EP2162567A2

EP2162567A2 - Method for treating an at least partially metallised textile, treated textile and use thereof

Info

Publication number: EP2162567A2
Application number: EP08760975A
Authority: EP
Inventors: Dieter Kreysig
Original assignee: Militz Detlef
Current assignee: Militz Detlef
Priority date: 2007-06-12
Filing date: 2008-06-12
Publication date: 2010-03-17
Also published as: AU2008263866A1; US20100136075A1; DE102007027632A1; ZA201000173B; KR20100012881A; WO2008152121A2; JP2010529323A; CN101784697A; CA2690270A1; IL202626A0; WO2008152121A3

Abstract

The invention relates to a method for treating an at least partially metallised textile, according to which said textile is treated with at least one agent selected from the group consisting of reductants and complex formers. The invention also relates to a textile treated in this way and to the use thereof for the anti-microbial treatment of liquids or for producing hosiery, insoles, clothing, covers for seating furniture or mattresses. A textile that has been treated according to the invention is capable of an adjustable, purpose-specific metal delivery depending on the field of application.

Description

Title:

Process for the treatment of at least partially metallised textile, treated textile and its use

Description:

The present invention relates to a process for the treatment of at least partially metallised textile. Furthermore, the present invention relates to a textile obtained by the process according to the invention and its

Use.

For the purposes of the present patent application, a textile in a one-dimensional sense is, for example, a yarn composed of a plurality of yarns or a yarn which is formed as a monofilament or multifilament filament yarn or as a staple fiber yarn. In the two-dimensional sense, a textile is designed as a textile fabric, for example as a woven, knitted, braided, knitted or nonwoven fabrics. Furthermore, three-dimensional textiles are detected which, for example, have a textile fabric, of which thread portions extend transversely away from a plane defined by the textile fabric from the textile fabric.

At least partially metallized textiles are known from the prior art. These metallized textiles are either completely or partially coated with metal and optionally with metal ions. A textile can basically be metallized in the textile processing state in which it is used in its field of application. Alternatively, a textile can also be metallized and subsequently further processed by textile technology. This is optionally done together with another metallized or unmetallized textile.

Methods of metallizing textiles are known in the art. For example, US Pat. No. 4,681,591 describes a process for producing a metallized polyester fiber textile comprising the steps of pretreating the textile material with at least 15% by weight of polyester fibers with an aqueous solution of caustic alkali, activating treatment of the pretreated one Textile material comprising a stannous-containing compound and a palladium-containing compound and non-electrolytically coating the activating-treated textile material in a mixture containing nickel, copper, cobalt, chromium or their alloys to form a metal coating thereon , A metallized textile produced in this way is suitable as protection against electromagnetic radiation.

DE 34 19 755 A1 discloses a method for silvering non-metallic materials. In this case, a surface to be silvered is activated with at least one compound based on palladium and then silvered using a silver plating bath which contains, in addition to a silver salt, thiocyanate ions as complexing agent and hydroxylamine as reducing agent.

JP 2005105386 A describes a bath for silvering fibers. The bath contains a silver salt, a complexing agent, a stabilizing agent and a reducing agent.

JP 61281874 A discloses a process for the metallization of polyester, in which polyester is treated with sodium hydroxide solution, sensitized, activated and subsequently metallized with nickel or copper.

Furthermore, DE 10 2006 055763 discloses a process for the metallization of polyester, in which the polyester

- treated with a basic solution,

is treated with at least one compound selected from the group consisting of a primary amine, a secondary amine, a thiol, a sulfide or an olefin,

- treated with a solution containing at least one metal salt selected from the group consisting of a silver salt, a copper salt and a nickel salt, and at least one complexing agent, and

- Is treated with at least one reducing agent. A disadvantage of the methods indicated in the prior art is that due to an excess use of metal salts and / or due to incomplete conversion of metal salts to metals metal salts remain in the metallized material, resulting in increased and uncontrolled metal ion release when using the metallized material, for example in lead a liquid. In particular, with regard to environmental and disposal aspects, but also on the cost-effectiveness of such materials, an uncontrolled release of metal or metal ions is disadvantageous.

In particular, the uncontrolled, often too high delivery of metal or metal ions into a liquid prevents the use of metallized textile in fluid-carrying systems, because such textiles do not meet the system specifications or guidelines and regulations that, for example, to protect the environment or of the EU, such as EU Directive 98/83 on drinking water.

The present invention is therefore based on the object of providing a process for the production of at least partially metallised textile available, whose purpose-oriented metal delivery can be controlled according to the application field according to the respective regulations, guidelines and / or system specifications.

This object is achieved by a method having the features of claim 1.

According to the invention, in a process for treating an at least partially metallized textile, the textile is treated with at least one agent selected from the group consisting of reducing agent and complexing agent.

The active principles of the agent are the reduction of ionic metal portions in the region of the surface of the at least partially metallized textile or the removal of ionic metal portions of the at least partially metallized textile by means of complexing. These strategies of action serve - A - to prevent uncontrolled high metal or metal ion release from the metallized textile to the environment.

For the purposes of the present invention, therefore, the method of the invention serves as a method for the reduction of metal ions or for the complexation of metal ions in order to effect a purpose-oriented, depending on the application field controlled metal delivery. Thus, not only a higher economic efficiency, lower disposal costs and lower environmental damage are achieved, but also achieved a depot effect in the application. A depot effect in the application means that a metal delivery permitted in accordance with the respective guidelines, system specifications and regulations is constant over a long period of time. As a result, a long duration of action and thus a long operational capability of a textile produced by means of the method according to the invention are obtained.

In a preferred embodiment, the agent is a reducing agent. The reducing agent is preferably selected from the group consisting of glucose, ascorbic acid, sodium dithionite, sodium borohydride, sodium thiosulfate, sodium sulfite, sodium formate, formaldehyde and sodium hydrophosphite. More preferably, the reducing agent is ascorbic acid. More preferably, the reducing agent is glucose. Glucose or ascorbic acid is a very environmentally friendly reducing agent, easy to handle, readily available, water-soluble, approved for use in food. The reducing agent is preferably used in aqueous or alcoholic solution for the treatment of the at least partially metallized textile. After the treatment, the at least partially metallised textile is preferably washed and dried.

When the reducing agent is glucose, it is preferably used in the form of an aqueous solution having a concentration of 1.25 to 5 g / l and a pH in the range of 7 to 12, preferably 8 to 10.5. The pH of the solution can be adjusted, for example, by means of the addition of ammonia. The treatment of the at least partially metallized textile is carried out at a liquor ratio (ratio of the mass (kg) of the product to the volume (I) of the Reducing agent solution) of 1:10 to 1: 100, preferably 1: 50 to 1: 100 performed. The at least partially metallized textile is agitated in the reducing agent solution at 50 to 60 ^° C. for 30 to 60 minutes. The treated textile is preferably washed after the treatment with the reducing agent with water and optionally dried at a temperature of up to 140 ⁰ C.

When the reducing agent is sodium borohydride, the reduction is preferably carried out in ethanol, in particular at temperatures between 10 ° C and 50 ⁰ C, preferably 20 ° C and 30 ° C, over a period between 15 and 60 minutes. Subsequently, the treated textile is preferably washed with water and optionally dried at a temperature of up to 140 ⁰ C.

In another preferred embodiment, the agent is a complexing agent. The complexing agent is preferably selected from the group consisting of ammonia, thiosulfate, thioisocyanate, ethylenediamine, triethanolamine, ethanolamine, 1,3-diaminopropane, glycerol, sodium tartrate, sodium potassium tartrate and sodium citrate. Particularly advantageous is the complexing agent ammonia. Ammonia is volatile. Therefore, excess ammonia can be easily removed. The at least partially metallized textile is rinsed with the complexing agent, which may be present as an aqueous solution. Subsequently, the treated textile is optionally washed with water and optionally dried at a temperature of up to 140 ° C.

In an alternative or additional embodiment, a polymer may be used as the means for treating an at least partially metallized textile. The polymer is preferably selected from the group consisting of polyurethane, polyacrylate and finishing equipment. The treatment of the at least partially metallized textile with a polymer includes the use of a polymer for the partial or complete coating of the at least partially metallized textile, it being possible if appropriate to use adhesion promoters or adhesion-promoting layers. On the other hand, treating the at least partially metallised textile with a polymer excludes the application of at least one monomer at least partially metallized textile and polymerization of the at least one monomer. Processes for the preparation of polymers, in particular polyacrylates and polyurethanes, are known to the person skilled in the art. Likewise, those skilled in the process for coating a textile with polymers are known.

Polyacrylates generally have a controlled uptake and permeability to liquids, especially water, and therefore, despite coating of the at least partially metallized textile effect of the metal on the environment. Examples of polyacrylates include, but are not limited to, polyacrylic acid esters, polybutyl acrylate, polyhydroxyalkyl acrylate, and polymethyl acrylate.

The polyurethane is preferably polyurethane lacquer or polyurethane elastomer. High-grade finishing equipment includes common auxiliaries, processing and additives as well as commercially available polymers and copolymers.

The method is preferably designed such that the at least partially metallized textile is present as a thread system comprising a thread material with an at least partially metallized yarn, wherein the at least partially metallized thread material before the treatment of the textile alone or together with additional thread material textile technology to the thread system has been processed.

In this case, the thread material comprises at least one yarn and / or at least one thread. For the purposes of the present invention, a thread system can be designed one-dimensional, two-dimensional or three-dimensional. For example, a one-dimensional thread system is a thread. Two-dimensional thread systems are textile fabrics which can be designed, in particular, as a knitted fabric, woven fabric, knitted fabric, braid or fleece. A three-dimensional thread system is for example a spacer knitted fabric. On the one hand there is the variant to process thread material with at least one at least partially metallised yarn to form a thread system. Alternatively, additional, unmetallized thread material can be processed into the thread system. Again, alternatively, unmetallized thread material can be processed into a thread system, wherein the thread system is then at least partially metallized. Result of all manufacturing variants is in each case an at least partially metallized textile in the form of a thread system, which is then subjected to the described treatment process.

It has been found that the metal delivery of an at least partially metallised textile is influenced by each textile processing step of the at least partially metallized thread material contained therein. This is related to the mechanical stress of the metallized surfaces of the thread material. The mechanical stress is inevitably very high in the textile processing. If a metal release of the textile defined for the desired application is to be set by the treatment method, then it is preferable to avoid mechanical stresses on the metallized surfaces of the thread material contained in the textile after the treatment. In other words, it is preferable to complete the textile processing steps and the associated high mechanical stress of the thread material surfaces before the treatment of the textile is made.

In a preferred embodiment, a silvered polyamide yarn is processed with a non-metallized polyester yarn into a twist which is then processed by means of a spacer warp knitting machine in the production of a spacer knit. In this case, the two yarns are processed as thread material to a twist as a one-dimensional thread system, which in turn is further processed in a spacer knit as a three-dimensional thread system. In this case, the twist can form both the entire spacer knitted fabric and only individual regions of the knitted spacer fabric. After completion of the textile processing steps described above is the Spacer fabric preferably subjected to the treatment process according to the invention.

The technical textile processing of the thread material to the thread system preferably comprises at least one of the processing techniques: twisting, weaving, knitting and knitting. Usually, the thread system produced in this way is cut to the desired size, for example by means of laser or plasma cutting devices.

In a preferred embodiment, the textile contains polyamide, polyester, polyolefin or mixtures thereof and optionally one or more customary auxiliaries, processing or additives. For the purposes of the present invention comprise polyamide, polyester or polyolefin both homopolymers and copolymers. The polyamide used is preferably PA 6, PA 11, PA 12, PA 66, PA 46, PA 6 / 6T, PA 6 / 6I, PA 1212, PA 612, PA 6I, PA 6I / 6T, PA MXDI / 6I, PA MXDI / MXDT / 6I / 6T, PA MXDI / 121, PA MACMI / 12, PA MACMI / MACMT / 12, 6I / MACMI / 12, PA 6I / 6T / MACMI / MACMT / 12, PA PACM6 / 11, PA PACM12, PA PACMI / PACM12, PA MACM6 / 11, PA MACM12, PA MACMI / MACM12, PA MACM12 / PACM12, PA6I / 6T / PACMI / PACMT / PACM12 / 612, more preferably PA6, PA11, PA12, PA66 or PA 46, used. The polyester used is preferably polyethylene terephthalate, polybutylene terephthalate, poly-1, 4-cyclohexanedimethylene terephthalate, polyethyleneoxybenzoate or poly-1, 4-cyclohexylidenedimethylene terephthalate and mixtures thereof, particularly preferably polyethylene terephthalate or polybutylene terephthalate. The polyolefin used is preferably polypropylene or polyethylene, more preferably polypropylene. The usual auxiliaries, processing or additives include, but are not limited to, stabilizers, flame retardants, processing aids, antistatic agents, antioxidants, plasticizers, dyes, impact modifiers, adhesion modifiers, pigments, reinforcing agents and / or fillers. Preferred examples of the usual auxiliaries, processing or additives include short glass fibers, glass beads, C fibers, silica, carbon black, chalk, mica, talc, barite, mica, wollastonite, calcium carbonate, titanium dioxide, nanocomposites, graphite, M0S ₂ , silicates, Aluminum, copper, bronze, steel, lead, Zinc, nickel, but are not limited thereto. Furthermore, the term "additives" also includes thread materials of all kinds, which can be textile technology integrated into the at least partially metallized textile.

In the process according to the invention, the textile which is at least partially metallised and which is at least partially coated with an oligodynamically active metal is preferably used as the textile. Oligodynamically active metals include semi- and precious metals such as silver, copper, nickel, zinc and gold. A "textile which is at least partially coated with an oligodynamic metal" means a textile in which the oligodynamically active metal can either be provided in metallic form as particles embedded in the textile structure or layers arranged on the textile and optionally in suitable ionic form, for example as Of course, one or more intermediate layers can be arranged between the textile and the layer of oligodynamic metal.

The oligodynamically active metal imparts to the textile an oligodynamic, germicidal activity which is ensured, on the one hand, by liberation of metal atoms and / or metal ions into the liquid surrounding the textile and, on the other hand, by a contact reaction of bacteria on the surface of the at least partially metallised textile. That is, in addition to the action of the metal ions released into the water, the non-dissolving metal atoms or metal ions present on the thread surface - when using sparingly soluble metal salts - contribute to the overall oligodynamic effect of the textile, which is at least partially introduced into a liquid.

Articles of the present invention are also the textile obtained by the method according to the invention and its use.

The process according to the invention is advantageously used with a metallized polyamide or polyester which is metallized by treating the polyamide or the polyester with a basic solution. is treated with at least one compound selected from the group consisting of a primary amine, a secondary amine, a thiol, a sulfide or an olefin,

- Is treated with at least one reducing agent.

The above method of metallizing polyester or polyamide will be referred to as a metallization method hereinafter.

Preferably, in the metallization process, the basic solution is an aqueous and / or alcoholic solution containing sodium hydroxide or potassium hydroxide.

Preferably, in the metallization process, the compound selected from the group consisting of a primary amine, a secondary amine, a thiol, a sulfide, or an olefin is crosslinked prior to further treatment with a metal salt-containing solution. The crosslinking of the compound can be realized by self-crosslinking of the compound, for example by condensation. Alternatively, the crosslinking of the compound can be realized by adding at least one further compound and crosslinking with it, for example by an addition.

Preferably, the at least one compound selected from the group consisting of a primary amine, a secondary amine, a thiol, a sulfide and an olefin, is a compound of the formula

(R ¹ O) _X MR ₄ . _X (I), where

R ^{1 is} a branched or straight-chain alkyl having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, even more preferably 1 or 2 carbon atoms, x is a number from 1 to 3, preferably 3,

M is Si, Ti or Sn, and

R is selected from the group consisting of CH ₂ CH ₂ CH ₂ NH ₂ , CH ₂ CH ₂ CH ₂ SH,

CH = CH ₂ , (CH ₂ ) p NH (CH ₂ ) _n NH (CH ₂ ) ₁ NH ₂ and (CH ₂ ) _n NH _m [(CH ₂ ) _L NH ₂ ] _k , p an integer from 1 to 7 , preferably 2 or 3, n is an integer from 1 to 7, preferably 2 or 3, m is zero when k is 2, m is 1 when k is 1, and I is an integer from 1 to 7 , preferably 2 or 3, being in an even more preferred embodiment

R ^{1 is} methyl, ethyl, propyl or butyl, x is a number from 1 to 3,

M is Si, Ti or Sn, preferably Si, is and

R 1 is aminopropyl, 1-mercaptopropyl or vinyl.

Preferably, the metal salt is selected from the group consisting of silver halide, silver sulfate, silver nitrate, copper halide, copper sulfate, copper nitrate, copper acetate, nickel halide, nickel sulfate, nickel nitrate and nickel acetate, halide being chloride, bromide or iodide, more preferably silver nitrate, silver chloride or silver sulfate. The complexing agent and the reducing agent are the same as mentioned above.

More preferably, the process of the present invention is applied to a metallized polyamide or metallized polyester which is metallized according to the above process, which comprises treating with at least one compound selected from the group consisting of a primary amine, a secondary amine Amine, a thiol, a sulfide and an olefin,

contacting the basic solution-treated polyamide or polyester with at least one compound of formula (I),

(R ¹ O) _X MR ₄ . _X (I) wherein R and R ^{1 are} each independently a branched or straight-chain alkyl having 1 to 20 carbon atoms, preferably 1 to 10 Carbon atoms, more preferably of 1 to 8 carbon atoms, more preferably of 1 or 2 carbon atoms, x is 1 to 4 and M is Si, Ti or Sn,

optionally a first condensation,

contacting with at least one compound of formula (I) wherein R ^{1 is} a branched or straight chain alkyl of 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, more preferably 1 or 2 carbon atoms, x 1 to 3, preferably 3,

M is Si, Ti or Sn,

R is selected from the group consisting of CH ₂ CH ₂ CH ₂ NH ₂ ,

CH ₂ CH ₂ CH ₂ SH, CH = CH ₂ , (CH ₂ ) _p NH (CH ₂ ) _n NH (CH ₂ ) ₁ NH ₂ and

(CH ₂ ) _n NH _m [(CH ₂ ) ₁ NH ₂ ] _k , p is an integer from 1 to 7, preferably 2 or 3, n is an integer from 1 to 7, preferably 2 or 3, m is zero when k is 2, m is 1 when k is 1, and I is an integer from 1 to 7, preferably 2 or 3, and

- Includes a second condensation.

In the metallization process, examples of a preferred compound of formula (I) as functionalized alkoxysilane include 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane (3-trimethoxysilyl-1-propanethiol), triethoxyvinylsilane, N- (2-aminoethyl) -3- aminopropyltrimethoxysilane or 2- [2- (3-trimethoxysilylpropylamino) ethylamine] -ethylamine and as unfunctionalized alkoxysilane tetraethoxysilane, tetramethoxysilane, triethoxyoctylsilane or triethoxymethylsilane.

The process according to the invention is furthermore advantageously used in the case of a metallized polyamide or metallized polyester which is metallized in accordance with the above process, in which the treatment with at least one compound selected from the group consisting of consisting of a primary amine, a secondary amine, a thiol, a sulfide and an olefin,

(R ¹ O) _X MR ₄ . _X (I) where

Is methyl, ethyl, propyl or butyl, x is 4 and M is Si, Ti or Sn,

a first condensation,

- contacting with at least one compound of formula (I) wherein R ^{1 is} methyl, ethyl, propyl or butyl, x is 1 to 3, M is Si, Ti or Sn and R 1 is aminopropyl, 1-mercaptopropyl or vinyl , and

- Includes a second condensation.

In the metallization process, contacting the polyester or polyamide with a compound of formula (I) comprises padding. For this purpose, the compound of formula (I) in a solvent such as water and / or alcohol and optionally hydrochloric acid is applied to the polyamide or polyester and then padded. The condensation comprises heating the polyester or polyamide treated with at least one compound of the formula (I) up to 200 ^° C., preferably up to 170 ^° C., more preferably up to 140 ^° C.

In another preferred embodiment, the inventive method is used in a metallized textile, which is metallized by the fact that the textile

is treated with a compound having at least one amine group,

is treated with a compound which has at least one functional group which is suitable for performing an addition reaction with the amine group,

- treated with a solution containing at least one metal salt selected from the group consisting of a silver salt, a copper salt and a nickel salt, and a complexing agent, and - Is treated with at least one reducing agent, wherein the order of the first two steps is interchangeable.

In the above process for metallizing the textile, the compound having at least one amine group is, in an advantageous embodiment, a liquid, polyfunctional amine, which is preferably a compound of the formula

R ² NHR ³ (II)

wherein R ^{2 is} selected from the group consisting of H ₂ N (CH ₂ ) W, R ⁴ 3 Si (CH ₂ ) _w and

H ₂ NC ₆ H ₄ ,

R ^{3 is} selected from the group consisting of [(CH ₂ ) _x NH] _y (CH ₂ ) _z NH ₂ , R ₃ Si (CH ₂ ) _y and H ₂ NC ₆ H ₄ NH (CH ₂ ) _y , w an integer from 1 to 7, preferably 2 or 3, x is an integer from 1 to 7, preferably 2 or 3, y is zero or an integer from 1 to 7, preferably zero, 1 or 2 , z is an integer from 1 to 7, preferably 2 or 3, and

R ^{4 is} a branched or straight-chain alkyl or -O-alkyl having 1 to 10

Carbon atoms, preferably having 1 to 8 carbon atoms, more preferably having 1 or 2 carbon atoms.

Advantageously, the compound of formula (II) is selected from the group consisting of bis (3-aminopropyl) amine, N, N'-bis (2-aminoethyl) -1, 3-propanediamine, triethylenetetramine, tetraethylenepentamine, bis [3 (trimethylsilyl) propyl] amine and bis [3- (trimethoxysilyl) propyl] amine. Particularly advantageous is the compound of formula (II) bis (3-aminopropyl) amine or tetraethylenepentamine.

In an advantageous embodiment of the process for the metallization of the textile, the crosslinking of the compound of the formula (II) is carried out by contacting with a compound which has at least one isocyanate group, preferably two isocyanate groups. A compound of formula (II) leads with a compound having at least one isocyanate group, an addition reaction to form a urea. Advantageously, the compound having at least one isocyanate group, a diisocyanate. Preferably, the diisocyanate is selected from the group consisting of hexamethylene diisocyanate, tolylene diisocyanate, isophorone diisocyanate and 4,4'-methylene-bis (cyclohexyl isocyanate). Most preferably, the diisocyanate is hexamethylene diisocyanate. To effect crosslinking of the compound having at least one amine group with a compound having at least one isocyanate group, the textile is coated with the compound having at least one amine group, optionally padded, and then with a compound having at least one Has isocyanate group, coated and optionally padded. Of course, the coating order is freely selectable. Optionally, the corresponding compound may be dissolved in a solvent, preferably water.

Alternatively, an addition reaction of the compound having at least one amine group is carried out by contacting with a compound having at least one epoxy group. Examples of a compound having an epoxy group are propylene oxide, styrene oxide, 4-vinyl-1-cyclohexene-1, 2-epoxide, 2,3-dimethyl-2,3-epoxybutane and limonene-1, 2-epoxide. The compound having at least one epoxy group may be dissolved in a solvent. The solvent used is an aprotic solvent, more preferably an ether or an optionally chlorinated hydrocarbon. To carry out the addition reaction, the textile, which has either been treated with a compound having at least one amine group, or subsequently treated, is sprayed, wetted, dipped or laid with the compound having at least one epoxy group.

Preferably, in the process of metallizing the textile using an addition reaction of a compound having at least one amine, the metal salt selected from the group consisting of silver halide, silver sulfate, silver nitrate, copper halide, copper sulfate, copper nitrate, copper acetate, nickel halide, nickel sulfate, Nickel nitrate and nickel acetate, wherein Halide is chloride, bromide or iodide, preferably silver nitrate, silver chloride or silver sulfate. The complexing agent and the reducing agent are the same as mentioned above.

Particularly preferably, the at least partially metallised textile used in the process according to the invention is a besilbertes textile. A silvered textile is, in a preferred embodiment, treated with glucose as the reducing agent. The reducing action of aqueous solutions of glucose depends, inter alia, on the glucose concentration and the pH-dependent redox potential. For a textile which is treated with 0.5% glucose solutions at 60 ^° C. for one hour (hereinafter referred to as the standard), the pH is linearly dependent on the redox potential

of -25 mV at pH 7.5 and -275 mV at pH 12; for treatment with 1% glucose solution of ± 0 mV at pH 6.8 to -225 mV at pH 12.

The silver release of the treated standard material after treatment decreases linearly with increasing pH of the reducing solution and with increasing oxidation potential:

from 185 μg Ag / 1 at pH 7.5 to 20 μg Ag / 1 at pH 12 or from 185 μg Ag / l at -20 mV to 14 μg Ag / l at -280 mV.

That is, by treating the at least partially metallized textile with the method of the invention, the metal or metal ion release, in this case the silver or silver ion release, of the metallized textile into a surrounding liquid can be adjusted to a certain value.

In a preferred embodiment, the textile is formed as a yarn, a twine, a woven fabric, a knitted fabric, a braid, a knitted fabric or a fleece. Particularly preferably, the at least partially metallized textile is a spacer knitted fabric. In another particularly preferred embodiment that is at least partially metallized textile a spacer knitted fabric having only at one of its surfaces an at least partially metallized yarn material.

A textile obtained using the method of the invention is suitable for the antimicrobial treatment of liquids in a liquid-conducting system. For this purpose, in particular a besilbertes textile, since silver is by its excellent antimicrobial effect in a position to effectively inhibit especially bacteria, fungi and microalgae. Alternatively, the textile obtained by the process according to the invention is used for the production of stockings, insoles, clothing, upholstery for seating or mattresses. Again, a besilbertes textile is particularly suitable because of the particularly strong oligodynamic properties.

The textile obtained using the method according to the invention is used in particular in the treatment of a liquid in the form of a useful liquid or in the form of drinking water. These fluids may be in closed or open circuited, stagnant or recirculated systems in power plants, industrial plants, ballast water tanks of ships, swimming pools, whirlpools or in air conditioning systems. In any case, the metal elution of the textile according to the invention can be adjusted individually such that, for example, when used for the treatment of liquid in the form of drinking water, different national regulations regarding the maximum permissible metal concentration in drinking water are adhered to.

The term "useful liquid" serves as a generic term for a liquid which fulfills one or more functionalities such as, for example, cooling, lubricating, hydraulically switching and controlling, or which is consumed as a process or process fluid.

A preferred use is that the antimicrobial treatment of a liquid in a liquid-conducting system, the treatment of a liquid coolant in the cooling lubricant circuit of a metal processing plant includes. Such lubricating fluids are commonly used in industrial and commercial plants that process metals by a substance engagement, such as by turning, milling or drilling. Particularly advantageous is the use when the cooling lubricant liquid is used as a water-oil emulsion in a cooling lubricant system. The cooling lubricant remains characterized, without the usual biocides, especially on formaldehyde-based, are necessary microbiologically stable. This results in lower health burdens on operating personnel and lower costs due to longer service life. By means of the method according to the invention, the delivery of antimicrobial metal components can be optimally adjusted according to the requirements.

A further preferred use is that the antimicrobial treatment of a liquid in a liquid-conducting system comprises the treatment of a liquid switching medium in the hydraulic circuit of an industrial plant. Also in hydraulic circuits it happens that biomass growth is a problem. This applies in particular to circuits with areas through which material is routinely introduced into the hydraulic medium, which is suitable as food for large quantities of microorganisms. This applies, for example, to systems which have contact with cellulosic materials. The same applies to materials with natural fibers such as cotton, linen, wool, etc. The method is therefore particularly advantageous where the industrial or commercial plant is designed as a paper production and / or processing plant or as a plant for the production and / or processing of textiles. As mentioned above, the need-based adjustment of the elution of oligodynamically active metal ions is also given here.

A further preferred use provides that the antimicrobial treatment of a liquid in a liquid-conducting system in a laundry washing plant comprises the treatment of retained wash rinse water. This makes it possible to store the retained Waschgut- rinse water in a reservoir, without running the risk that this water due to microbial activity in the long term unusable. this applies always especially when, for example, when rinsing the laundry substances are washed out, which represent a good food base for microorganisms. This is the case in particular when washing natural fiber textiles. With particular advantage is therefore provided that the treated wash rinse water will be used as wash water for a new beginning wash cycle of the car wash. The fact that, for example, in washing machines, the rinse water of the last rinse cycle for use as the first wash water is stored in a new wash, a further reduction of the water consumption of washing machines can be realized in a simple manner. This effect can be transferred to other washing systems and washing processes for different laundry items.

A further preferred use provides that the antimicrobial treatment of a liquid in a fluid-carrying system in a medical device comprises the treatment of germ-free working water. It is regularly necessary to ensure high requirements with regard to a permanent sterility of the water and a thus coming in contact with the pipeline system. This can be ensured in a simple and reliable manner by the use of a three-dimensional suture system with oligodynamic activity.

Further features and advantages of the invention will be explained in connection with the description of examples. However, the present invention is not limited to the examples explained below. example 1

150 ml of aqueous 1.25 g / l glucose solution was brought to a pH of 9 by addition of ammonia. 1 g of silver-coated textile of polyamide was placed in the glucose solution and treated for 1 hour at 60 ⁰ C, rinsed with water and dried.

1 g of textile thus obtained was placed in 100 ml of water and shaken for 72 hours. A measurement of the silver output of the textile into the water was made via Atomic absorption spectrometry. The measurement showed a release of 80 μg silver per liter of water.

Example 2

150 ml of aqueous 5 g / l glucose solution was brought to a pH of 9 by addition of ammonia. 1 g of silver-coated textile of polyamide was placed in the glucose solution and treated for 1 hour at 60 ⁰ C, rinsed with water and dried.

1 g of textile thus obtained was placed in 100 ml of water and shaken for 72 hours. The silver output of the textile into the water was measured by atomic absorption spectrometry. The measurement showed a release of 4 μg silver per liter of water.

Example 3

A jacketed with heating mats and heating jacket vessel (size: 1 m ³⁾ was completely lined with a besilberten treated with glucose solution 3D-spacer fabric of polyamide / polyester filled with water, heated to 45 ⁰ C and constant at the temperature of 45 ⁰ C held. The silver content of the water was determined quantitatively over a period of 47 days. The results are shown in Table 1.

Comparative example

A mantle-jacketed heating mantle (size: 1 m ³ ) was fully lined, filled with water, heated to 45 ^° C. and kept constant with a blackened 3D polyamide / polyester spacer knitted fabric which had not been subjected to the process according to the invention the temperature of 45 ⁰ C held. The silver content of the water was determined quantitatively over a period of 47 days. The results are shown in Table 1.

Table 1

Table 1: Dissolved silver in micrograms / liter of water

As can be seen from Table 1, the silver elution according to Example 3 is significantly lower than the silver elution according to the comparative example. The silver ion concentration according to Example 3 is in the range of 45 to 69 ug Ag / 1 water, while the silver ion concentration according to the comparative example increases continuously and at the conclusion of the experiment has a value of about 2,800 ug Ag / l water. Table 1 shows that treating solubilized 3D material with glucose solution allows limiting the release of silver ions in water. In the examples and comparative examples, the water was sampled according to DIN 38402 A 14. The measurements for silver determination were carried out with a Varian GTA 96 (Graphite Tube Atomizer) spectrometer according to DIN 38406 (E18) Part 18. The evaluation of the measurements was based on DIN ISO 8466-2.

Claims

claims

A process for the treatment of an at least partially metallised textile, characterized in that the textile is treated with at least one agent selected from the group consisting of reducing agent and complexing agent.

2. The method according to claim 1, characterized in that the reducing agent is selected from the group consisting of glucose, ascorbic acid, sodium dithionite, sodium borohydride, sodium thiosulfate, sodium sulfite, sodium formate, formaldehyde and sodium hydrophosphite.

3. The method according to claim 1 or 2, characterized in that the complexing agent is selected from the group consisting of ammonia, thiosulfate, thioisocyanate, ethylenediamine, triethanolamine, ethanolamine, 1, 3-diaminopropane, glycerol, sodium tartrate, sodium potassium tartrate and sodium citrate.

4. The method according to any one of the preceding claims, characterized in that the at least partially metallized textile is in the form of a thread system having thread material with an at least partially metallized yarn, wherein the thread material before the treatment of the textile alone or together with additional thread material to textile technology the thread system has been processed.

5. The method according to claim 4, characterized in that the textile-technical processing of the thread material comprises twisting, weaving, knitting or knitting.

6. The method according to any one of the preceding claims, characterized in that the textile contains polyamide, polyester, polyolefin or mixtures thereof and optionally one or more customary auxiliaries, processing or additives.

7. The method according to any one of the preceding claims, characterized in that the at least partially metallized textile is an at least partially coated with an oligodynamically active metal textile.

8. textile, obtained according to one of the methods according to claims 1 to 7.

9. A textile according to claim 8, characterized in that it is formed as a yarn, a thread, a fabric, a knitted fabric, a braid, a knitted fabric or a non-woven.

10. Use of a textile obtained by any of the methods according to claims 1 to 7, for the antimicrobial treatment of a liquid in a liquid-conducting system or for the production of stockings, insoles, clothing, upholstery for seating or mattresses.

11. Use according to claim 10, characterized in that the antimicrobial treatment of a liquid in a liquid-conducting system, the treatment of drinking water or industrial water in closed or open to the surrounding atmosphere, stagnant or circulatory systems in power plants, industrial plants, ballast -Water tanks in ships, swimming pools, whirlpools or in air conditioning includes.

12. Use according to claim 10, characterized in that the antimicrobial treatment of a liquid in a liquid-conducting system comprises the treatment of a liquid cooling lubricant in the cooling lubricant circuit of a metal processing plant.

13. Use according to claim 10, characterized in that the antimicrobial treatment of a liquid in a liquid-conducting system comprises the treatment of a liquid switching medium in the hydraulic circuit of an industrial plant.

H. Use according to claim 10, characterized in that the antimicrobial treatment of a liquid in a liquid-conducting system in a washing machine for a laundry comprises the treatment of retained laundry rinse water.

15. Use according to claim 10, characterized in that the antimicrobial treatment of a liquid in a fluid-carrying system in a medical device comprises the treatment germ-free working water.