HK1135741B - Method for providing textiles with desensitised silver components - Google Patents

Description

Method of providing a textile with desensitized silver component

Technical Field

The present invention relates to a method for the antimicrobial modification of fibers and textiles, to antimicrobial formulations and to fibers and textiles modified with specific antimicrobial components. The active antimicrobial agents described herein consist essentially of a desensitizing silver component, such as silver chloride. The active antimicrobial agents are particularly useful as aids for modifying fibers, yarns, nonwoven webs, and textiles.

Background

Most textiles comprise a microbially degradable material. They are often made wholly or partly of microbially degradable fibres such as cotton, cellulose (e.g. viscose and Tencel (Tencel)), hemp, flax, linen, silk, acetate or wool. Textiles made from synthetic fibers such as polyester, polyacrylonitrile, polyamides (e.g., aramid, Nomex, Kevlar, nylon-6, nylon-66) or polypropylene may also be colonized by bacteria, particularly when treated with modifiers such as softeners, hydrophobing agents, antistatic agents and/or adhesives, or when obtaining microbial degradable materials such as organic substances from the environment in use.

Colonization by microorganisms such as bacteria can negatively affect the performance characteristics of textiles as well as their appearance. In addition, the breakdown of their metabolites in the case of bacteria can, for example, produce unpleasant odors and be a health hazard. Thus, for example, in order to be able to control colonization by microorganisms, such as bacteria, it is necessary to modify the fibers or textiles with preservatives, in particular antimicrobial components.

However, difficulties often arise when attempting to modify fibers or textiles with active antimicrobial agents, which difficulties not only relate to the modification operation itself but also to the phenomena resulting from the modification.

The textile industry expects antimicrobial components for the modification of fibers and textiles to meet high demands. For example, in order to achieve "relaxation" and complete polymerization of the polymeric component, the modified fiber or textile is dried at a temperature of 100 ℃ and 130 ℃ and subsequently treated at a temperature of up to 180 ℃. In this process, the antimicrobial component may be destroyed or the high evaporation rate of the antimicrobial component may result in loss of active ingredient. Due to the large surface area of the textile and the small thickness of the finish, the active antimicrobial component remaining on the fiber after finishing can be washed away during the cleaning operation in practical applications of the textile. Over time, this washing off results in further loss of active ingredient. In addition, in the preparation of photosensitive antimicrobial agents, the effects of light can cause the active antimicrobial components to decompose. Upon modification, the interaction of the antimicrobial component with the other ingredients produces a visible color change of the textile.

There is a description in the prior art of effective antimicrobial actives that have low evaporation rates and remain largely on the fibers during the cleaning operation. However, antimicrobial active ingredients which are satisfactory in themselves are not well suited for the modification of textiles, due to their toxic effects or other disadvantages. For example, when a textile that has been modified to be antimicrobial is cut (e.g., cut, sewn, etc.), skin irritation can result because skin contact occurs during the intended application even in the event that the textile does not contact the human body.

The German patent application DE-A4339374 relates to a process for preparing fibers modified with antimicrobially active components. The antimicrobial active used is a silver-containing inorganic biocide which is used in the treatment solution together with a discoloration inhibitor. The discoloration inhibitor consists of benzotriazole derivatives.

International patent application WO 1996/01119 describes an antimicrobial composition comprising a stabilising component in addition to silver ions. The technical teaching in WO 1996/01119 aims to achieve photostability of said antimicrobial composition which can be used in various fields (sector). A polyether polymer is used and a stabilizing anion is added. The antimicrobial compositions so stabilized are useful, for example, in the preparation of foams.

EP-A0446993 discloses organic substances useful for desensitization involving photographic developers. In particular, the compound pinacryptol yellow (6-ethoxy-1-methyl-2- (3-nitrostyryl) quinolinium methyl sulfonate) is described as a desensitizing component of photographic development. Other documents also disclose dyes for photography, such as the compound pinacryptol green.

Due to the above-mentioned volatility of the biocidal or antimicrobial active ingredient, despite the loss of active ingredient, it is often necessary to use high concentrations, often expensive, of active agents with high Minimum Inhibitory Concentration (MIC) values, which requires a significantly high cost, in order for the desired antimicrobial effect to be sufficient for the practical requirements. In addition, high use concentrations and high loss of antimicrobial activity impact the environment during production and during use of these articles.

Therefore, there is a constant need for the development of antimicrobial formulations that meet as many of the following criteria as possible:

● they should be applicable using the usual standard methods of the textile industry;

● they should be compatible with as many other textile effects as possible;

● they should be very durable to washing, including in particular the case where the textile consists of polyester or polyamide;

● they should have very little, if any, impact on textile employees;

● the antimicrobial active ingredient should ideally be informed to authorities (e.g., EPA and BPD);

● they should be of competitive price, i.e. simple to produce;

● the antimicrobial microbiologically active component should be durable and should be usable in an environmentally friendly manner.

Disclosure of Invention

It is an object of the present invention to provide a method and a formulation for antimicrobial modification of textiles or fibers which substantially avoid the above disadvantages. The cost and environmental impact of modifying the textile to control harmful microorganisms should be reduced. The antimicrobial effect of the biocide used to modify the fiber or textile should be ensured over a long period of time.

In particular, antimicrobial agents and pesticides have long been used in many areas of daily life in general, such as to control harmful bacteria, fungi or algae. In view of the increasing need for antimicrobial components, for example in terms of cost, health and environmental protection, there is a need to further develop these known articles.

Silver and silver compounds have been known for centuries to have a bactericidal or antimicrobial effect. However, the use of silver compounds as antimicrobial agents is limited to a particular field for a variety of reasons. The silver formulations described for preservation purposes include, for example, elemental silver in colloidal form, dispersions of nanoparticulate silver, silver compounds such as silver oxide or inorganic and organic silver salts. Silver or silver compounds can be embedded in a carrier material such as silica, titania, zeolites or glass.

One of the disadvantages of preservation by means of silver is that silver compounds can lead to discoloration, in particular in the presence of reducing compounds and under the influence of light. The use of higher concentrations of silver increases the risk of discoloration, which is undesirable in particular in the field of fiber and textile finishing. Furthermore, silver-containing formulations are also expensive when compared to many other commercially available antimicrobial formulations, which obviously limits their use in practice.

Examples of common areas of silver as an antimicrobial agent are coatings for household appliances, medical and pharmaceutical and water treatment areas. Silver is also known in the field of industrial corrosion protection, for example involving adhesives, sealants, coatings and plastics. DE-A10346387 lists silver as an example of a possible preservative and describes the use of silver-containing preparations for the antimicrobial modification of hard and soft surfaces. This reference also describes the use of silver ions or carrier silver in solutions and dispersions for treating textiles and other materials.

The present invention aims to provide novel biocidal compositions comprising a stable or desensitized silver component which provides durable protection to fibers and textiles. Another object of the present invention is a method for modifying fibers and textiles using the above antimicrobial components. The durable protection for fibers and textiles should also reduce the impact on the environment and reduce the cost of controlling harmful microorganisms.

The silver component and the phlegmatiser component are preferably formulated together, but may in principle also be formulated separately. Likewise, the above-mentioned components can be applied simultaneously to the fibers or textiles, if appropriate also in succession.

It has been found that the above objects are achieved according to the present invention by providing a method for modifying fibers and/or textiles with a biocidal active component comprising a silver component desensitized with additional components and optionally one or more other antimicrobial components.

The invention provides, inter alia, a method of modifying fibers and/or textiles with an antimicrobial active ingredient comprising a silver component desensitized with other components and optionally one or more additional antimicrobial components, wherein the other components used comprise at least one compound selected from quinoline derivatives. Preferably, the antimicrobial active component applied to the fiber or textile is a silver component desensitized with an additional component comprising pinacol yellow.

Frequently, the antimicrobial active components used comprise silver salts as silver component.

In one embodiment of the present invention, the antimicrobial active component used comprises an in situ formed silver salt as the silver component and pinacol yellow as the other component.

In one embodiment of the present invention, the antimicrobial active component used comprises a silver salt as silver component and at least one quinoline derivative and an additional benzotriazole derivative as phlegmatizer component.

The invention also provides a method characterized in that the silver component is used in an amount of 0.0001 wt.% to 1.5 wt.% (including, for example, 0.0001 to 0.5 wt.%), based on the total weight of the fiber or textile.

One embodiment of the invention uses a process characterized in that the phlegmatizer component used is a quinoline derivative in an amount of 0.1ppm to 500ppm, based on the total weight of the fiber or textile.

One embodiment of the present invention uses a process which is characterized in that an antimicrobial active component is used which comprises a water-insoluble silver salt as silver component and at least one quinoline derivative as phlegmatising component and a benzotriazole derivative in an amount of from 0.5ppm to 2500ppm, based on the total weight of the fiber or textile.

One embodiment of the present invention uses a method characterized in that the water-insoluble silver component comprises one or more salts selected from the group consisting of chloride, bromide, iodide, sulfate, and tosylate.

The invention also provides a process characterised in that the water insoluble silver component comprises silver chloride prepared in situ from silver nitrate and a metal chloride.

The invention also provides a method characterized in that the phlegmatizing component comprises, as a single component, pinacryptol yellow or a combination of pinacryptol yellow with at least one other phlegmatizing component.

The invention also provides a method for modifying fibers and/or textiles, comprising padding, venting, foam application, coating or spraying.

The invention also provides an antimicrobial formulation for modifying fibers and/or textiles with an antimicrobial active component, comprising as antimicrobial active component at least one silver component, an additional phlegmatizer component and optionally one or more auxiliaries and additive materials, wherein the additional phlegmatizer component used comprises at least one compound selected from the group of quinoline derivatives.

The invention also provides a formulation comprising from 0.01% to 10% of a silver component and from 0.001% to 2% of pinacryptol yellow.

The invention also provides an antimicrobially modified fiber and textile obtained according to the method as described above.

The invention also provides antimicrobially modified fibers and textiles, characterized in that they consist essentially of cotton, cellulose, silk, polyester, polyamide, other synthetic or natural fibers or mixtures thereof.

The invention also provides antimicrobially modified textiles, which are characterized in that they comprise woven, knitted, nonwoven webs or yarns.

The present invention also generally provides the use of the formulations described above to protect fibers and textiles from bacterial attack.

The invention also provides the use of a formulation characterized in that it comprises a silver salt and, as desensitizing component, at least one quinoline derivative and benzotriazole derivative, for protecting fibres and textiles against bacterial attack.

It is preferred to use an antimicrobial active component comprising at least one silver salt as silver component and at least one organic phlegmatizing component as additional component.

Another embodiment of the present invention uses an antimicrobial active ingredient comprising at least one water insoluble silver salt as the silver ingredient and at least one quinoline derivative as the phlegmatizer ingredient.

In particular, the quinoline derivatives are substituted quinoline compounds having desensitization properties and salts thereof. As a preferred representative of such derivatives, the compound pinacol yellow (6-ethoxy-1-methyl-2- (3-nitro-. beta. -styryl) quinolinium sulfonic acid methyl ester; CAS 25910-85-4) and other salts of this compound are used herein. However, quinoline derivatives are also understood to comprise pinacol green (1, 3-diamino-5-phenyl-phenazinium chloride; CAS19220-17-8) and pinacol white. However, pinacol yellow is preferably used.

Another embodiment of the present invention uses an antimicrobial active component comprising at least one water insoluble silver salt as the silver component and at least one quinoline derivative and/or benzotriazole derivative as the phlegmatizing component.

In particular, the benzotriazole derivative is a compound or salt of the general formula (I)

Wherein R1 is hydrogen or C1-C4 alkyl, and

r2 is hydrogen or a metal, preferably an alkali metal.

The preferred benzotriazole derivative is 1, 2, 3-benzotriazole which itself cannot withstand washing.

In principle, any other UV stabilizer may be used instead of the benzotriazole derivatives of formula (I). Quinoline compounds may also be used in combination with benzotriazole derivatives and other UV stabilizers.

Another embodiment of the invention uses from 0.0001% to 0.5%, in particular from 0.001 to 0.05% by weight of the silver component, based on the total weight of the fiber or textile.

The antimicrobial compositions of the present invention preferably contain a specific amount of a silver component (e.g., a silver compound). In this connection and in the context of the present invention, this amount is always silver (Ag) used as a calculation reference⁰) The content of (a). For example, when 100mg of silver chloride is included per kg of a formulation of the invention, the silver content is 73.53mg/kg, i.e. 0.007% by weight.

The textile pre-or post-treatment compositions which comprise the antimicrobial component of the invention and can be in solid, liquid or flowable form, as a gel, powder, granulate, paste or spray, comprise silver (calculated as Ag) preferably in a range from 0.00005% to 5% by weight and in particular in a range from 0.0001% to 1.5% by weight. Another embodiment uses from 0.0001% to 0.5% by weight silver and specifically from 0.001% to 0.5% by weight silver, based on the composition.

The amount of said quinoline derivative used as phlegmatising component is preferably from 0.1ppm to 500ppm, in particular from 1ppm to 150ppm, based on the total weight of the fibre or textile.

The ratio (by weight) of the silver component and the desensitizing component in the antimicrobial composition is, for example, 0.1: 1 to 1: 500. It can also be from 1: 10 to 1: 500 and preferably from 1: 10 to 1: 100.

A particular embodiment of the present invention is characterized in that the antimicrobial active component used comprises at least one water-insoluble silver salt as silver component and at least one quinoline derivative as phlegmatizer component, and additionally a benzotriazole derivative. The additional use of benzotriazole is particularly advantageous for some fiber types.

The benzotriazole derivatives are preferably used in an amount of from 0.5ppm to 2500ppm, especially from 5ppm to 500ppm, including for example from 5ppm to 150ppm (especially from 20ppm to 50ppm in the padding process), based on the total weight of the fiber or textile.

The water-insoluble silver component may comprise, for example, one or more salts selected from chloride, bromide, iodide, sulfate, and tosylate. In this regard, the term "water insoluble" is not to be understood as meaning that no ions enter the solution, but rather as meaning that the salt has only minimal solubility in water.

In one embodiment of the invention, the silver salt is formed in situ, for example, by direct reaction of a soluble silver salt (e.g., silver nitrate) with some other soluble salt (e.g., sodium chloride).

Another embodiment of the present invention uses a method wherein the phlegmatizing component is a combination of the compounds pinacryptol yellow and benzotriazole. These components may be used as such or together or separately pre-formulated into a solution or dispersion for use.

The process of the present invention may comprise, for example, padding, venting, foam application, coating or spraying.

The invention also provides an antimicrobially modified fiber or textile obtained by following one of the methods described above. The antimicrobial modified fiber or textile may comprise, for example, a fiber or textile consisting essentially of cotton, cellulose, silk, polyester, polyamide, or other synthetic or natural fibers.

The antimicrobial modified textile may preferably comprise a woven fabric, a knitted fabric, a nonwoven web or yarn, but other textiles may also be modified.

Another embodiment of the present invention provides the use of a composition comprising a silver component desensitized by an additive for protecting fibers and textiles from microbial attack. The composition itself, which may comprise the components or be provided as a kit of parts for the components, is also part of the subject matter of the present invention.

The formulations of the present invention comprise, for example (based on the total weight of the formulation) from 0.01% to 10%, especially from 0.1% to 3%, of a silver component and from 0.001% to 2%, especially from 0.01% to 0.5%, of a phlegmatizer component (e.g. the compound pinacol yellow). The formulation may also contain solvents (e.g. water and/or alcohols) and adjuvant materials (e.g. surfactants or wetting agents and binders).

More particularly, the present invention provides the use of the above-mentioned composition, when comprising a water-insoluble silver salt and, as phlegmatizing component, at least one quinoline derivative and/or benzotriazole derivative, for protecting fibers and textiles against bacterial attack, including gram-positive and gram-negative bacteria.

It is known in the art that silver and silver ions exert a blocking effect on thiolase in microorganisms, and thus exert a high bactericidal effect. The terms "antimicrobial effect" and "antimicrobial active ingredient" are used herein in the usual sense in the art, e.g. as described in k.h. wallhusser in "Praxis der Sterilisation, desinfection-kontervierung: identified in Keimmentifying running-Betriebsheygiene, (5 th-Stuttgart; New York: Thieme, 1995).

According to the invention, the silver component is preferably used in the form of its compounds, for example in the form of the silver salts mentioned above. The formulations according to the invention may comprise the silver component in the form of a plurality of particle sizes. They may comprise, for example, silver particles (e.g., silver chloride particles) having a particle size of 0.001 to 100 μm, including, for example, 0.04 to 80 μm.

In a particularly preferred embodiment, the silver component used comprises nanoparticles having a particle size of 0.001 to 0.1 μm, preferably 0.002 to 0.05 μm and in particular 0.004 to 0.01 μm. The particles may also be present in colloidal form, in whole or in part. The antimicrobial particles may be included in a pre-formulated or freshly prepared formulation.

The processability of the silver component having a low particle size can be improved by applying the silver component to a carrier material. For this purpose, suitable support materials can be impregnated with colloidal solutions or mixed with finely divided silver compounds, for example. The silver component may also be granulated with the carrier material in the presence of a suitable granulation aid. Particularly useful support materials include builders or framework materials such as zeolites. In addition to these, it is also possible to use highly porous materials such as silicas, for example fumed silica, bentonite, polymeric materials or diatomaceous earth ("kieselguhr") as support materials, and ceramic materials capable of ion exchange, for example based on zirconium phosphate, or glasses. Likewise, activated carbon, apatite, phosphate activated carbon, activated alumina, silica gel, hydroxyapatite, zirconium phosphate, titanium phosphate, potassium titanate, antimony oxide hydrate, bismuth oxide hydrate, zirconium oxide hydrate and hydrotalcite may in principle also be used.

The method for applying silver ions to these inorganic compounds is not limited to a specific method. There are various application methods such as a method by physical or chemical adsorption, a method by ion exchange reaction, a method by using a binder, a method by introducing a silver compound into an inorganic compound, and a method by forming a thin layer of a silver compound on the surface of an inorganic compound by a process of forming a thin layer, such as a vapor deposition method, a dissolution method, and a precipitation method or a sputtering method.

The composite particles formed from the carrier material and silver component may optionally include other ingredients. It was found to be advantageous to use, for example, an active noble metal, such as gold, which activates the antimicrobial effect of the silver component.

The method of modifying fibers and/or textiles with an antimicrobial active component comprising a silver component desensitized by an additional component can be used to make antimicrobial fibers and textiles. The antimicrobial fiber obtained by this method does not cause any discoloration.

The antimicrobial modified fibers can be used as starting products for a variety of materials for different fibrous articles, such as garments (e.g., women's outerwear, men's wear, children's wear, sportswear and casual wear, work wear, socks, stockings and undergarments), bedding (e.g., bedspreads and sheets), household textiles, seat covers, upholstery fabrics, textiles for shoes, shower curtains, filter cloths, carpets, protective articles (e.g., masks and bandages), and the like.

The fibers modified with the antimicrobial component (hereinafter referred to simply as antimicrobial fibers) may optionally undergo multiple treatment steps during the process, such as stretching, rinsing, dyeing, bleaching, spinning of blended fibers, and weight reduction, and treatment with different treatment solutions such as textile oils, aqueous alkali metal hydroxide solutions, bleaching agents, and detergents. During the treatment process, a portion of the silver ions present in the antimicrobial component dissolve in the treatment solution or react with various components of the treatment solution, which can lead to discoloration of the antimicrobial fiber in conventional processes.

In order to protect the antimicrobial formulation against discoloration, stabilizers have been suggested in the literature. For example, the stabilizers described in EP-A0288063 for antimicrobial resin compositions each comprise a) an antimicrobial zeolite carrying silver ions, and b) a resin, and c) a benzotriazole compound, an oxanilide compound, a salicylic acid compound, a hindered amine compound and/or a hindered phenol compound. However, when these stabilizers are added to fibers to prepare a resin and the resin is spun into antimicrobial fibers, it cannot subsequently sufficiently inhibit the discoloration of the antimicrobial fibers.

This is not possible even when the antimicrobial fibres are treated with different treatment solutions in the treatment step or the spinning solution used for preparing the antimicrobial fibres contains a large amount of solvent.

It is an object of the present invention to develop a process for the preparation of antimicrobial fibres which does not lead to any discoloration during the different fibre treatment steps.

The present invention provides a process for preparing antimicrobial fibers wherein the fibers are substantially free of discoloration during or after preparation due to the use of a treatment solution or due to the spinning solution alone.

The base fibers used in the present invention may be, for example, natural or synthetic (prepared) fibers. The natural fibers preferably comprise plant fibers such as cotton, hemp, flax, coir and reed. In principle, animal fibres such as goat, mohair, cashmere, camel and silk, and mineral fibres can also be modified by the method.

Examples of manufactured fibers are cellulose fibers such as viscose, protein fibers such as casein and soy protein, regenerated semi-synthetic fibers such as regenerated spun or alginate fibers. The modifiable synthetic fibres are in particular: polyamide fibers, polyester fibers, and mixtures thereof. In principle, the method of the invention can also be applied to polypropylene fibres, polyethylene fibres, polyacrylic fibres, polyurethane fibres, polyethylene fibres, polyvinylidene chloride fibres and polystyrene fibres. However, the process can also be used on blended fibers.

For antimicrobial use in textiles, silver in ionic form may be incorporated into synthetic fibers during, for example, spinning operations. Such articles have long been sold by different manufacturers and are based on silver compounds such as salts or silver oxides, incorporated on different support materials such as titanium dioxide, zinc oxide or glass supports or those consisting of ceramics. Ion exchangers and zeolites can also be used as support materials.

These products are often sold in the form of a masterbatch, a concentrated form of the active compound in a polymeric carrier that is compatible with the final product, such as a fiber, throughout the manufacturing operation. The intermediate stage of the masterbatch makes the industrial process significantly simpler, since the dilution of the concentration from the pure active compound into the final product is accomplished in two or more stages. In addition, the active compound is in a form that is easy to handle and easy to integrate into the industrial operations of fiber production.

However, the incorporation of this product presents technical difficulties. The biocidal component must have a consistency or composition such that the number of broken ends does not increase during the spinning stage. This can be influenced, for example, by the choice of the maximum size, the particle size distribution, the geometry of the killing particles and their wetting properties by the fibre material. In practice, however, fine or very fine fibers, microfibers, are rapidly restrained when the active ingredient is not melted under the process conditions, which is not the case with the silver compound nor with the above-mentioned carrier.

Another decisive aspect of the antimicrobial modification of the fibers is fiber abrasion, which by using antimicrobial components can shorten the service life of the spinning machine. The silver component may also affect the finishing steps after spinning, such as dyeing operations. Flexibility is also particularly important in the spinning of the fibers. For example, the handling of multiple fiber grades is difficult for the introduction performance. Product changes on equipment used today are often uneconomical and should therefore be avoided.

Metering of additives during spinning operations is difficult because not only pure synthetic fibers but also blended yarns and blended fabrics are produced from the primary spun product. Especially when natural fibers are used as other components, the textiles produced therefrom are only partially antimicrobial and therefore not sufficiently antimicrobial.

The use of metallic silver for coating any kind of textile or of using a yarn consisting of or containing silver is also known.

Disadvantages of these solutions include specific processes, the inherent color of the textile, the different properties of the fibers in post-treatments such as dyeing, the feel of the textile, the inconsistency of the antimicrobial properties and the high price of these textiles.

Another aspect of the invention is the modification of textiles in a final modification operation, where textile properties such as touch, hydrophobicity, hydrophilicity, stain repellency, ironing, sewing, thread shear strength and other properties are well-tuned. In addition, there are also hygienic modifications (for example for antimicrobial properties). The advantage of applying an antimicrobial hygienic finish in this step is that only textiles requiring such a finish are actually finished in this manner. Therefore, there is no stray effect (stray effect) as if the entire production of the textile mill had to be modified. Technically, it is a decisive advantage of the above-described method to modify the entire textile, not only a part thereof, for example the specific type of fibres. When the modification is applied in a final modification operation, the modification is not stopped until deemed effective, in the case of antimicrobial modification, the modification is usually performed on a surface.

A disadvantage of applying antimicrobial finish in the final finishing operation is that the finish often has poor durability in the wash. This can occur when the modifying chemical is unable to react with the textile or is bound to the textile by itself or reacting with other blocks to form macromolecules and/or agglomerates, which are durable by virtue of cross-linking. In the case of antimicrobial components, there should be a certain minimum utilization in order for them to function in any situation. Thus, these active compounds cannot be completely incorporated onto or into the fibers. This process requirement is divergent with respect to the desire to achieve a very large number of wash cycles of the finished article while maintaining a high consistent level of antimicrobial effect.

A variety of antimicrobial components based on silver (or silver ions) have long been sold in the market. These include, for example, various types of Nano Ag such as those available from Air Products, Silpure available from Thomson Research Associates, Dorafresh AG available from Dohmen, various JMAC grades available from Clariant, Rucobac AGP available from Rudolf Chemie.

However, in order to obtain durability of the modification to laundering, all of these products must be applied to the textile with a polymeric binder. One reason is that the silver salt is applied to a support and has to be immobilized on the textile together with the support, since the affinity of the particles, which are not immobilized, is not sufficient to obtain a relatively high permanence to the wash.

ALPHASAN, a product on an ion exchanger along with silver ions, obtained from Milliken (USA) was used as an example to demonstrate wash durability in US 6,821,936. It shows that the antimicrobial efficacy against Staphylococcus aureus as tested by AATCC 100-. When the product is applied with an adhesive, up to 10 wash cycles can be achieved with a somewhat good antibacterial effect.

For example, when using the AmpZ200 product from DuPont-a product using titanium dioxide as a silver ionophore-instead of ALPHASAN, wash durability is poor. As described in US 6,821,936, the loss of antimicrobial properties is even more pronounced in the case of the ZEOMIC AJ 80H product.

Indoor testing using commercial products has shown that some known products tend to cause discoloration of textiles finished therewith and exposed directly to sunlight. The metallic silver-based product is in some cases already dark grey to black in itself, which is clearly visible on light-coloured or even white textiles decorated with it.

There have been numerous proposals in the literature to achieve stability against fading of silver salts on textiles. DE-A4339374 describes the use of benzotriazoles and derivatives thereof for stabilizing Ag of the general formula_pM¹ _qM² ₂(PO₄)₃x nH₂Use of silver compounds of O, wherein M¹Selected from alkali metal ions, alkaline earth metal ions, ammonium ions and hydrogen ions, and M²P, which is a tetravalent metal selected from Ti, Zr, and Sn, ultimately indicating the concentration of the silver ions, is set to 0.01-0.5. In addition, silver ions on the inorganic ion exchanger are broadly referred to as active components. Spinning bath (spin) in the fiber production processbath), the fading inhibitor is applied to the textile.

JP 2003212993(Chugai Shashin, published 30/7/2003) obtains a stabilizing effect of silver compounds against discoloration, particularly on textiles for clothing, by using copolymers with hydroxyamino groups.

It is an object of the present invention to provide a silver ion based composition which can be applied to textiles, for example by padding and exhaust methods, and which does not change colour or does not actually change when the textiles are exposed to sunlight.

The stabilizing effect of the antimicrobial component can in principle also be applied without a polymer or copolymer binder system. Furthermore, wash durability should be at least 20 wash cycles. The washing can be carried out at 40 ℃ according to EN ISO 6330(6A) standard. For example, washing with ECE 77 permanent color detergent, according to JISL 1902: 2002 and/or ASTM E21-49 test the antimicrobial efficacy against Staphylococcus aureus (ATCC 6538).

Detailed Description

The improvement in washing durability was tested using fine silver salt particles in some cases below. The examples which follow illustrate the invention. Some commercially available adjuvants were used, including the following:

list of commercially available products used below

Comparative example 1

Precipitation of silver chloride from dissolved silver nitrate is attempted by adding a sodium chloride solution directly to the application solution, so that the silver chloride particles are small enough to achieve a much improved adhesion on the textile than with silver chloride or other silver salts applied directly on the carrier material. Comparative tests were performed using silver nitrate which was not precipitated using a sodium chloride solution.

For the coating in the examples described below, 7.87g of silver nitrate was dissolved in 100ml of deionized water. This solution is used as a raw material solution and used only by dilution or used by dilution and mixing with other chemicals. The purpose of this is to improve the distribution of silver chloride on the textile and to improve the fixation of silver chloride on the textile. A further object is to obtain a more stable bath for application.

Except as in example 2, silver chloride was precipitated from the application bath (in situ) by addition of a 20% aqueous sodium chloride solution.

3.3g of silver nitrate solution (7.87g of silver nitrate and 100g of water) are dissolved in 243g of water and mixed with 3.3g of sodium chloride solution (20% aqueous NaCl solution) by stirring. This bath, which had a very pronounced tendency to separate, was applied to a basis weight of 198g/m using a padding machine immediately after preparation²On cotton goods. The coating amount (pick-up) was 88%. Thus, the silver ion concentration on the textile is believed to be about 580 ppm. The fabric was dried on a tenter at 120 ℃ for two minutes.

Comparative example 2

3.3g of silver nitrate solution (7.87g of silver nitrate and 100g of water) was dissolved to form a solution with 200g of water and 5.0g of Komplexon III (disodium ethylenediaminetetraacetate) was added with stirring. Then 1.0g of sandozin MRN (wetting agent from Clariant), 17.5g of aprestan TT 50 (anionic solvent-free aliphatic polyester polyurethane dispersion for soft elastic hand of the textile, binder from Clariant) were added sequentially followed by 2.0g of acetic acid (80%). The pH of the liquid was 6.4. Finally, an additional 21.2g of water was added.

This bath, which is very stable during application, is applied in turn to the same cotton fabric as described in example 1 using a padding machine. The coating amount was 76%. Thus, the silver ion concentration on the textile is considered to be about 500 ppm. The fabric was dried on a tenter at 120 ℃ for two minutes and then cured at 150 ℃ for 90 seconds. The textile and the bath fade under room light.

Comparative example 3

220g of deionized water were initially charged while stirring

To this was dissolved 5.0g of Komplexon III and

1.0g of SandozinNRW (polyethylene glycol ether, manufacturer: Clariant) was added as a wetting agent.

17.5g of Apreten N92111 (acrylate copolymer dispersion from Clariant with soft hand) were added as binder and then

3.3g of silver nitrate solution are added with stirring and subsequently

3.0g of sodium chloride solution was added

This bath, which is very stable during application, is applied in turn to the same cotton fabric as described in example 1 using a padding machine. The coating amount was 72%. Thus, the silver ion concentration on the textile is believed to be about 475 ppm. The fabric was dried on a tenter at 120 ℃ for two minutes and then cured at 150 ℃ for 90 seconds. The textile and the bath fade under room light.

Comparative examples 4 and 5

These examples were carried out analogously to example 3, except that the product Apretan TT 50 and the crosslinker Arkofix NDF (melamine resin from Clariant) were used together with Catalyst NKS instead of the Apretan N92111.

Almost all samples discolor in daylight even indoors and within minutes to hours after window glazing. The sample of example 1 took several hours to fade. Likewise, the liquid fades quickly due to the silver deposits on the walls of the container used for storage.

As is known from finely divided metallic silver, the fading of the textile sample is in the orange, purple to purple and not (as expected in practice) black shades. It is known that extremely finely pulverized metallic silver (including nanoparticles) is no longer black but corresponds to the above-mentioned color.

As noted above, the samples were used to perform wash tests for up to 20 cycles without concern for severe discoloration that is unacceptable in commercial practice (unless the article is a very dark color or an article not visible in the application, such as a fiber or nonwoven web for a fibrous filler material).

The washed samples were then used for microbiological testing. These tests are positive. Even after 20 washes, the microbial load was measured by japanese microbial-count method JISL 1902: the kill rate for Staphylococcus aureus (ATCC6538) tested in 2002 is at least equal to the second power of ten. This result was obtained for all modifications with and without binder/crosslinker.

The results are therefore better or comparable to the values given in US 6,821,936(Milliken & Company; 2004) after only one wash.

Example 6

Long-lasting inhibition of the discoloration of the precipitated silver chloride can be obtained, for example, by using the components described below.

The "freshly precipitated silver chloride" is so light-stable that it can be applied to a support and the fabric modified with it does not fade immediately in the sun, neither in the washed nor in the unwashed state. However, as a result of the reduction of the silver ions to elemental silver under the action of light, discoloration occurs after a certain time. The use of desensitizing silver salts has been found to prevent or at least substantially reduce durable fading.

The following are examples of materials for use in desensitization photography, where the film is exposed even at retardation rates:

a) ammonium hexachlororhodium (III), CAS No.: 15336-18-2,

b) pinacryptol dyes, e.g. pinacryptol green or pinacryptol white, or

c) Pinacryptol yellow, IUPAC: having empirical formula C₂₁H₂₂N₂O₇S methyl 6-ethoxy-1-methyl-2- (3-nitro-. beta. -styryl) quinolinium sulfonate, with a relative molecular weight of 446.47 g/mol and a CAS number of 25910-85-4. Photographic emulsions were also prepared using gelatin in photography.

Since textiles are exposed to intense sunlight and are frequently washed, both intensely and for a long period of time, it is very surprising that the aforementioned phlegmatizer components can also be used on textiles.

In accordance with the described embodiment, it is,

dissolving 1.57g of silver nitrate in

45g of a 1% gelatin solution (porcine gelatin dissolved in hot deionized water).

50g of Apprenan N92111 (Clariant acrylate copolymer for forming a flexible film) was added.

2.0g of a saturated aqueous solution of pinacryptol yellow at about 20 ℃ and

2.0g of a 20% sodium chloride solution.

Example 7

84.4g of a 1% gelatin solution (porcine gelatin dissolved in hot deionized water) was initially added and mixed with

1.57g of silver nitrate and

5.0g of saturated aqueous solution of pinacryptol yellow at about 20 ℃ and

5.0g of Imbentin C125/55/90 (ethoxylated C-12/15 fatty alcohol having CAS number 68131-39-5 available from Kolb, Hedinggen),

subsequently 5.0g of a saturated aqueous solution of pinacol yellow at about 20 ℃ and

3.0g of a 20% sodium chloride solution and

1.0g of 80% acetic acid.

The dispersed yellow product was pad-dyed at a basis weight of 198g/m²On cotton fabric. The product of example 6 was applied to a basis weight of 220g/m²On a woven polyester fabric.

In particular, the product of example 6 was used to prepare a coating solution containing 20g/l of product and applied to polyester fabrics by pad dyeing. A coating level of 40% gives a 0.8% concentration of the product from example 6.

The product of example 7 was applied to cotton fabric. In particular, the application solution comprises 15 to 16g/l of the product of example 6 and 0.7 to 1.4g/l of Sandozin NRW wetting agent is applied to the cotton fabric without other textile chemicals together with 70g/l of Apreten TT 50 or Apreten 92111.

The coating amount was between 76 and 80%, so 1% product comprising silver chloride was applied in each case. The textile is dried at 140 ℃.

These textile samples were then hung outdoors for one week. All samples showed pink spots, and in some cases, reddish discoloration of the entire sample occurred. However, the samples were washed 20 times and then tested for their antimicrobial efficacy. The polyester sample showed a reasonably moderate kill rate, while the cotton sample without binder was tested in accordance with JISL 1902: 2002, showed a kill rate of ten to the power of 2.5 of staphylococcus aureus ATCC6538, and each sample with the adhesive showed a kill rate of more than ten to the power of four in the same test.

The product of the example also faded very quickly (in uncoated form) in the glass bottle. Therefore, the stabilizing effect of the formulation itself is still insufficient. The stability of the products themselves is also inadequate, since they can be separated off very quickly.

Example 8

In the following experiments, the amount of gelatin was increased to at most 2% and the amount of pinacol yellow solution was significantly increased to at most 10% (in case of a saturated solution at 20 ℃). The light stability of both the textile and the test product is improved but still not satisfactory. The settling velocity of the dispersed particles in the product is also very high.

To further improve the photosensitizing effect, the concentration of pinacol yellow was increased to up to 0.1% of the total formulation and the compound benzotriazole (CAS number 95-14-7) was used as an additional stabilizer. In addition to gelatin, other products were tested as thickeners for the formulations. For example, a stable QM carboxymethyl cellulose (CMC) was tested, which reacted visibly with silver nitrate instead of precipitated silver chloride, using which a formulation was prepared in which CMC was used as a thickener. Bentone EW (copolymer adhesive from Clariant) was also tested, such as apretan N92111, apretan TS (aqueous polyvinyl acetate dispersion) and apretan TT 50.

In addition to the quinoline derivative pinacol yellow as a stabilizer alone and together with benzotriazole, the test was carried out using benzotriazole alone in an amount of up to 5g of benzotriazole per g of silver ions and additionally using hydroxylamine hydrochloride in an amount of up to 3g of hydroxylamine hydrochloride per g of silver ions (CAS number: 5470-11-1).

However, the two compounds benzotriazole and hydroxylamine hydrochloride do not permanently inhibit the discoloration of the formulations themselves or of the textiles resulting from the formulations used at the concentrations used. Less favorable results were also obtained when the concentration of pinacol yellow was reduced below, for example, 0.025%, whether or not benzotriazole was included in the formulation.

Example 8b

In the following tests

930g of water was subjected to deionization,

1.0g of pinacol yellow is added with stirring and dissolved as far as possible,

16.0g of silver nitrate was added, followed by stirring at room temperature for 5 minutes and then with stirring 35.0g of a sodium chloride solution prepared from 20g of sodium chloride containing < 0.001% of higher halides (bromides and iodides) dissolved in 80g of deionized water.

Adding into the yellow fine dispersion

4.0g Rhodopol 23 heteropolysaccharide dispersion, CAS number: 11138-66-2, and

14.0g of Veegum F colloidal magnesium aluminum silicate as a dispersing aid, available from R.T. Vanderbilt Company, Inc.

The mixture was dispersed for 30 minutes using a mixer (dissolver) to form a yellow low-viscosity dispersion that was stable at room temperature.

A woven fabric composed of cotton, polyamide and polyester was pad-dyed with this formulation such that 1% of the formulation (based on fabric weight) was applied. These samples were exposed directly to sunlight for three days. The polyamide samples showed very weak pink coloration, while the other fabrics did not show any fading.

The above formulations can also be prepared and used without the use of the dispersing aid.

To improve the stability of the dispersion and to improve the ease of introducing the formulation into the application bath, a small amount of propylene glycol is added to the formulation as a solvent other than water. Instead of propylene glycol, other alcohols or commercially available wetting agents or surfactants may also be used, alone or in combination. In order to further improve the lightfastness of the product itself and in particular of the applied product, in addition to the quinoline derivative pinacol yellow, benzotriazole is used. These means have not proved to be absolutely necessary, but do improve the utility and stability of the product. A consistency for application is obtained.

Example 9

Example 9 describes the preparation of a formulation suitable for industrial production.

The open-topped steel vessel was initially charged with 84.3kg of deionized water.

100g of pinacryptol yellow was added with stirring using a dissolver.

Dissolve as much as possible for 15 minutes at 600rpm and disperse the residue.

500g of benzotriazole were added and treated with the dissolver for a further 5 minutes.

1600g of silver nitrate are added, followed by stirring with a dissolver at room temperature for 5 minutes, then over about 2 minutes

700g of sodium chloride

A solution in 2.8kg of deionized water.

After an additional 5 minutes of dissolution with the dissolver, the yellow fine dispersion is added in succession by spraying

400g Rhodopol 23 heteropolysaccharide, CAS number: 11138-66-2, and

1400g of Veegum F colloidal magnesium aluminum silicate available from r.t. vanderbilt Company, inc.

8.2kg of propylene glycol were added.

The mixture was dispersed using a dissolver at 1000rpm for 30 minutes to form a yellow, low viscosity, very easily metered stable dispersion.

The formulation of example 9 was used for multiple applications. The pad application for each formulation was performed by initially adding water and adding a wetting agent. The wetting agent serves to minimize the length of the wet area (wettingsector) in the padding machine, but this does not prove necessary. For example, Sandozin MRN liquid (also known as Hostapal MRN) is used.

Acetic acid is used so that the coating can be carried out in the weakly acidic range, corresponding to one of the standards of the textile industry, but as such is not strictly necessary for the formulation. In some cases, additional textile chemicals for other textile effects are included in the liquid, examples being polymeric binders, cross-linking agents, softeners, and fluorocarbons. The formulations prepared as described above, in each case as the final component, were then stirred into the aqueous liquid. These liquids are applied to the textile to be finished in a completely standard manner using a padding machine. The samples were dried and partially cured on a tenter, but the formulations of the present invention do not require curing per se. Curing may be necessary to crosslink and/or fix other textile chemicals in various modifications, and curing is apparent from technical documentation for a particular product.

The textiles so modified were tested for antimicrobial effect against staphylococcus aureus ATCC6538 with and without pretreatment. According to the standard JISL 1902: 2002 and ASTM E21-49.

The results of both tests are given as the base ten log kill rate after 18 hours incubation. The kill rate is based on the microbial count of the inoculum (inoculum) or more precisely on the control sample after 18 hours of incubation. The dilution series were collapsed and then incubated, and then the number of microorganisms was counted.

The very excellent antibacterial effect gives a value of 2 or more, and a killing rate of 1.5 or more up to 2 is satisfactory.

Smaller values are unsatisfactory for modifying the sample and fall within the range of differences between the two test methods.

The textile was pretreated by sunlight and obtained by outdoor exposure of the test specimens. For this purpose, the test specimens were hung outdoors under a canopy and evaluated by visual inspection of each specimen. Testing the samples after varying number of wash cycles (performed using ECE 77 permanent wash detergent according to EN ISO 6330(6A) at 40 ℃); in some cases, the sample is exposed to sunlight after washing.

In each case, the textile used was a cotton-composed basis weight of 198g/m²Of a woven fabric having a basis weight of 160g/m²And a basis weight of 220g/m²Of Trevira polyester, or 120g/m²Dacron 54 spin (spun), or a basis weight of 230g/m from Tersuisse²9046 article and basis weight from Interlock of 160g/m²1880 the product of (1).

The following results show that the results are not dependent on the type of polyester used.

Examples 10 to 15

Typical examples of uses of textiles modified as described above are clothing textiles, in particular work clothes, uniforms and in particular sportswear and sportswear, bedding, textile wall finishing materials, seat covers, upholstery fabrics and carpets, table cloths, fabrics for umbrellas, household textiles such as cleaning cloths, wipes, towels, any articles made of heavy-pile cloth and textile toys.

Examples 16 to 20

Example 10 is repeated to modify cotton fabric with 0.3, 0.4, 0.5, 0.6 and 0.8% of the formulation of example 9. The difference was that the pH was not adjusted but in each case 1g/l of 80% acetic acid was added.

After 30 washes, a test for inhibition of Staphylococcus aureus ATCC 6338 was performed according to EN ISO 6330(6A) at 40 ℃. The log kill rate results were in the usual range of variation of the process, 2.6-3.8, and thus were excellent even at significantly lower concentrations of silver ion used than in the previous examples, with concentrations of about 100ppm silver ion in each case based on the mass of the textile being modified.

Examples 21 to 25

Example 11 is repeated to modify cotton fabric with 0.3, 0.4, 0.5, 0.6 and 0.8% of the formulation of example 9. The difference was that the pH was not adjusted but in each case 1g/l of 80% acetic acid was added.

The amount of Apprenan N92111 adhesive was kept constant at 70 g/l. After 30 washes, a test for inhibition of Staphylococcus aureus ATCC 6338 was performed according to EN ISO 6330(6A) at 40 ℃. Log kill rate results are in the usual variation of the process, 3.2 to > 4.9 and are therefore excellent. Good results are also obtained with the selected binders at use concentrations of 30-80ppm silver ion, estimated from the use application concentration and the coating amount.

Examples 26 to 31

Example 12 was repeated to finish a woven polyester fabric with 0.3, 0.4, 0.5, 0.6 and 0.8% of the formulation of example 9. The difference was that the pH was not adjusted but in each case 1g/l of 80% acetic acid was added. After 20 and 30 washes, a test was performed to inhibit staphylococcus aureus ATCC 6338 at 40 ℃ according to EN ISO 6330 (6A). No samples gave good results after 30 wash cycles. Log kill rate results after 20 wash cycles were within the usual variation of the method, but were a considerable 2.2 at only 0.3% formulation of example 9 and even 2.6 at 0.4% formulation.

These results are excellent for woven polyester fabrics, which are silver salt based products without the application of a binder after finishing.

Examples 32 to 36

Example 13 was repeated to finish a woven polyester fabric with 0.3, 0.4, 0.5, 0.6 and 0.8% of the formulation of example 9. The difference was that the pH was not adjusted but in each case 1g/l of 80% acetic acid was added. The amount of Apprenan N92111 binder was kept constant at 120 g/l. After 30 washes, a test for inhibition of Staphylococcus aureus ATCC 6338 was performed according to EN ISO 6330(6A) at 40 ℃. Log kill rate results are within the usual variation of the process, but a value of at least 3.0 is obtained.

Examples 37 to 41

Example 14 was repeated to modify a polyamide jersey knit with the 0.3, 0.4, 0.5, 0.6, and 0.8% formulations of example 9. The difference was that the pH was not adjusted but in each case 1g/l of 80% acetic acid was added. After 20 washes, a test was performed to inhibit staphylococcus aureus ATCC 6338 at 40 ℃ according to EN ISO 6330 (6A). However, the samples did not achieve the desired kill rate values.

Examples 42 to 46

Example 14 was repeated to modify a polyamide jersey knit with the 0.3, 0.4, 0.5, 0.6, and 0.8% formulations of example 9. The difference is that the pH is not set, but in each case 1g/l of 80% acetic acid is added. The amount of Apprenan N92111 adhesive was kept constant at 70 g/l. After 20 and 30 washes, a test was performed to inhibit staphylococcus aureus ATCC 6338 at 40 ℃ according to EN ISO 6330 (6A).

After 30 washes, samples using 0.6% and 0.8% formulations according to example 9 gave good values. However, the range of variation is considerable. In these tests, the inhibition of staphylococcus aureus ATCC 6538P was tested instead of the standard microorganism staphylococcus aureus ATCC6538, the 0.6 and 0.8% concentration of the inventive formulation of example 9 gave good values in all tests, i.e. a kill log value higher than 2, even after 20 washes the 0.5% formulation gave a value of 3.1, but undeniably only 0.5 after 30 washes.

The polyamide fabric used proved to be a difficult material to modify in all tests. This is consistent with wash durability and fading in sunlight.

Examples 47 to 50

Examples 51 to 54

Examples 55 to 58

Examples 59 to 62

Typical examples of uses of textiles modified as described above are apparel textiles, in particular work clothes, uniforms and in particular sportswear and sportswear, bedding, textile wall finishing materials, seat covers, upholstery fabrics and carpets, tablecloths, fabrics for umbrellas, skylights and sight protection.

Examples 63 and 64

Test for applying an easy-to-iron finish based on a crosslinked melamine resin to cotton

These tests were also carried out using other formulations whose preparation is not specifically described here, for example formulations with 10% of a 20 ℃ saturated solution of pinacol, formulations with 10% of a 20 ℃ saturated solution of pinacol and 0.5% of benzotriazole, and formulations with 1.5% of carboxymethylcellulose as thickener. All of these formulations provided had very excellent wash durability and did not exhibit any discoloration when applied in the formulations of examples 63 and 64 as described above.

Typical examples of uses for textiles modified as described above are easy-care, modified apparel textiles, such as shirts, gowns, household textiles, such as tablecloths and diapers.

The formulation of example 9 was also tested for application performance with fluorocarbon and polymer binders. To this end, various fluorocarbons from Clariant were tested. Specifically, these fluorocarbons are NuvaTTC (perfluoroacrylate/polyurethane dispersion), Nuva HPS liquid and Nuva HPC (which are all perfluoroacrylate copolymers), and Nuva HPU (perfluoroalkylacrylate copolymers).

Examples 65 and 66

All examples were performed in a similar manner. On the Trevira polyester, the concentration of the fluorocarbon and the binder were increased to 90 and 100g/l, respectively, so that the application amount remained comparable to that on the cotton fabric. On the polyamide, the same concentration as on the cotton fabric was used. All samples showed outstanding antibacterial effect up to 20 wash cycles. In the unwashed state, all samples showed 100% complete water repellency in the AATCC 22 spray test.

Typical examples of uses of textiles modified as described above are apparel textiles, in particular work clothes, uniforms and waterproof sportswear and sportswear, bedding, textile wall finishing materials, seat covers, upholstery fabrics and carpets, table cloths, and fabrics for umbrellas, skylights and sight protection.

The formulations according to example 9 were also tested for application properties together with flame retardants. To this end, various flame retardants obtained from Clariant were tested. On cotton, it is applied together with a cross-linking agent. These flame retardants are in particular Pekoflam DPN 1 (nonionic phosphate) and Pekoflam HSD liquids (formulation for application on cotton and cotton polyester blend fabrics with ammonium polyphosphate and urea) and Pekoflam PES (mixture of cyclic di-and triphosphonates for modifying the polyester).

Examples 67 and 68

Typical examples of uses of the textile modified as described above are apparel textiles, in particular work clothes, uniforms, bedding, textile wall finishing materials, seat covers, upholstery fabrics and carpets, table cloths, and fabrics for umbrellas, skylights and sight protection.

The application properties of the formulations according to example 9 were also tested by means of the venting method. Attempts to apply the formulation to a substrate were made by means of a degassing process. As examples shown later, outstanding results were surprisingly obtained.

Examples 69 to 71

It has been established that in principle the described venting method can be used with good results on standard fabric types. The uses of textiles that have been modified by the following method are various. In some cases, venting methods are often used to dress knitted fabrics when more or less cut into garments. This is done because the knitted fabric tends to twist on the tenter. Meanwhile, the exhaust method often includes other gray cloth converting steps such as dyeing, adding a softener, etc. Examples of articles that can be modified by the following method are stockings, pantyhose, T-shirts, sweaters and sweaters.

Example 72

Other series of tests were carried out on silk and blended fabrics consisting of cotton and polyester, using silver salt + pinacol yellow, and good antimicrobial results were obtained both with and without the use of a binder (ApprotonN 92111). The preservative is still satisfactory after 20 washing cycles.

Example 73

In the venting method, the application properties in the standard industrial methods for knitwear and in particular for knitted articles such as socks or T-shirts depend critically on the venting rate. The rate of exhaustion, which determines on the one hand the yield and on the other hand the gradual disappearance of said textile chemicals that remain in the effluent and are water pollutants, also relates to all chemicals that are not degraded in the waste water treatment stage and therefore adversely affect the drain opening. To determine the gassing rate of the formulation according to example 9, the residual content of silver or silver salt in the liquid after the gassing process was determined by means of atomic absorption spectroscopy in an instrument (Labomat model BFA from Mathis Werner AG, CH-8156 Oberhasli/Surich).

The exhaust conditions were:

● the mass ratio of the liquid to the textile is always 10: 1,

● substrate: CO is 198g/m²Of cotton (gabardine), PA is a bleached knitted fabric having a basis weight of 160g/m²White loomstate fabric (plain knit) of polyamide (ii) PES having a basis weight of 220g/m²White loomstate fabric of polyester (Trevira),

● the amount of the formulation used according to example 9 was always 0.5% or 0.8% based on the mass of the dry textile. This corresponds to an initial concentration of 5 or 8ppm Ag, respectively⁺，

● the pH is adjusted to 4-5 with 80% acetic acid,

● the heating and cooling rates were 3 deg.C/min in all cases,

● exhaust temperature was 60 deg.C, samples with polyester used for testing were additionally modified by a High Temperature (HT) process at 120 deg.C,

● at a discharge temperature of 60 ℃ for a discharge time of 30 minutes and at a discharge temperature of 120 ℃ for 20 minutes,

● separating the liquid after cooling and analyzing it,

● rinse the samples once in cold water (obtained from a municipal net) for 2 minutes,

● the samples were dried on the tenter at 120 ℃ tenter temperature for 2 minutes.

Analytical results of silver test

Substrate	Example 9 formulation concentration [%, based on the mass of the textile]	Temperature [ deg.C ]]	Ag [ ppm ] in liquids]	Yield [% ]]
					CO	0.5	60	1.2	76
CO	0.8	60	1.1	86
					PA	0.5	60	0.3	94
PA	0.8	60	0.3	96
					PES	0.5	60	0.9	82
PES	0.8	60	0.4	95
					PES	0.5	120	0.5	90
PES	0.8	120	0.4	95

The samples were washed with ECE 77 detergent at 40 ℃ according to EN ISO 6330(6A) and tested for inhibition of staphylococcus aureus ATCC6538 by the shake flask test of ASTM E21-49 after 20, 30 and 50 wash cycles. In this test panel, all kill rates were significantly higher than 90% compared to the inoculum after 30 wash cycles. With the exception of the polyester fabric modified at 60 ℃, the kill rate values remained above 90% after 50 wash cycles.

The comparative test using JMAC LP 10 gave no antibacterial effect on polyester only after 20 wash cycles, with silver concentrations in the off-gas liquid of 1Ppm (PA) -4ppm (PES and CO, both initial concentrations). In the high temperature process, the liquid from the application of PES still contains 3ppmAg from the initial concentration of 7.5⁺Or contains 12ppm Ag in the batch⁺. The yield in the case of application of the product according to example 9 is significantly better than in the case of the reference starting material using titanium dioxide as support for the silver compound. Despite the significantly reduced amount of silver compound in a composition ratio of 3: 2, an at least equal and even clearly superior wash durability on photosensitive substrates was measured.

All of the examples that follow were carried out on production scale machines. The amount of textiles used in all cases corresponded to the amount used for the pilot test, i.e. several tens of linear meters in the case of pad application and about ten or more kilograms of fabric in the case of the exhaust process. Embodiments including socks were implemented using standard production sizes for a batch. The washing was carried out according to EN ISO 6330 by using the standard colour fastness detergent ECE 77. In addition to standard temperatures of 40 and 60 ℃, a unique wash program was programmed to run at the wash and rinse times of the 60 ℃ program, but including heating to 72 ℃. This is the highest washing temperature in the chamber of the industrial scrubber tube used here as a reference for the experiment. The washing test was stopped after 100 cycles, since this was already much higher than the value associated with the service life of most textiles in operation, even higher than the value currently required by the market, although the standards are in constant progress.

The durability of the antimicrobial modification is expected to be 20-30 wash cycles, and in particular cases equal to 50 wash cycles. 100 wash cycles, if any, are of interest only in the hotel/restaurant and care areas, although the washes herein are much shorter in duration and more mechanically gentle than the wash standards that follow normal european household washes.

Examples 74 and 75

30kg of a knitted cotton polyester black sock was placed in a Lavatec spray dryer. A mixture of 900g of Hydroperm HV, 600g of Hydroperm RPU and 200g of the formulation according to example 9 in 10 liters of water is sprayed by means of steam nozzles onto the socks in a running horizontal drum from a spray head mounted on a rotating shaft. The sock is then dried in the drum. The socks were tested for inhibitory properties against Staphylococcus aureus ATCC6538 by the shake flask test according to ASTM E21-49 after 20 and 30 washing cycles. After 30 washing cycles, the killing rate is still higher than 99%.

The same tests were carried out using the silver product on titanium dioxide and other identical formulations in the same test apparatus. The use of steam nozzles does not allow for uniform spraying of the product. Because the method was not applicable to the product, the test was stopped and no further samples were tested.

To 80kg of woven cotton polyester gray socks in a cage containing a degassing bath containing 1000 litres of water, a mixture of 1kg of the formulation according to example 9 in 10 litres of water was added. Since the liquid circulates at the bottom of the sink, i.e. below the cage, it is removed and pumped via a heat exchanger to a higher position where it is returned to the product via a distributor, heated to 60 ℃, held at 60 ℃ for 15 minutes and then added to 2.4kg of Hydroperm HV and 1.6kg of Hydroperm RPU in 15 litres of water, and kept at a constant temperature of 60 ℃ for a further 30 minutes while continuing the circulation. The liquid is then dripped into the same apparatus and the articles are rinsed in the same apparatus with cold water, the rinsing water is likewise removed, and the articles are drained, spun and subsequently dried.

The socks were tested for inhibitory properties against Staphylococcus aureus ATCC6538 by the shake flask test according to ASTM E21-49 after 20 and 30 washing cycles. With this modification, the kill rate still exceeded 99% after 30 washes.

Example 76

12kg of purple knitted fabric consisting of 80% polyamide and 20% Lycra were treated in a jet with a liquid consisting of 180g of the formulation according to example 9 in 80 l of water at 60 ℃ for 30 minutes. After cooling, water was added dropwise. Fresh water for rinsing was added and dropped after 5 minutes as well. The woven fabric was dried on a tenter having six heating zones and a length of 18 meters at 150 ℃ and a line speed of 10 meters per minute. The textiles were used for wash tests at 40, 60 and 72 ℃, and the samples were dried and tested after 1, 3, 5, 10, 20, 40, 50, 60, 80 and 100 wash cycles. After 100 wash cycles, the experiment was stopped. All samples gave a kill rate of at least 90% when tested for inhibition performance against staphylococcus aureus ATCC6538 according to the shake flask test of ASTM E21-49.

Example 77

A red knit fabric consisting of polyester (for jersey) was modified by padding with 1.5% of the formulation described according to example 9, 0.03% Hostapal MRN wetting agent and 4.0% Solusoft MW softener and 0.5% Velustrol P40 softener. Then dried and cured on a tenter at 150 ℃.

The samples were tested for inhibitory properties against Staphylococcus aureus ATCC6538 by the shake flask test of ASTM E21-49 after 50 and 100 wash cycles at 72 ℃. For both samples, the kill rate was above 99%.

Example 78

In the same way, the same formulation as in example 76 but additionally using a 5.0% aprestan N92111 soft acrylate adhesive was applied to the same substrate.

The samples were tested for inhibitory properties against Staphylococcus aureus ATCC6538 by the shake flask test of ASTM E21-49 after 50 and 100 wash cycles at 72 ℃. For both samples, the kill rate was significantly higher than 99%.

Examples 79 and 80

Dark blue polyester textiles (for sportswear) were each individually finished once by pad dyeing with and without 4.0% Appretan N92111 with a formulation described according to 1.2% of example 9. The fabric was dried on a tenter having six heating zones and a length of 18 meters at 150 ℃ and a line speed of 10 meters per minute.

The samples were tested for inhibitory properties against Staphylococcus aureus ATCC6538 by the shake flask test of ASTM E21-49 after 50 and 100 wash cycles at 72 ℃. The kill rate was significantly higher than 99% for all samples.

Example 81

In the exhaust method, the application is carried out in a jet stream on a blue textile with elasticity composed of polyamide in a large liquor ratio of 40: 1. The formulation according to example 9 (always based on the mass of the dried unmodified textile) was applied at 60 ℃ at a pH of 5 (set with acetic acid).

The samples were tested for inhibitory properties against Staphylococcus aureus ATCC6538 by the shake flask test of ASTM E21-49 after 50 and 100 wash cycles at 72 ℃. Even with these samples, the kill rate was still significantly higher than 99%.

Claims (19)

1. A method of modifying a fiber or textile using an antimicrobial active component comprising a silver component desensitized with additional components and optionally one or more other antimicrobial components; wherein the silver component is present in an amount of from 0.0001 wt.% to 1.5 wt.%, based on the total weight of the fiber or textile; wherein said additional component used comprises at least one compound selected from the group consisting of quinoline derivatives selected from the group consisting of pinacol yellow, pinacol green and pinacol white, and wherein said quinoline derivatives are used in an amount of 0.1ppm to 500ppm, based on the total weight of the fiber or textile.

2. The method of claim 1, wherein the additional component to desensitize comprises pinacol yellow.

3. The method as claimed in claim 1 or 2, characterized in that the antimicrobial active ingredient used comprises a silver salt as silver ingredient.

4. A method as claimed in claim 1 or 2, characterized in that the antimicrobial active ingredient used comprises an in situ formed silver salt as silver ingredient and pinacol yellow as additional ingredient.

5. The process according to claim 1 or 2, wherein the antimicrobial active ingredient used comprises a silver salt as silver ingredient and at least one quinoline derivative and an additional benzotriazole derivative as phlegmatizer ingredient, wherein the benzotriazole derivative is a compound or salt of the general formula (I)

Wherein R is¹Is hydrogen or C1-C4 alkyl, and

R²is hydrogen or a metal.

6. The method of claim 5, wherein R is²Is an alkali metal.

7. The method according to claim 1 or 2, characterized in that the antimicrobial active ingredient used comprises a water-insoluble silver salt as silver ingredient and at least one quinoline derivative as phlegmatising ingredient and a benzotriazole derivative in an amount of 0.5ppm to 2500ppm based on the total weight of the fiber or textile, wherein the benzotriazole derivative is a compound or salt of the general formula (I)

Wherein R is¹Is hydrogen or C1-C4 alkyl, and

R²is hydrogen or a metal.

8. The method of claim 7, wherein R is²Is an alkali metal.

9. The method of claim 1 or 2, wherein the water insoluble silver component comprises one or more salts selected from the group consisting of chloride, bromide, iodide, sulfate, and tosylate.

10. The method of claim 1 or 2, wherein the water insoluble silver component comprises silver chloride prepared in situ from silver nitrate and a metal chloride.

11. The method according to claim 1 or 2, wherein the phlegmatizing component comprises, as a single component, pinacryptol yellow or a combination of pinacryptol yellow and at least one other phlegmatizing component.

12. The method of claim 1 or 2, wherein the method of modifying the fiber or textile comprises padding, air-venting, foam application, coating, or spraying.

13. An antimicrobial formulation for the modification of fibers or textiles with an antimicrobial active component comprising as antimicrobial active component at least one silver component, an additional phlegmatizing component and optionally one or more auxiliaries and additive materials, wherein the additional phlegmatizing component used comprises at least one compound selected from the group consisting of quinoline derivatives selected from the group consisting of pinacryptol yellow, pinacryptol green and pinacryptol white, the silver component being present in an amount of from 0.01% to 10% by weight, calculated as Ag, and the additional phlegmatizing component being present in an amount of from 0.001% to 2% by weight, based on the total weight of the formulation.

14. The formulation of claim 13, comprising 0.001% to 2% pinacryptol yellow, based on the total weight of the formulation.

15. An antimicrobially modified fiber or textile obtained by the method of any of claims 1-2.

16. The antimicrobially modified textile of claim 15, comprising a woven fabric, a knitted fabric, a nonwoven web, or a yarn.

17. Use of a formulation according to claim 13 or 14 for protecting a fibre or textile against bacterial attack.

18. Use of a formulation according to claim 17, comprising a silver salt and, as phlegmatising component, at least one of a quinoline derivative and a benzotriazole derivative, wherein the benzotriazole derivative is a compound or salt of formula (I) for protecting a fiber or textile against bacterial attack

Wherein R is¹Is hydrogen or C1-C4 alkyl, and

R²is hydrogen or a metal.

19. As claimed inUse of the formulation of claim 18, wherein R is²Is an alkali metal.