilic or hydrophobic; and the French standard in preparation, a quantitative test that measures the fungistatic properties by agar contact.

The control knit, to validate the microbiological tests and to calculate the bacteriostatic and fungistatic efficiency, is made of a 100% cotton thread.

Table 1

The knits are steam sterilized before any microbiological test. Before carrying out the microbiological tests, a portion of the knitted test pieces is washed 10 times at 40 ° C., according to the ISO 6330 standard, in the presence of ECE detergent at 3 g / l, and rinsed with cold. Table 2 shows the results of the microbiological tests obtained using the qualitative standards SNV 195 920 and SNV 195 921. Table 3 shows the results of the microbiological tests obtained using the quantitative standard XP G 39-010, for the different knitwear samples, the different strains, before and after the 10 washes at 40 ° C.

The strains used for the tests are: Staphylococcus aureus (Gram +), strain present on the skin and responsible for infection, Candida albicans (yeast), strain responsible for infection of the mucous membranes and Ospergillus niger (fungus), common strain present in the 'environment.

Table 2

From the results shown in the table above, corresponding to the qualitative tests, and in the sense of the standards used, the absence of inhibition zone means low activity. In fact, the absence of an inhibition zone means a weak release of metal ions in the agar. As a first approximation, a weak release of metal ions in the agar prefigures a weak diffusion of the metal ions towards the surface which will be in contact during the use (the skin in the case of an undergarment, a food in the case packaging, etc.). This weak diffusion foreshadows a good biocompatibility.

The bacterial concentrations are expressed in CFU (Colony Forming Units), in CFU log, in CFU log difference (values appearing in Table 3 below), for a contact time of 24 hours. The concentrations of fungi or yeast cells are expressed in CFU (Colony Forming Units), in CFU log, in CFU log difference (values appearing in Table 3 below), for two contact times of 24. hours and 7 days.

Table 3

Under the experimental conditions, Tricot No. 3, composed of 20% copper and

20% silver in mass, presents a fungistatic activity on Aspergillus niger (qualitative tests).

Tricot No. 4 (40% silver) and Tricot No. 5 (40% tinned copper) have a bacteriostatic activity on Staphylococcus aureus before washing and after 10 washes at 40 ^° C. This activity is due to the presence of metal in the knit: presence of silver on the flat wire (blade), presence of copper and tin on the surface of the round wire.

Knit # 7 (silver and copper base) has a fungistatic activity on Aspergillus niger before washing. This activity is due to the presence of a mixture of copper and silver in the wire of rectangular section which constitutes the knitting.

The yarns that make up knits # 4, 5 and 7 therefore have bacteriostatic and / or fungistatic activity with respect to the same strains, respectively.

A flat yarn (or blade: knit 4) is more active than a round yarn (knit 1) vis-à-vis Staphyloccocus aureus because of its structure. The tinned round copper wire (knit 5) is more active than the other round yarns (knit 2) with respect to Staphyloccocus aureus because of the presence of tin on the surface due to tinning.

The present invention is not limited to the embodiments described and illustrated. Many modifications can be made, without leaving the framework defined by the scope of the set of claims.

The uses of the yarn and the textile according to the invention are extremely varied. For example, wire winding in pool filter cartridges, for air conditioning filter, wire for assembling textiles, leathers for shoes, fabrics for furnishing, mattresses, towels, clothing, food packaging, geotextiles for agriculture, horticulture, viticulture, and others.

Claims

Composite yarn comprising a core (16) and a sheath (17, 19), characterized in that the core (16) is made from at least one wire made of one or more metallic materials with biocidal properties and in that the sheath (17, 19) is made from one or more textile fibers directly covering all or part of the core

(16).

2. Thread according to claim 1, characterized in that the son or son of the core (17) are made of one or more metal materials with biocidal properties.

3. Thread according to claim 1 or 2, characterized in that the core (16) may have an apparent surface with a structure forming attachment points for the textile fiber or fibers of the sheath (17, 19).

4. Thread according to any one of the preceding claims, characterized in that the one or more metal materials with biocidal properties are chosen, alone or in alloy, in the group comprising zinc, silver, tin, copper, gold and nickel.

5. Yarn according to any one of the preceding claims, characterized in that the textile fiber or fibers of the sheath (17,19) are chosen, alone or as a mixture, from the group comprising fibers of natural origin, preferably the cotton, wool, silk, linen, cellulose, artificial fibers and synthetic fibers, preferably acrylics, polyamides, polypropylenes.

6. Thread according to any one of the preceding claims, characterized in that the sheath (17, 19) is made by a textile mechanical bonding process, spinning, milling, wrapping, guimpage, twisting, friction spinning Dref ™.

7. Thread according to any one of the preceding claims, characterized in that all or part of the core is covered by a porous coating, so as to facilitate the attachment of the or textile fibers of the sheath.

8. Textile, characterized in that it comprises at least one composite yarn (18, 21) according to any one of the preceding claims.

9. Textile according to claim 8, characterized in that it is achieved by a method of weaving, knitting, braiding, embroidery, topping, nonwoven.

10. article of clothing, characterized in that it is assembled using at least one composite yarn (18, 21), according to any one of claims 1 to 7.