WO2009080458A1

WO2009080458A1 - Process for preparing dyeable polypropylene

Info

Publication number: WO2009080458A1
Application number: PCT/EP2008/066766
Authority: WO
Inventors: Paolo Francesco Stellini; Eugenio Magni
Original assignee: Paolo Francesco Stellini; Eugenio Magni
Priority date: 2007-12-19
Filing date: 2008-12-04
Publication date: 2009-07-02
Also published as: ITMI20072383A1

Abstract

A composition of dyeable polypropylene comprising polypropylene and a component based on a dyeable polymer that is compatible with the extrusion temperatures of polypropylene; a process for producing the dyeable polypropylene by way of the mixing of a polypropylene and of a component based on a dyeable polymer that is compatible with the extrusion temperatures of the polypropylene; a process for dyeing the dyeable polypropylene and dyed or printed textile products prepared with the dyeable polypropylene.

Description

PROCESS FOR PREPARING DYEABLE POLYPROPYLENE

Technical Field

The present invention relates to a process for producing dyeable polypropylene. Background Art

The use of thermoplastic polymers in everyday life is widespread, thanks to the workability, perfect impermeability and light weight that characterize such materials and have made them popular to the point that an average use of 4 kg per year per person over the last 50-60 years has been estimated.

Polypropylene (or polypropene or PP) is one of the most important thermoplastic polymers in the world, due both to its diffusion in many production sectors and to the quantities absorbed by the world market. Its good mechanical and thermal qualities, its resistance to chemical attack and its low cost make polypropylene a widely utilized polymer. It is sufficient to consider that polypropylene is transformed by the thermoplastics industry into a broad range of items of everyday use: components for cars, kitchen utensils, textile fiber for garment fabrics, coverings for packaging and, more generally, articles in the medical and electrical sector, toys, technical items, and so forth.

Historically, the development of technologies for polymerization of polypropylene is due to the studies performed by Natta in the 1960s. Due to the chemical nature of propene, the precursor of polypropylene, at least two forms of polypropylene, known as PP-A (atactic) and PP-I (isotactic), are obtained from the polymerization of this monomer. While the former is a material whose properties are scarcely useful in the commercial and industrial field, the second one lends itself much more easily to utilization in these sectors. The development by Natta of a catalyst capable of giving a high yield of isotactic polypropylene, where all the methyl groups that substitute propene units are oriented in the same direction with respect to the polymeric chain (isotactic PP), thus opened the way to the diffusion of polypropylene. Over the years, polymerization techniques and catalysts have evolved, so that in the 1990s the transition occurred from polymerization by precipitation at low pressure in propane gas with Ziegler-Natta type catalysts, to new systems for polymerization in gaseous phase with the addition of a minimum percentage of high-yield catalysts that can be adjusted selectively (PP-I up to 97%). With this type of technology it is possible to set in a targeted manner the characteristics of the polypropylene, including those of the chemical and physical type, so much that the formulations of PP that are currently available are extremely numerous.

The polymer can be obtained in the form of a fiber following two operations: spinning and stretching.

In spinning, the polymer is passed through spinnerettes, which are provided with gauged holes in order to reduce it to thin yarns of indefinite length in melted form or in the form of a solution in a suitable solvent, and then the material is solidified by cooling, solvent evaporation or solvent removal in a bath of a liquid in which the polymer, differently from the solvent, is not soluble. In particular, the polypropylene can be extruded only when hot through melting, whereas polymers such as acetates and acrylics are dissolved in a solvent.

In stretching, a force is applied in the direction of the length of the yarn, which entails a considerable elongation of the yarn and the reduction of up to one tenth of the diameter on the one hand and, on the other hand, the reorientation of the polymeric chains, with a consequent increase in toughness, luster and resistance to wear. Further finishing operations cause the resulting yarn to have all the characteristics typical of polypropylene fiber suitable for underwear, sportswear, children's clothes and for fabrics in general.

However, in contrast with the numerous advantages of polypropylene and its wide diffusion also in the textile field, this polymer cannot be dyed, giving rise to considerable logistic and economic complications.

Among the solutions to this problem that have been developed so far, dyeing has been possible only by adding colored pigments in the form of a master batch before spinning the polypropylene. This method allows to obtain dyes that are very fast to light and washing, but it is not a versatile process and moreover it does not allow production economies. It is in fact necessary to purchase and thus keep in stock considerable quantities of yarn that is already colored in order to obtain articles in the different colors as required by fashion and the market. The background art also includes several patents and researches of a worldwide nature to obtain a dyeable polypropylene, so as to allow dyeing of the polypropylene fiber in different colors that are fast after spinning, but they have yielded few practical results.

There is, therefore, still the need by all textile users to be able to dye polypropylene.

The aim of the present invention is to provide a process that allows to dye a fiber that is not dyeable, such as polypropylene.

Within this aim, an object of the invention is to provide a process that leads to the production of polypropylene that can be dyed also after spinning.

Another object of the invention is to provide a dyeable polypropylene and textile products prepared with such polypropylene.

Still another object of the invention is to provide a process that is highly reliable, relatively simple to perform and at competitive costs. Summary of the invention

This aim, as well as these and other objects that will become better apparent hereinafter, are achieved by a process for producing a dyeable polypropylene (PP), which comprises the step of mixing a polypropylene and a component based on a dyeable polymer that is compatible with the extrusion temperatures of polypropylene. The aim and objects of the invention are also achieved by a process for obtaining a dyed polypropylene, comprising the steps of: producing a dyeable polypropylene according to the present invention; dyeing said dyeable polypropylene or an article produced with it.

Moreover, the aim and objects of the invention are also achieved by a composition of dyeable polypropylene that comprises polypropylene and a component based on a dyeable polymer that is compatible with the extrusion temperatures of polypropylene. Moreover, the aim and objects of the invention are also achieved by a fiber, yarn, fabric, mesh or spunbond or meltblown or nonwoven fabric provided by means of a composition according to the present invention.

Moreover, the aim and objects of the invention are also achieved by a fiber, yarn, fabric, mesh or spunbond or meltblown or nonwoven fabric that are dyed or printed and obtained by dyeing a fiber, yarn or flock according to the present invention or by printing a fabric obtained with a fiber, yarn or flock according to the present invention.

Further objects, characteristics and advantages of the invention will become apparent in the detailed description that follows. Detailed description

According to the invention, the process of the present invention comprises mixing a polypropylene (PP) and a dyeable polymer that is compatible with the extrusion temperatures of polypropylene. Compatibility with the extrusion temperatures of polypropylene entails that the dyeable polymer may be characterized by a melting point from 180⁰C to 310⁰C, preferably from 220⁰C to 28O⁰C. These temperature intervals are in fact compatible with the temperatures that are necessary for PP extrusion.

The combination of the non-dyeable polymer (PP) with a dyeable polymeric material whose melting point is compatible with the PP allows to prepare a composition that can be easily processed and converted into fibers and then dyed. The dyeable polymer mixed with PP in fact allows dyes to penetrate easily into the fibers of the composition and to retain the color inside them.

In an embodiment of the present invention, the dyeable polymer that is compatible with the extrusion temperatures of polypropylene may be a polyethylene terephthalate (PET), a polyethylene terephthalate modified for cationic dyeability, polylactic acid (PLA), a polymer of bio-natural origin, or a mixture thereof.

Moreover, the PET and the PET modified for cationic dyeability may be characterized in that they have an intrinsic viscosity (IV) of less than 1 dl/g measured in dichloroacetic acid according to the ASTM D 2857 standard, more preferably an intrinsic viscosity ranging from 0.4 dl/g to 0.7 dl/g, even more preferably from 0.45 dl/g to 0.65 dl/g. Intrinsic viscosity is calculated according to the following formula: IV = SV x 0.0006907 + 0.063096 where SV indicates the specific viscosity of the polymer measured in dichloroacetic acid.

By way of example, the PET modified for cationic dyeability may be the PET identified by the code RT2511 produced by Invista. The polylactic acid may be for example PLA 4042D produced by Nature Works. The PET may be for example the PET identified by the code RT 12 or the PET copolymer identified by the code 4041 , both of which are produced by Invista.

The expression "PET modified for cationic dyeability" is intended to refer to a PET containing an agent that allows dyeing with cationic dyes (basic dyes). Preferably, such dyeing agent that allows dyeing with cationic dyes may be selected from the group consisting of sodium dimethyl-m- phthalate-5-sulfonate, tricalcium phosphate, 5-sulfoisophthalic acid sodium salt (SIPNa or NaSIP) and 5-sulfoisophthalic acid lithium salt (SIPLi or LiSIP). By way of example, the 5-sulfoisophthalic acid sodium salt may be NaSIP A-Ultrapure^®, marketed by DuPont.

In the process according to the invention, the PET modified for cationic dyeability may comprise 1% to 50% by weight of the agent that allows dyeing, preferably 1% to 40%, more preferably 1% to 25%, even more preferably 1% to 10%.

In an embodiment of the process according to the present invention, the dyeable polymer may be mixed with the PP in a proportion from 1% to 50% by weight relative to the total weight of the resulting final fiber (PP fiber plus dyeable polymer). Preferably, the proportion may be 2% to 40%, more preferably 2% to 30%, even more preferably 2% to 20%.

In another embodiment of the present invention, the process may further comprise the step of mixing the PP and the dyeable polymer with one or more additives that are known to the person skilled in the art of polymeric materials. These additives may be UV stabilizers, such as for example polymeric HALS (Hindered Amine Light Stabilizers), flame retardants, such as for example brominated compounds, or biocidal compounds, such as for example nanoceramic silver.

In the process according to the present invention, the mixing of the PP with the dyeable polymer may occur by using a gravimetric mixing/dosage unit, a volumetric mixing/dosage unit, a simple mechanical mixing tower or by direct injection into the spinning head of another extruder.

Once the PP and the dyeable polymer have been mixed, the composition may be processed by means of the techniques and corresponding instruments that are generally known to the person skilled in the art in the field of the processing of polymeric materials. In particular, according to the present invention, the process may comprise a further processing step, which consists in extruding the mixture of PP and dyeable polymer. In another aspect, the present invention relates also to a process for obtaining a dyed PP. This process provides for the step of preparing a composition of PP and of a dyeable polymer according to the process herein described and the step of dyeing such composition or, alternately, an article prepared with it. Preferably, the dyeing step occurs by using a disperse dye, a type of dye that is commonly used to dye synthetic fibers and particularly polyester fibers.

Disperse dyes are divided into several classifications, mainly according to the size of the molecule of the dye and therefore to its steric hindrance. These parameters affect the result of dyeing, allowing to obtain dyes that are more or less fast with respect to light or washing. Generally, a dye characterized by molecules with a high steric hindrance encounters greater difficulties in penetrating into the polymeric fiber and therefore requires a higher addition of heat energy during the dyeing step. This, however, leads also to superior wash fastness of the final product, since the steric hindrance also affects the capacity of the dyeing molecule to exit from the fiber. In the case of dyes that contain molecules with a low steric hindrance, the behavior is substantially reversed, and therefore one observes easier access to the fibers by the dye, allowing to use gentler dyeing temperatures, and higher sensitivity during washing of the finished product. By way of example, such disperse dyes may be the Foron^® dyes marketed by Clariant, the Terasil^® dyes marketed by Huntsman, or the Dianix^® dyes marketed by Dystar.

In the process according to the invention, the dyeing step may be performed at a temperature ranging from 70⁰C to 130⁰C, more preferably from 98°C to 12O⁰C. Moreover, the dyeing step may be performed by working at different pressure values, starting from standard atmospheric pressure up to values of 2-3 bars under pressure. Although dyeing under pressure is more expensive in energy terms, its use leads to higher yields in terms of dyeing of the polymeric material, with a consequent saving of dyes. Moreover, the dyeing step may be performed in an acid bath, which can be characterized by a pH of approximately 4.5. In a preferred embodiment, the acid bath may contain acetic acid. Of course, the acetic acid may be replaced with any other acid having equivalent properties. In another embodiment of the process for obtaining dyed PP, the dyeing step may be characterized by the further use of a dye dispersant, in order to achieve good dyeing uniformity. Preferably, such dispersant may be a sulfonated aromatic polyether. By way of example, the dispersant may be Lyocol^® RDN, marketed by Clariant. Optionally, during the dyeing step it is further possible to use a retardant leveling agent. Preferably, the retardant leveling agent may be an oxyethylation product based on fatty acids. By way of example, the retardant leveling agent may be Eganal^® RAP, marketed by Clariant.

In another embodiment of the process according to the invention, it is possible to provide the additional step of cleaning the dyed PP with a reducing agent. Preferably, cleaning may be performed with sodium hydrosulfite in the presence of alkali (bases), such as for example caustic soda (sodium hydroxide). The combined use of caustic soda and hydrosulfite allows to remove effectively the dye that has not fixed to the polymeric material.

The temperature of the reducing cleaning treatment may be performed in a range from 50⁰C to 80⁰C, preferably 50⁰C to 70⁰C.

In another aspect, the present invention relates also to a composition of dyeable PP, which comprises PP and a dyeable polymer that is compatible with the extrusion temperatures of polypropylene. Preferably, this composition comprises PP and a dyeable polymer, such as for example a PET, a PET modified for cationic dyeability, polylactic acid, a polymer of bio-natural origin, or a mixture thereof.

Of course, the composition of dyeable PP may further comprise one or more additives that are known to the person skilled in the art of polymeric materials. Such additives may be UV stabilizers, such as for example polymeric HALS (Hindered Amine Light Stabilizers), flame retardants, such as for example brominated compounds, or biocidal compounds, such as for example nanoceramic silver. The dyeable PP composition according to the invention may be used to provide textile products such as a fiber, a yarn, a fabric, a mesh, a spunbond, meltblown or nonwoven fabric, and these textile products represent another aspect of the present invention. The dyeable PP of the present invention may therefore be used for production both of continuous yarn and of discontinuous yarn (flock). In particular, discontinuous yarn lends itself more easily to combination in an intimate mixture of dyeable PP with natural fibers (for example wool or cotton), artificial and synthetic fibers (including polyamide fibers, polyesters, acrylic fibers and viscose), also in the form of flock. For example, the combination of polypropylene both with wool and with cotton gives lightness to the manufactured articles, quicker drying thereof and easier maintenance during use and during domestic washing.

Also in combination with artificial or synthetic fibers, PP fiber allows to obtain advantages that cannot be achieved with other fibers, such as a substantial increase in lightness and comfort during wearing that cannot be obtained with these fibers used individually.

The textile products provided with the dyeable PP of the present invention can then be dyed or printed after their preparation. These dyed or printed textile products constitute another aspect of the present invention. Examples of the process according to the invention are provided hereinafter. These examples are to be considered by way of non-limiting example of the present invention. Examples

In order to evaluate the dyeability of the polypropylene prepared according to the process of the invention, mixtures of polypropylene and of a dyeable polymer were prepared by using the materials and the quantitative ratios indicated in Table 1, where the polypropylene used is an Ecolen HZ40S homopolymer PP produced by Hellenic Petroleum or a Moplen HP552R homopolyer PP produced by Basell; PET CD (Cationic Dyeable) RT2511 is a polyethylene terephthalate modified for cationic dyeing with code RT2511 produced by Invista; PET RTl 2 is a polyethylene terephthalate with code RT 12 produced by Invista; PET 4041 is a PET copolymer with code 4041 produced by Invista; and PLA is a polylactic acid with code 4042D produced by Nature Works.

Table 1

Sample !

Polypropvlene Dveable polvmer

1 85% 15% PET CD RT2511

2 80% 20% PET CD RT2511

3 80% 15% PET CD RT251 1 + 5%

4 85% 15% PET RT 12

80% 20% PET RT12

6 80% 15% PET RT 12 + 5% PLA

7 85% 15% PLA

8 80% 15% PLA + 5% PET RTl 2

9 80% 15% PLA + 5% PET CD RT i 10 85% 15% PET 4041

11 80% 20% PET 4041

12 80% 15% PET 4041 + 5% PLA

13 80% 15% PLA + 5% PET 4041

Example 1 (deep blue dve) A dyeing bath with a pH of 4.5 was prepared which contained 2.5% Foron^® RDS (Clariant) blue dye, 1% Lyocol^® RDN (Clariant) dispersal agent, 1 g/1 of 60% acetic acid. Dyeing was performed with a bath ratio of 1 : 10 and at the temperature of 12O⁰C. The dyeing process is the following: start at ambient temperature with all the auxiliary components and the dye; rise with a gradient of l°C/min up to the temperature of 12O⁰C; hold for 45 minutes at the temperature of 120⁰C; cooling the bath to 60⁰C.

Subsequently, the material is rinsed while hot and cleaning is performed with a reducing agent in order to eliminate the dye that has not been fixed. This operation is performed at the temperature of 75⁰C for 20 minutes in a bath prepared with the following products: 3 cc/1 of caustic soda 36 Be, 1.5 g/1 of sodium hydrosulfite, 0.5 g/1 of Lyocol^® RDN.

Tests of wash fastness at 40⁰C (ISO 105C06 standards) and of acid and alkaline sweat fastness (ISO 105-E04 standards) were conducted and showed good values both in terms of shade degradation (value 4/5) and in terms of fading on multifiber material (average value = 4).

The procedure of Example 1 was repeated also at the temperature of 98⁰C, obtaining a slightly lower dyeing yield. After reducing cleaning performed with the same recipe indicated above, the same good values of wash fastness and acid and alkaline sweat fastness were observed. Example 2 (brown dye)

A dyeing bath with a pH of 4.5 was prepared which contained 2.1% Foron^® RD 4GRL (Clariant) yellow dye, 0.9% Foron^® RDS (Clariant) ruby dye, 1.4% Foron^® RDS blue dye, 1% Lyocol^® RDN (Clariant) dispersal agent, 1 g/1 of 60% acetic acid. Dyeing and subsequent cleaning with reducing agent were performed according to the same procedure of Example 1.

Tests of wash fastness at 40⁰C (ISO 105C06 standards) and of acid and alkaline sweat fastness (ISO 105-E04 standards) were conducted and showed good values both in terms of shade degradation (value 4/5) and in terms of fading on multifiber material (average value = 4/5).

The procedure of Example 2 was repeated also at the temperature of 98⁰C, obtaining a slightly lower dyeing yield. Example 3 (hazelnut dye) A dyeing bath with a pH of 4.5 was prepared which contained 0.73%

Foron^® RD 4GRL, (Clariant) yellow dye, 0.25% Foron^® RDS (Clariant) ruby dye, 0.35% Foron^® RDS blue dye, 1% Lyocol^® RDN (Clariant) dispersal agent, 1 g/1 of 60% acetic acid. Dyeing and subsequent cleaning with reducing agent were performed according to the same procedure of Example 1.

Tests of wash fastness at 4O⁰C (ISO 105C06 standards) and of acid and alkaline sweat fastness (ISO 105-E04 standards) were conducted and showed good values both in terms of shade degradation (value 4/5) and in terms of fading on multifiber material (average value = 4/5). The procedure of Example 3 was repeated also at the temperature of

98⁰C, obtaining a dyeing yield equal to that of the procedure performed at 120⁰C. Example 4 (olive green dye)

A dyeing bath with a pH of 4.5 was prepared which contained 2.62% Foron^® S2RFL 150% (Clariant) yellow brown dye, 0.43% Foron^® S3GLF (Clariant) scarlet dye, 1.22% Foron^® S2RN blue dye, 1% Lyocol^® RDN (Clariant) dispersal agent, 0.7% Eganal^® RAP (Clariant) retardant leveling agent, 1 g/1 of 60% acetic acid. Dyeing and subsequent cleaning with reducing agent were performed according to the same procedure of Example 1.

Tests of wash fastness at 40⁰C (ISO 105C06 standards) and of acid and alkaline sweat fastness (ISO 105-E04 standards) were conducted and showed good values both in terms of shade degradation (value 4/5) and in terms of fading on multifiber material (average value = 4/5). The procedure of Example 4 was repeated also at the temperature of 98⁰C, obtaining a lower dyeing yield (30% lighter) due to the use of disperse dyes characterized by large steric hindrance.

In practice it has been found that the process according to the invention fully achieves the intended aim, since it allows to obtain a dyeable form of a fiber that is per se non-dyeable, as is polypropylene.

It has also been found that the process according to the invention leads to the production of a form of polypropylene that can be dyed even after spinning.

Moreover, it has been observed that the process according to the invention is inexpensive and easy to provide, since it allows to use the tools already available in the textile field to prepare textile articles and for dyeing.

Moreover, the possibility to dye the polypropylene after weaving allows to work on volumes of material that are optimized according to market demand, avoiding an excessive accumulation of the finished product. Moreover, it has also been observed that the process according to the invention allows to purchase just raw (undyed) fiber and to prepare with this yarn the several textile articles and only later, depending on market demand, dye the textile article produced in the different colors required by fashion.

Moreover, it has been observed that the process according to the invention allows to use the dyeing procedures on textile articles made of polypropylene, an activity that until now was prevented by the need to dye the fibers before producing the article.

The process thus conceived is susceptible of numerous modifications and variations, all of which are within the scope of the appended claims; all the details may further be replaced with other technically equivalent elements.

The disclosures in Italian Patent Application no. MI2007A002383, from which this application claims priority, are incorporated herein by reference.

Claims

1. A process for producing a dyeable polypropylene, comprising the step of mixing a polypropylene and a component based on a dyeable polymer that is compatible with the extrusion temperatures of the polypropylene.

2. The process according to claim 1, characterized in that said dyeable polymer compatible with the extrusion temperatures of polypropylene is selected from the group consisting of a polyethylene terephthalate (PET), a polyethylene terephthalate modified for cationic dyeability, polylactic acid (PLA), a polymer of bio-natural origin, and mixtures thereof.

3. Process according to claim 2, characterized in that said polyethylene terephthalate modified for cationic dyeing is a polyethylene terephthalate containing an agent that allows dyeing with cationic dyes.

4. The process according to claim 3, characterized in that said dyeing agent that allows dyeing with cationic dyes is selected from the group consisting of sodium dimethyl-m-phthalate-5-sulfonate, tricalcium phosphate, 5-sulfoisophthalic acid sodium salt and 5-sulfoisophthalic acid lithium salt.

5. The process according to any one of claims 2-4, characterized in that said polyethylene terephthalate modified for cationic dyeability contains 1% to 50% by weight of agent that allows dyeing with cationic dyes.

6. The process according to any one of the preceding claims, characterized in that said dyeable polymer is mixed in a proportion of 1 % to 50% by weight relative to the total weight of the resulting final fiber.

7. The process according to any one of the preceding claims, characterized in that said mixing occurs in a mixing/dosage unit that is selected from the group consisting of a gravimetric mixing/dosage unit, a volumetric mixing/dosage unit, a mechanical mixing tower and by direct injection into the spinning head with another extruder.

8. The process according to any one of the preceding claims, characterized in that it comprises a further step of extrusion of the mixture of polypropylene and dyeable polymer.

9. A process for obtaining a dyed polypropylene, comprising the steps of: producing a dyeable polypropylene according to the process of any one of claims 1 to 8; dyeing said dyeable polypropylene or an article produced with it.

10. The process according to claim 9, characterized in that said dyeable polypropylene is dyed with a disperse dye.

1 1. The process according to claim 9 or 10, characterized in that said dyeing step occurs at a temperature from 70⁰C to 130⁰C, preferably from 98⁰C to 120⁰C.

12. The process according to any one of claims 9 to 1 1 , characterized in that said dyeing step occurs at a pressure from atmospheric pressure to under pressure at 2-3 bars.

13. Process according to any one of claims 9 to 12, characterized in that said dyeing step occurs in an acid bath, preferably at a pH of approximately 4.5.

14. The process according to claim 13, characterized in that said acid bath contains acetic acid.

15. The process according to any one of claims 10 to 14, characterized in that in said dyeing step a dispersant of said disperse dye, preferably a sulfonated aromatic polyether, and optionally a retardant leveling agent, preferably an oxyethylation product based on fatty acids, is further used.

16. The process according to any one of claims 9 to 15, characterized in that it comprises the additional step of cleaning the dyed polypropylene with a reducing agent.

17. The process according to claim 16, characterized in that said cleaning with a reducing agent is performed with sodium hydrosulfite in the presence of alkali, preferably caustic soda.

18. The process according to claim 16 or 17, characterized in that said cleaning with a reducing agent is performed at a temperature from 50⁰C to 80⁰C.

19. A composition of dyeable polypropylene, comprising polypropylene and a component based on a dyeable polymer that is compatible with the extrusion temperatures of polypropylene.

20. The composition according to claim 19, comprising polypropylene and a component based on a dyeable polymer that is compatible with the extrusion temperatures of the polypropylene, selected from the group consisting of a polyethylene terephthalate (PET), a polyethylene terephthalate modified for cationic dyeability, polylactic acid (PLA), a polymer of bio-natural origin, and mixtures thereof.

21. A fiber, yarn, fabric, mesh or spunbond or meltblown or nonwoven fabric provided with a composition according to claim 19 or 20.

22. The fiber, yarn, fabric, mesh or spunbond or meltblown or nonwoven fabric, dyed or printed, obtained by dyeing a fiber, yarn or flock according to claim 21 or by printing a fabric obtained by means of fiber, yarn or flock according to claim 21.