DE102007003649A1 - Polyester-based molding material containing divalent copper, used for production of blends, powder, molded parts, film, fabric or fibres with an antimicrobial action, e.g. for medical products - Google Patents

Abstract

Polyester-based molding material containing 0.001-10 (preferably 0.05-10) wt.% copper(II). Copper-containing polyester-based moulding materials (MM), containing (i) 0.001-10 (preferably 0.05-10) wt.% copper(II), (ii) 0.001-99.999 (preferably 0.01-99.95) wt.% polyester(s) based on aromatic dicarboxylic acids and aliphatic or aromatic diols and/or (iii) 0-99.999 wt.% polyester(s) derived from (A) aliphatic or cycloaliphatic dicarboxylic acid(s) (or their ester-forming derivatives), (B) a diol component comprising 2-12C alkanediol(s) and/or 5-10C cycloalkanediol(s) and optionally (C) hydroxy-acid(s) of formula HO-(CO-G-O)p-H (Ia) or cyclo- -(CO-G-O)r- (Ib), in which p : 1-1500; r : 1-4; G : phenylene, -(CH2)q-, -CHR- or -CHR-CH2-; q : 1-5; R : methyl or ethyl and in which (ii) and (iii) together make up at least 0.001 wt.%, and (iv) 0-300 (preferably 0-80) wt.% normal auxiliary substances and additives (based on (i)-(iii)). Independent claims are included for (1) methods for the production of MM by mixing the components or by adding component (i) during the production of (ii) or (iii) (2) blends, micro-powder, molded parts, film or fibres containing MM, or products made from these (3) fibres obtained from MM, with a fineness of at least 0.5 dtex per single filament .

Description

The The present invention relates to a thermoplastic copper (II) containing Polyester molding compound, its preparation, its use in manufacture of blends, moldings, films, fibers, spunbonded fabrics, microparticles or as a coating and the products obtained therefrom Blends, micropowders, moldings, films or fibers or from this manufactured products.

State of the art

From the DE 601 02 291 T2 (= EP 1 272 037 B1 = WO 01/74166 = US 020040247653 A1 ) is an antimicrobial and antiviral polymer material formed from a single polymer component selected from the group consisting of, inter alia, a polyamide, a polyester, an acrylic or a polypropylene, wherein the material is in the form of a fiber or a yarn and a single antimicrobial and comprising an antiviral agent consisting essentially of microscopic water-insoluble particles of ionic copper oxides in powder form embedded directly into the component with some of the particles exposed and protruding from the surfaces in front of which particles release copper (II). Unlike the present invention sets this prior art product in that Cu (II) is not embedded in the compound, but protrudes from the surface, significantly larger amounts of Cu (II) free, so »50 mg / kg, as in the Products of the present invention is the case.

task

Of the present invention is based on the object, a copper (II) containing To provide molding compound of a special polyester, both as such but also in your processing products and the products obtained from it, is antimicrobial to act, d. H. d. H. the settlement and / or spread of microorganisms to prevent, in particular of (pathogenic) fungi, bacteria or Mould.

These The object is solved by the features of claim 1.

• i. 0,001 Gew.-% bis 10 Gew.-%, vorzugsweise 0,05 Gew.-% bis 10 Gew.-%, bezogen auf das Gesamtgewicht der Komponenten i) bis iii) Kupfer(II),
• ii. 0,001 Gew.-% bis 99,999 Gew.-%, vorzugsweise 0,01 Gew.-% bis 99,95 Gew.-%, mindestens einem Polyesters auf Basis von aromatischen Dicarbonsäuren und einer aliphatischen oder aromatischen Dihydroxyverbindung und/oder
• iii. 0 Gew.-% bis 99,999 Gew.-%, mindestens eines Polyesters aufgebaut aus A) einer aliphatischen oder mindestens einer cycloaliphatischen Dicarbonsäure oder deren esterbildende Derivate oder Mischungen davon, B) einer Diolkomponente aus mindestens einem C₂-bis C₁₂-Alkandiol oder einem C₅- bis C₁₀-Cycloalkandiol oder Mischungen davon und ggf. C) mindestens einer Hydroxycarbonsäure der Formel Ia oder Ib.
  
  in der p eine ganze Zahl von 1 bis 1500 und r eine ganze Zahl von 1 bis 4 bedeuten, und G für einen Rest steht, der ausgewählt ist aus der Gruppe bestehend aus Phenylen, -(CH₂)q-, wobei q eine ganze Zahl von 1 bis 5 bedeutet, -C(R)H- und -C(R)HCH₂, wobei R für Methyl oder Ethyl steht und wobei ii und iii zusammen mind. 0,001 ausmachen,
• iv. darüber hinaus 0 Gew.-% bis 300 Gew.-%, vorzugsweise 0 Gew.-% bis 80 Gew.-%, bezogen auf das Gewicht von Komponente i bis iii) üblicher Hilfs- und Zusatzstoffe.

The present invention thus initially relates to a copper-containing molding composition of polyester containing

• i. 0.001% by weight to 10% by weight, preferably 0.05% by weight to 10% by weight, based on the total weight of components i) to iii) copper (II),
• ii. 0.001 wt .-% to 99.999 wt .-%, preferably 0.01 wt .-% to 99.95 wt .-%, of at least one polyester based on aromatic dicarboxylic acids and an aliphatic or aromatic dihydroxy compound and / or
• iii. 0 wt .-% to 99.999 wt .-%, at least one polyester composed of A) an aliphatic or at least one cycloaliphatic dicarboxylic acid or its ester-forming derivatives or mixtures thereof, B) a diol component of at least one C _{2 to} C ₁₂ alkanediol or a C ₅ - to C ₁₀ -cycloalkanediol or mixtures thereof and, if appropriate, C) at least one hydroxycarboxylic acid of the formula Ia or Ib.
  
  in which p is an integer from 1 to 1500 and r is an integer from 1 to 4, and G is a radical selected from the group consisting of phenylene, - (CH ₂ ) q-, where q is an integer Number from 1 to 5 means -C (R) H- and -C (R) HCH ₂ , where R is methyl or ethyl and in which ii and iii together make up at least 0.001,
• iv. beyond 0 wt .-% to 300 wt .-%, preferably 0 wt .-% to 80 wt .-%, based on the weight of component i to iii) of conventional auxiliaries and additives.

Component i)

As component i) copper (II) = a copper (II) compound with a particle size of 0.1 nm to 200 μm, preferably 1 nm to 100 μm, in particular from 0.1 μm to 50 μm, in which copper (II) is bonded covalently or ionically. This is in the chemicals trade z. B. at Sigma-Aldrich Chemical GmbH, Steinheim or Alfa Aesar GmbH & Co KG, Karlsruhe available or can be generated on site in a conventional manner by grinding coarser copper (II) connection qualities. For the purposes of the present invention, copper (II) compound is understood as meaning a copper (II) compound having a purity of 97 to 99%, a corresponding fine chemical having purities of about 99 to 99.999%. This compound should be stable at the application temperatures for the preparation of the compounds between 150 and 300 ° C and preferably be inert to the other components. Examples of copper (II) compounds are cupric oxide, cupric hydroxide, cupric fluoride, cupric chloride, cupric bromide, cupric nitride, copper (II) sulfate. Very particular preference is given to the use of copper (II) oxide.

Component ii)

When Component ii) of the molding compound are known per se polyester Base of aromatic dicarboxylic acids and aliphatic or aromatic dihydroxy compounds.

A first group of preferred polyesters ii) are polyalkylene terephthalates, in particular with 2 to 10 carbon atoms in the alcohol part.

Such polyalkylene terephthalates are known per se and described in the literature. They contain an aromatic ring in the main chain derived from the aromatic dicarboxylic acid. The aromatic ring may also be substituted, for. As by halogen such as chlorine and bromine or by C ₁ -C ₄ alkyl groups such as methyl, ethyl, i- or n-propyl and n-, i- or t-butyl groups.

These Polyalkylene terephthalates can be prepared by reaction of aromatic Dicarboxylic acids, their esters or other ester-forming Derivatives with aliphatic dihydroxy compounds in a conventional manner getting produced.

When preferred dicarboxylic acids are 2,6-naphthalenedicarboxylic acid, Terephthalic acid and isophthalic acid or their To name mixtures. Up to 20 mol%, preferably not more than 10 mol% of the aromatic dicarboxylic acids can by aliphatic or cycloaliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, Dodecanedioic and cyclohexanedicarboxylic acids replaced become.

From the aliphatic dihydroxy compounds are diols having 2 to 6 Carbon atoms, in particular 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and neopentyl glycol or mixtures thereof.

When particularly preferred polyesters ii) are polyalkylene terephthalates, which are derived from alkanediols having 2 to 6 carbon atoms, to name. Of these, mainly polyethylene terephthalate, polypropylene terephthalate and polybutylene terephthalate or mixtures thereof, in particular Polybutylene terephthalate, preferred. Further preferred are PET and / or PBT, which also up to 1 wt .-% 1,6-hexanediol and / or 2-methyl-1,5-pentanediol may contain as further monomer units.

The Viscosity number of suitable as component ii) polyester is generally in the range of 50 to 220 ml / g, preferably from 80 to 160 ml / g (measured in a 0.5% by weight solution in a phenol / o-dichlorobenzene mixture (weight ratio 1: 1 at 25 ° C) according to EN ISO 1628-1.

Farther are as component ii) of the invention Molding compounds PET Re-cycled (also called scrap-PET), if necessary in mixture with polyalkylene terephthalates such as PBT.

• 1) sog. Post Industrial Rezyklat: hierbei handelt es sich um Produktionsabfälle bei der Polykondensation oder bei der Verarbeitung z. B. Angüsse bei der Spritzgussverarbeitung, Anfahrware bei der Spritzgussverarbeitung oder Extrusion oder Randabschnitte von extrudierten Platten oder Folien.
• 2) Post Consumer Rezyklat: hierbei handelt es sich um Kunststoffartikel, die nach der Nutzung durch den Endverbraucher gesammelt und aufbereitet werden. Der mengenmäßig bei weitem dominierende Artikel sind blasgeformte PET Flaschen für Mineralwasser, Softdrinks und Säfte.

Recyclates are generally understood as:

• 1) so-called Post Industrial Recyclate: this is production waste in the polycondensation or processing z. B. Sprues in the injection molding, Anfahrware in the injection molding or extrusion or edge portions of extruded sheets or films.
• 2) Post Consumer Recyclate: These are plastic items that are collected and processed after use by the end user. By far the dominating items in terms of volume are blow-molded PET bottles for mineral water, soft drinks and juices.

Both types of recycled material can be present either as regrind or in the form of granules. In the latter case, the slag cyclates are melted after separation and purification in an extruder and granulated. This usually facilitates the handling, the flowability and the metering for further processing steps.

Either granulated as well as regrind present recyclates can be used, the maximum edge length 6 mm, should preferably be less than 5 mm.

by virtue of the hydrolytic cleavage of polyesters during processing (by traces of moisture) it is advisable to pre-dry the recyclate. The residual moisture content after drying is preferably <0.2%, in particular <0.05%.

When another group of compounds suitable as component ii) to name fully aromatic polyesters that are different from aromatic ones Derive dicarboxylic acids and aromatic dihydroxy compounds.

When aromatic dicarboxylic acids are already in use the polyalkylene terephthalates described compounds. Prefers are used for fully aromatic polyester blends of 5 to 100 mol% isophthalic acid and 0 to 95 mol% terephthalic acid, in particular mixtures of about 80% terephthalic acid with 20% isophthalic acid to about equivalent mixtures used of these two acids.

in der Z eine Alkylen- oder Cycloalkylengruppe mit bis zu 8 C-Atomen, eine Arylengruppe mit bis zu 12 C-Atomen, eine Carbonylgruppe, eine Sulfonylgruppe, ein Sauerstoff- oder Schwefelatom oder eine chemische Bindung darstellt und in der m' den Wert 0 bis 2 hat. Die Verbindungen können an den Phenylengruppen auch C₁-C₆-Alkyl- oder Alkoxygruppen und Fluor, Chlor oder Brom als Substituenten tragen.The aromatic dihydroxy compounds preferably have the general formula (II)

in which Z represents an alkylene or cycloalkylene group having up to 8 C atoms, an arylene group having up to 12 C atoms, a carbonyl group, a sulfonyl group, an oxygen or sulfur atom or a chemical bond and in the m 'is the value 0 until 2 has. The compounds may also carry C ₁ -C ₆ -alkyl or alkoxy groups and fluorine, chlorine or bromine as substituents on the phenylene groups.

When The parent of these compounds are, for example, dihydroxydiphenyl, Di (hydroxyphenyl) alkane, di (hydroxyphenyl) cycloalkane, di (hydroxyphenyl) sulfide, Di (hydroxyphenyl) ether, di (hydroxyphenyl) ketone, di- (hydroxyphenyl) sulfoxide, a, a'-di (hydroxyphenyl) dialkylbenzene, di (hydroxyphenyl) sulfone, Di- (hydroxybenzoyl) benzene, resorcinol and hydroquinone and their N-alkylated or ring-halogenated derivatives mentioned.

From these are 4,4'-dihydroxydiphenyl, 2,4-di- (4'-hydroxyphenyl) -2-methylbutane a, a'-di- (4-hydroxyphenyl) -p-diisopropylbenzene, 2,2-di (3'-methyl-4'-hydroxyphenyl) propane and 2,2-di- (3'-chloro-4'-hydroxyphenyl) propane, and especially 2,2-di (4'-hydroxyphenyl) propane, 2,2-di (3 ', 5-dichlorodihydroxyphenyl) propane, 1,1-di- (4'-hydroxyphenyl) cyclohexane, 3,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenylsulfone and 2,2-di (3 ', 5'-dimethyl-4'-hydroxyphenyl) propane or mixtures thereof are preferred.

Of course As component ii) it is also possible to use mixtures of polyalkylene terephthalates and wholly aromatic polyesters. These generally include 20 to 98% by weight of the polyalkylene terephthalate and 2 to 80% by weight of wholly aromatic polyester.

Of course, it is also possible to use polyester block copolymers, such as copolyether esters, as component ii). Such products are known per se and in the literature, for. B. in the US Pat. No. 3,651,014 , described. Also in the trade corresponding products are available, for. Hytrel ^® (DuPont).

worin Q eine Einfachbindung, eine C₁- bis C₈-Alkylen-, eine C₂- bis C₃-Alkyliden-, eine C₃-bis C₆-Cycloalkylidengruppe, eine C₆- bis C₁₂-Arylengruppe sowie -O-, -S- oder -SO₂- bedeutet und n' eine ganze Zahl von 0 bis 2 ist.As the polyester ii) should also be understood according to the invention polycarbonates. Suitable polycarbonates are, for example, those based on diphenols of the general formula (III)

in which Q denotes a single bond, a C ₁ -C ₈ -alkylene, a C ₂ -C ₃ -alkylidene, a C ₃ -C ₆ -cycloalkylidene group, a C ₆ -C ₁₂ -arylene group and -O- , -S- or -SO ₂ - and n 'is an integer from 0 to 2.

The diphenols may also have substituents on the phenylene radicals, such as C ₁ - to C ₆ -alkyl or C ₁ - to C ₆ -alkoxy.

preferred Diphenols of the abovementioned formula III are, for example, hydroquinone, Resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) -propane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,1-bis (4-hydroxyphenyl) cyclohexane. Particularly preferred are 2,2-bis (4-hydroxyphenyl) propane and 1,1-bis (4-hydroxyphenyl) cyclohexane, and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane.

Either Homopolycarbonates as well as copolycarbonates are used as component ii) suitable, are preferred in addition to the bisphenol A homopolymer Copolycarbonates of bisphenol A.

The suitable polycarbonates can be branched in a known manner be, preferably by the incorporation of 0.05 to 2.0 mol%, based on the sum of the diphenols used, at least trifunctional Compounds, for example those with three or more than three phenolic OH groups.

When Particularly suitable polycarbonates have proven to be the relative Viscosities [eta] rel, from 1.10 to 1.50, in particular from 1.25 to 1.40. This corresponds to average molecular weights Mw (weight average) from 10,000 to 200,000, preferably from 20,000 to 80,000 g / mol.

The Diphenols of the general formula III are known per se or according to produced by known methods.

The polycarbonates can be prepared, for example, by reacting the diphenols with phosgene by the phase boundary process or with phosgene by the homogeneous phase process (the so-called pyridine process), the molecular weight to be set in each case being achieved in a known manner by a corresponding amount of known chain terminators. (For polydiorganosiloxane-containing polycarbonates, see for example DE-OS 33 34 782 ).

Suitable chain terminators are, for example, phenol, pt-butylphenol but also long-chain alkylphenols such as 4- (1,3-tetramethyl-butyl) -phenol, according to DE-OS 28 42 005 or monoalkylphenols or dialkylphenols having a total of 8 to 20 carbon atoms in the alkyl substituents according to DE-A 35 06 472 such as p-nonylphenyl, 3,5-di-t-butylphenol, pt-outylphenol, p-dodecylphenol, 2- (3,5-dimethyl-heptyl) -phenol and 4- (3,5-dimethylheptyl) -phenol.

As further suitable components ii) may be mentioned amorphous polyester carbonates, wherein phosgene was replaced by aromatic dicarboxylic acid units such as isophthalic acid and / or terephthalic acid units in the preparation. For more details at this point on the EP-A 711 810 directed.

Further suitable copolycarbonates with cycloalkyl radicals as monomer units are in EP-A 365 916 described.

Furthermore, bisphenol A can be replaced by bisphenol TMC. Such polycarbonates are available under the trademark APEC ^HAT® from Bayer AG.

Prefers it is, as component ii, a modified polyethylene terephthalate It is from the Invista Resins and Fibers GmbH, Gersthofen under the designation PET RT 20 or as GL6105 from KUAG Elana GmbH, Heinsberg.

Component iii)

The According to the invention suitable aliphatic dicarboxylic acids A in component iii generally has 2 to 10 carbon atoms, preferably 4 to 6 carbon atoms. You can both be linear as well as branched. In the context of the present invention usable cycloaliphatic dicarboxylic acids are in usually those with 7 to 10 carbon atoms and in particular those with 8 carbon atoms. In principle, however, can also dicarboxylic acids with a larger Number of carbon atoms, for example up to 30 carbon atoms, be used.

Examples which may be mentioned are malonic acid, succinic acid, glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, fumaric acid, 2,2-dimethylglutaric acid, suberic acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1 , 3-cyclohexanedicarboxylic acid, diglycolic acid, itaconic acid, maleic acid and 2,5-norbornane dicarboxylic acid, among which adipic acid is preferred.

Suitable ester-forming derivatives of the abovementioned aliphatic or cycloaliphatic dicarboxylic acids which are likewise usable are in particular the di-C ₁ - to C ₆ -alkyl esters, such as dimethyl, diethyl, di-n-propyl, di-isopropyl To mention di-n-butyl, di-iso-butyl, di-t-butyl, di-n-pentyl, di-iso-pentyl or di-n-hexyl ester. Anhydrides of dicarboxylic acids can also be used.

there may be the dicarboxylic acids or their ester-forming Derivatives used singly or as a mixture of two or more thereof become.

Examples of the aliphatic polyesters contemplated are aliphatic copolyesters as described in U.S. Pat WO 94/14870 in particular aliphatic copolyesters of succinic acid, its diesters or mixtures thereof with other aliphatic acids.

The star such as glutaric acid and butanediol or mixtures of this Diol with ethylene glycol, propanediol or hexanediol or mixtures thereof.

aliphatic Polyesters of this type generally had molecular weights Mn in the range of 1000 to 100000 g / mol.

As well For example, the aliphatic polyesters may be random or block copolyesters be containing other monomers. The proportion of other monomers is usually up to 10 wt .-%. Preferred comonomers are hydroxycarboxylic acids or lactones or mixtures thereof.

Of course may also be mixtures of two or more comonomers and / or other building blocks, such as epoxides or polyfunctional aliphatic or aromatic acids or polyfunctional alcohols be used for the preparation of aliphatic polyesters.

in the In general, diols B of component iii are branched or linear alkanediols having 2 to 12 carbon atoms, preferred 4 to 6 carbon atoms, or cycloalkanediols having 5 to 10 carbon atoms selected.

Examples suitable alkanediols are ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,5-pentanediol, 2,4-dimethyl-2-ethylhexane-1,3-diol, 2,2-dimethyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol, 2,2,4-trimethyl-1,6-hexanediol, in particular ethylene glycol, 1,3-propanediol, 1,4-butanediol and 2,2-dimethyl-1,3-propanediol (neopentyl glycol); Cyclopentanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol or 2,2,4,4-tetramethyl-1,3-cyclobutanediol. It is also possible to use mixtures of different alkanediols be used.

Dependent whether an excess of acid or OH end groups is desired, either the component A or the Component B are used in excess. After a preferred embodiment, the molar ratio of the components A to B used in the range from 0.4: 1 to 1.5: 1, preferably in the range of 0.6: 1 to 1.1: 1.

In a preferred embodiment, in addition and in component iii), the hydroxycarboxylic acid C used is a glycolic acid, D-, L-, D, L-lactic acid, 6-hydroxyhexanoic acid, whose cyclic derivatives such as glycolide (1,4-dioxane-2,5-dicarboxylic acid). dione), D-, L-dilactide (3,6-dimethyl-1,4-dioxane-2,5-dione), p-hydroxybenzoic acid as well as their oligomers and polymers such as 3-polyhydroxybutyric acid, polyhydroxyvaleric acid, polylactide (for example, as EcoPLA ^® (Fa. Cargill)), or a mixture of 3-polyhydroxybutyric acid and polyhydroxyvaleric acid (the latter is available) under the name Biopol ^® by Zeneca, particularly preferably for the preparation of partially aromatic polyester low molecular weight and cyclic derivatives thereof.

The Hydroxycarboxylic acids C can be used, for example, in Quantities of 0.01 to 50, preferably from 0.1 to 40 wt .-% based to be used on the amount of A and B.

The copper-containing molding compositions according to the invention usually comprise from to wt .-%, preferably from to, wt .-%, particularly preferably from to wt .-% component i) and from to wt .-%, preferably from to wt .-%, especially preferably from to wt .-% component ii) and iii), wherein the weight percent in each case based on the total weight of components i) to iii).

Component iv)

The Polyester molding compositions according to the invention can Auxiliaries and additives iv) which are obtained during the polymerization process in any stage or subsequently, for example, in a melt of the polyester, or together with the incorporation of component i), ii) and iii) can incorporate. exemplary are dispersants, stabilizers, neutralizing agents, Lubricants and release agents, antiblocking agents, dyes or fillers called. For masterbatch production is preferred Polybutylene terephthalate used.

Based on the components i) to iii) can be added from 0 to 300 wt .-%, preferably up to 80 wt .-% additives. Suitable additives are, for example, dispersants, fillers, stabilizers or lubricants and mold release agents. Such additives are for. In Ullmann's Encyclopedia of Industrial Chemistry, Volume 15, 4th ed. 1978, pp. 253-271 and Franck, Kunststoffkompendium, 6th ed. Würzburg 2006, p. 154f described.

Examples of dispersion auxiliaries are liquid or paste-like substances at room temperature, which facilitate the dispersion of the copper particles in a polyester by lowering the interfacial tension between the two components, thus causing wetting. These are known in the art and z. B. from Berndt Schwegmann GmbH & Co KG, County Gelsdorf, under the brand Schwego ^® z. B. Schwego ^® Wett 8080, a modified polyurethane, or Byk Chemie GmbH, Wesel, sold under the product name Disperplast, z. B Disperplast 1150 is a polar acid ester of long-chain alcohols. The proportion of dispersants is generally 0.5 wt .-% to 10 wt .-%, based on the total weight of the inventive molding composition, in particular 1 wt .-% to 5 wt .-%.

Examples for fillers are particulate substances such as calcium carbonate, clay minerals, calcium sulfate, barium sulfate, Titanium dioxide, soot, lignin powder, iron oxide, also as coloring Components can act as well as fiber materials, eg. Cellulose fibers, sisal and hemp fibers. The proportion of fillers is usually not more than 40 wt .-%, based on the total weight of the molding composition according to the invention of polyester, in particular not more than 20% by weight.

stabilizers are z. As tocopherol (vitamin E), organic phosphorus compounds, Mono-, di- and polyphenols, hydroquinones, diarylamines, thioethers, Melamine or urea. As antiblocking agents come z. Talc, Chalk, mica or silicon oxides into consideration. Lubricant and mold release agent are usually substances based on hydrocarbons, Fatty alcohols, higher carboxylic acids, metal salts higher carboxylic acids such as calcium or zinc stearate, Fatty acid amides such as erucic acid amide and wax types, z. Paraffin waxes, beeswax, montan waxes and the like. Preferred release agents are erucic acid amide and / or wax types and more preferably combinations of these two types of release agents. Preferred wax types are beeswaxes and ester waxes, in particular Glycerol. Particularly preferred are those for the production used the molding compositions according to the invention Polyester i) with 0.05 to 2.0 wt .-% erucic acid or 0.1 to 2.0 wt .-% wax types, each based on the plastic content the molding compounds, equipped. Very particularly preferred are for the preparation of the molding compositions of the invention used polyester iii) with 0.05 to 0.5 wt .-% erucic acid amide and 0.1 to 1.0% by weight of wax types, in particular glycerol monostearate, each based on the plastic content of the molding compositions equipped.

manufacturing

The used according to the invention as component i) Copper powder can by various methods in the / the polyester ii), iii). For example, the Polyester ii) with one or more of the monomer components for Preparation of the polyesters iii), z. As the dicarboxylic acids and / or diols already mixed in the preparation of component iii) become. According to another procedure, the polyester ii) the melt of the reacted polyester iii) are incorporated. The addition of component i) to the polyester can be in any of the aforementioned Process steps take place, including in the production of the polyester even.

The component ii) can be introduced by known methods and with the aid of known mixing devices in the previously prepared polyester iii), wherein also component i is introduced at the same time (see, for example Ullmanns Encyclopadie der technischen Chemie, Volume 15, 4th ed. 1978, pp. 282-288 ,). Thus, component ii) before, at the same time and following component i), for example by means of a screw machine, z. As an extruder, either in pure form or as a so-called "masterbatch", in component iii) are mixed. This occurs at the melting temperatures of the polyesters used below the decomposition temperature, ie in the case of aromatic polyesters in the range from 250 ° C. to 300 ° C.

in the In general, these masterbatches are special ones Molding compounds in which the required additives or additives, for example, component iv), in a matrix of, for example thermoplastic polymer, for example component ii) or iii), embedded, but the additive content compared to conventional additized molding compositions significantly higher, for example in the range of 10 to 70% by weight. By adding appropriate Amounts of a masterbatch to a non-additive, for example Thermoplastics can then molding compounds with conventional Be prepared additive contents.

use

The thermoplastic molding compositions according to the invention are especially for the production of blends, moldings, foils, micropowder and products made thereof, or fibers and spunbonded nonwovens and products made therefrom.

Fibers and fiber products

The Fiber made of the copper-containing molding material made of polyester is preferably a staple fiber, and preferably about 2.5 cm to about 10 cm long, most preferably 3.5 cm to 5 cm long. Preferred thickness is from 0.6 dtex to 6/67 dtex, more preferably 1.0 dtex, 1.3 dtex, 1.67 dtex, 3.33 dtex and 6.67 dtex, most preferably 1.3 dtex and 1.67 dtex, but also any other fiber thickness be used.

alternative is made of the copper-containing molding composition of polyester Fiber is an endless fiber (filament). Preferred thickness is from 0.6 dtex-6.67 dtex, more preferably 1.0 dtex, 1.3 dtex, 1.67 dtex, 3.33 dtex and 6.67 dtex, most preferably 1.3 dtex and 1.67 dtex, but any other fiber thickness can be used become.

The Copper-containing polyester molding compound can be found in one of these be produced yarn. It is particularly preferred that it made from the molding composition of the invention Fiber in the form of staple fibers (fiber cut) or filaments (Continuous fiber) contains. It contains depending on the application area and required material properties different amounts of the Fiber material according to the invention, preferably at least 1 wt .-%, particularly preferably from 1 wt .-% to 99 wt .-%, most preferably from about 10% to about 60% by weight, and most especially preferably from about 25% to about 50% by weight. The yarn is in the Spinning process produced by twisting the individual fibers.

All copper-containing materials of the invention and the products made therefrom are preferably washable So an antimicrobial effect, which also after one or more times Washing is available. It is particularly preferred that this wash resistance over the entire life of the materials or of the product exists.

One Inventive nonwoven can either directly from a copper-containing polyester compound by spunbonding or by any known method of nonwoven production from the invention Fiber can be produced. The proportion of the invention Fibers on the total amount of fibers in the fleece or felt is of the requirements depending on the material. He is usually from about 1 to 100% by weight, preferably from 1 to 99% by weight, especially preferably from about 10% to about 60% by weight, most especially preferably from about 25% to about 50% by weight. The fleece production by mechanical (needling or hydroentanglement), chemical (addition of binders) or thermal (thermobonding) Solidification of fiber webs. Felt does not become the fleece counted; however, in the context of the present application also felts from the term "fleece" or "nonwovens" be recorded.

The from the copper-containing shaped body according to the invention produced materials and products have the ability to Kill microorganisms. This killing comes This is due to the fact that the cell wall of the microorganism on contact collapsed with the material of the invention and as a result the organism dies.

The material according to the invention has an excellent killing effect on pathogenic bacteria, yeasts and fungi, z. B. pyrogenic cocci (streptococci such as Streptococcus pyrogenes, Streptococcus pneumoniae, and β-hemolytic Streptococcus, Staphylococcus aureus, Meningococcus, Neisseria gonorrhoea and the like), Enterobaeteriaceae (such as Escherichia coli, Schmitz's Bacillus, Salmonella typhi, Salmonella paratyphi, Salmonella typhimurium Salmonella enterica, Salmonella enteritidis, Salmonella choleraesuis, Morgan's Bacillus, Bacillus pneumonia, Pseudomonas aeruginasa and the like), pathogenic Fungi (such as Candida albicans, Cryptococcus neoformans, Trichophyton rubrum, Trichophyton rosaceum, Microsporum gypseum, filamentous fungi and the like), etc. In particular, the material acts microbicidally Brevibacterium, MRSA, S. aureus, T. rubrum and other athlete's foot (such as T. mentagrophytes), C. albicans, E. coli, Citrobacter koseri, S. epidermisis and S. enterica. Furthermore, because of the high Bactericidal or fungicidal also a bacteriostatic and fungistatic effect on such germs, which are less strong respond to the material, included. Also for products, which the material of the invention in proportions contained below 1 wt .-%, is an at least bacteri or fungistatic effect expected.

The Material has an antimicrobial effect (preventing "multiplication") to "killing to 99.9%"), especially bactericidal (Killing of 99.9% of bacteria within 6 hours (DIN standard) or killing 99.9% of the bacteria within 24 Hours (American standard), but also fungicidal, bacteriostatic and fungistatic.

The antimicrobial molding material or its derivatives is or will incorporated in the products or with the surface of the Products, or the products are or are wholly made of the antimicrobial material. The particles become in semi-solid and liquid materials such as engineering gels, Foams, creams or materials for treating surfaces (Paint, wall paint, adhesive, etc.), and in composite materials such as foams, Leather composite, cellulose composite, glass fiber composite, etc. blended become. Further, the materials can also be made into solid materials as PU foams, rubber, plastics are incorporated. The incorporation of the fiber according to the invention in Textiles are done in a preferred aspect by conventional Process for the production of textiles such as spinning, processing a fiber containing chamois or nonwoven fabric. In other Products can use the fiber in the same way as for the microparticles be incorporated described.

The Products contain or consist of fleece, felt, fabric, knitted fabric, Knitwear, foam, plastic, rubber, foil, paints, varnishes, Glue and / or paper. Particularly preferred products are textile products. The use of the material according to the invention can but not just in textiles. Also a use in non-textile Such as ceramics, plastic, flexible polyurethane foams, rubber, Paints, lacquer, polyshield, building coatings, latex, Glue and glue, creams, gels and powders, composite materials and Binder materials is possible.

One preferred aspect is the use of the invention Materials in plastic products. These plastics can processed into moldings, semi-finished products, fibers or films be, in particular to packaging of polymer films, technical Parts, building materials, hygiene articles, chemical gloves etc.

Except the material of the invention can in the products up to 99%, preferably up to 90%, more preferably up to 75% other materials may be present. In a very special preferred aspect, however, the products consist of the invention Material.

Splits one the fields of application for the products and uses there are two major preferred applications: Household goods and medical products (including Products for use in medical practices and clinics, such as protective clothing, Surgical products, personal care products, bedding, interior design and means of transport). These include products for the purpose cleaning, drying, filtering, storage and protection of objects and persons.

• a) medizinische Anwendungen für textile Gewebe. Gestricke. Gewirke. Vliese und Filze: Arbeitskleidung für Krankenhaus und Pflegeeinrichtungen, Patientenkleidung für Krankenhaus, Krankenhausbesucherkleidung, Abdecktücher und OP-Auflagen, Krankenhausbettwäsche, Krankenhausmatratzenbezüge, Bezüge für Liegen, Sitze, Matten im Krankenhaus Verbandmaterial und Wundauflagen OP-Mundschutzmasken Sperr- und Saugvliese wie Windeln und Inkontinenzunterlagen Stilleinlagen und Slipeinlagen
• b) Haushaltanwendungen für Textilstoffe wie Gewebe, Gewirke und Gestricke, Vliese und Filze: Möbelstoffe, Dekostoffe, Tischdecken, Schlafdecken Putz- und Wischtücher, Handtücher, Kosmetiktücher, Handtücher und Bettwäsche, Matratzenauflagen, Matratzenbezüge und Möbelbezugsstoffe sowie Bezüge für Matten aller Art (Sport-, Tierhygienematten) Teppiche aller Art sowie Fußmatten, Textiltapeten, Gardinen Behältnisse aller Art wie Müll- und Staubsaugerbeutel, Lebensmittelverpackungen Hygieneauskleidungen aller Art im Haushalt
• c) Bekleidung aus Textilstoffen (gewebt, gewirkt, qestrickt), Vlies, Filz: Bekleidung aller Art einschließlich Unterwäsche, Strümpfe Schuheinlagen sowie Schuhfutter und Heimfutter Einwegtextilien aller Art
• d) Reinraumanwendungen für Textilstoffe (gewebt, gewirkt, qestrickt), Vlies, Filz: Filtervliese, -filze aller Art für Abluftanlagen und Klimaanlagen sowie Staubsauger Boden-, Wand-, Deckenverkleidungen aller Art Arbeitskleidung aller Art Heimtextilien wie Gardinen und Möbelbezugsstoffe
• e) Anwendungen im Gartenbau: Abdeckvliese zur Verwendung beim Anbau von Pflanzen und Gemüse.

The use of the fiber according to the invention is preferably carried out in textiles, in particular in semi-finished and finished semi-finished products including yarns, woven fabrics, knitted fabrics, knitted fabrics, nonwovens, felts and textile finished goods, including clothing. For the fibers and textiles according to the invention, the following fields of application are preferred:

• a) medical applications for textile fabrics. Knits. Knitted fabric. Nonwovens and felts: Hospital and nursing work clothing, hospital patient clothing, hospital attendants clothing, drapes and surgical drapes, hospital bed linen, hospital mattress covers, bed covers, seats, hospital mats Dressing material and wound dressings Surgical masks Surgical masks and diapers, such as diapers and incontinence pads Breast pads and panty liners
• b) household applications for textile fabrics such as woven, knitted or crocheted fabrics, nonwovens and felts: upholstery fabrics, decorative fabrics, tablecloths, quilts, cleaning and wiping cloths, towels, facial tissues, towels and bed linen, mattress toppers, mattress covers and upholstery fabrics, and covers for mats of all kinds (sportswear) , Animal hygiene mats) Carpets of all kinds and floor mats, textile wallpaper, curtains Containers of all kinds such as garbage and vacuum cleaner bags, food packaging Hygiene linings of all kinds in the household
• c) clothing of textile materials (woven, knitted, knitted), non-woven, felt: clothing of all kinds, including underwear, stockings, shoe insoles, shoe linings and linings, disposable linens of all kinds
• d) Clean room applications for textile fabrics (woven, knitted, qestrickt), fleece, felt: Filter fleece, felts of all kinds for exhaust air systems and air conditioners and vacuum cleaners Floor, wall, ceiling coverings of all kinds Workwear of all kinds Home textiles such as curtains and upholstery fabrics
• e) Applications in horticulture: Covering fleeces for use in growing plants and vegetables.

The Fields of application for the invention Fleece are very diverse and contain geotextiles, Filters (for liquid and gas filtration), medical Textiles (such as disposable surgical clothing, wound plasters, incontinence Diapers), clothing (steep), shoe (part) s, cleaning cloths, Flooring, home textiles and building materials.

Also PUR foams which are the inventive Containing material possess an excellent antimicrobial Activity and can be used in hospital and hygienic applications be used, in particular as a mattress or hygiene mat. Further Applications are the automotive sector and Cleaning sponges.

The by far preferred use of the invention Materials is the use in textiles, especially in medical Textiles and textiles, such as surgical clothing, protective masks, blankets, Barrier and absorbent non-woven fabrics, surgical tablecloths, but also in other body-close textiles, where one microbial action is desired, such as underwear, Bed linen and mattress.

preferred Fields of application of the nonwovens according to the invention are Protective clothing and protective masks as well as filters and containers (eg for vacuum cleaners). This is especially true for Nonwovens produced by the hot pressing process were. Needle nonwovens, on the other hand, are mainly used in textiles especially in filter fleece, mattresses and clothing.

textiles including yarns can basically like any other textiles processed, processed or through additional equipment steps / equipment be refined. Such additional equipment steps / equipment means include textile finishing, which is especially common in washed Textiles is advantageous, the sizing and application of Sizing aids, the pretreatment of textiles (eg by Activators, stabilizers and peroxide killers for peroxide bleaching, Extractants, complexing agents, wetting agents and detergents, reducing bleach, Pretreatment agents for printing wool, etc.), optical brighteners, Dyeing auxiliaries (stripping and brightening agents, antireducing agents, Dispersants and protective colloids, leveling agents, adjuvants against wrinkling, padding aids, complexing and sequestering agents for the dyebath, aftertreatment agent, wetting agent, Oxidizing agents, pH regulators, reducing agents, foam suppressants, Wool protection agents etc.), equipment additives for Finishing (smoothing and softening agent, anti-fungal treatment, Antisetting treatment, binders and auxiliaries for pigmenting, Filling and stiffening agents, hydrophilizing agents, water repellents, Wetting agents, defoamers, crosslinkers, etc.), pigment printing and printing with fiber-based dyes, textile coating.

A special use in which both non-textile and textile products of the material according to the invention are used are so-called protection systems (protective systems). These are combinations of different antimicrobial products, their combined Application to prevent a spatial spread of pathogenic microorganisms.

Microparticles and microparticles

Splits one the fields of application for the products and uses there are two major preferred applications: Household goods and medical products (including Products for use in medical practices and clinics, such as protective clothing, Surgical products, personal care products, bedding, interior design and means of transport). These include products for the purpose cleaning, drying, filtering, storage and protection of objects and persons.

• a) medizinische Anwendungen in PUR-Weichschaumstoffen und Verbundschaum: Krankenhausmatratzen, Liegen, Sitze Matten im Krankenhaus, Wundauflagen sowie Schaumstoffauflagen zur Prophylaxe;
• b) medizinische Anwendungen mit anderen Trägermaterialien aller Art: Wundauflagen, Verbandmaterial, Beschichtung medizinischer Geräte sowie Kunststoffe für Medizinprodukte, Einbringung in Cremes, Gele und Puder für medizinische Anwendungen, Einbringung in Implantatkunststoffe, Folien;
• c) Haushaltsanwendungen einschließlich Anwendungen im Krankenhaus- sowie Pflegebereich und Homecare: Einweg- oder Mehrweg-Putz- und -Wischtücher sowie Handtücher, Einweg- sowie Mehrwegbettwäsche und Matratzenauflagen, Matratzenbezüge und Möbelbezugsstoffe sowie Bezüge für Matten aller Art (Sport-, Tierhygienematten für Nutz- und Haustierhaltung), Teppichträgermaterialien aller Art sowie Fußmatten, Weichschaumtapeten, Behältnisse aller Art einschließlich Müll- und Staubsaugerbeutel, Lebensmittelverpackungen, Folien, Hygieneauskleidungen aller Art (Papier, Folien, Schäume, Vliese, Gewebe) in Haushalt, Krankenhaus und Pflege, und Einwegmaterialien für den Haushalt wie Filter, Folien, Putztücher, Wischtücher, Haushaltschwämme sowie Kosmetikschwämme;
• d) Bekleidung: Bekleidungstextilien aller Art einschließlich Strümpfen, Schuheinlagen sowie Schuhfutter, Schuhspanner und Heimfutter;
• e) Reinraumanwendungen: Abluftanlagen und Klimaanlagen sowie Staubsauger, Boden-, Wand-, Deckenverkleidungen aller Art; und
• f) Anwendungen im Rahmen von Protection-Systemen; zur Senkung von nosokomialen Infektionen im Krankenhaus, zur systemischen Dekubitus- und Fußpilz-Prophylaxe, zur systemischen Behandlung von Neurodermitikern und bei Massentierhaltung.

In detail, the following fields of application for the microparticles open up:

• a) medical applications in flexible polyurethane foams and composite foam: hospital mattresses, couches, seats mats in hospital, wound dressings and foam pads for prophylaxis;
• b) medical applications with other substrates of all types: wound dressings, dressings, medical device coatings and plastics for medical devices, incorporation in creams, gels and powders for medical applications, incorporation into implant plastics, films;
• (c) Household applications including hospital, nursing and homecare applications: Disposable and reusable cleaning and wiping cloths and towels, disposable and reusable bed linen and mattress toppers, mattress covers and upholstery fabrics and covers for all types of mattresses (sports, animal hygiene mats for use) and pet care), all types of carpet carrier materials, as well as floor mats, soft foam wallpapers, containers of all kinds, including garbage and vacuum bags, food packaging, films, sanitary linings of all kinds (paper, foils, foams, nonwovens, tissues) in household, hospital and nursing, and disposable materials for use Household such as filters, films, cleaning cloths, wipes, household sponges and cosmetic sponges;
• d) Clothing: Clothing textiles of all kinds, including stockings, shoe inserts and shoe linings, shoe trees and home food;
• e) Clean room applications: exhaust air systems and air conditioning systems as well as vacuum cleaners, floor, wall and ceiling coverings of all kinds; and
• f) applications in the context of protection systems; for the reduction of nosocomial infections in the hospital, for systemic decubitus and athlete's foot prophylaxis, for the systemic treatment of atopic dermatitis and mass animal husbandry.

Prefers are the microparticles of the invention by Coating applied to the aforementioned products. The invention Microparticles are particularly suitable in the non-textile field for equipment of filters and containers of all kinds including vacuum cleaner bags, trash bags Etc.

Besides can the particles of the invention as constituents of dispersions, colloids, gels and sols and are used for the production of such products.

These it is at the particles of the invention to Nanoparticles, so is the use for the production of nanospheres and nanotubes ("nanotubes") possible.

Other uses

• 1) Krankenhaus und Altenheim: Durch räumlich/personelle Barrierezonen können mikrobielle Besiedelung, Kontamination, Infektionsherde und Übertragungsrisiken eingegrenzt werden, Infektionen und Reinfektionen werden unterbunden und Eradikationsprozesse abgekürzt. Dies verkürzt unter anderem die Isolierphase bei MRSA-Patienten (infiziert mit Antibiotikamultiresistenten S. aureus), senkt nosokomiale Infektionen und senkt das Risiko unkontrollierter Ausbreitung von Pathogenen. Zentrum ist der Patient und sein Bett mit folgenden Produkten: Patientenkleidung (z. B. Hemd, Pantoffel, Handschuhe, Serviette, Mundschutz), Hygieneartikel: (z. B. Inkontinenzprodukte, Handtücher, Waschlappen), Bettartikel (Einweg-Bettwäsche, Textil-Bettwäsche, Matratzen, Matratzenauflagen). Das Bett wird umschlossen von antimikrobiell ausgerüsteten Oberflächen im Raum (Fußboden, Wände, Klimaanlage, Mobiliar, Gardinen, Putztücher). Ergänzend zu der räumlichen antimikrobiellen Ausrüstung wirkt Schutzkleidung für andere Personen neben dem Patienten, insbesondere Personal- und Besucherkleidung, OP-Bekleidung, Masken, Abdecktücher, Schuhe, Kopfschutz und Putztücher.
• 2) häusliche Pflege: Vermeiden unnötiger oder zusätzlicher Infektionsrisiken durch Bettwaren, auch Matratzen und Leibwäsche, Inkontinenzartikel, Schutzauflagen und hautstabilisierende Hautpflege, welche das erfindungsgemäße Material enthalten.
• 3) Haus und Bau: Schwerpunkt mikrobieller Belastungen im Haus ist der Pilz Aspergillus niger. An potentiellen Feuchtstellen und in schlecht belüfteten oder Klimaanlagen belüfteten Räumen finden Pilze hervorragende Lebensbedingungen. Neben den optischen Unannehmlichkeiten haben die Sporen der Schimmelpilze ein hohes allergenes und krank machendes Potential. Für eine vorsorgliche Anti-Schimmelpilz-Ausrüstung in unterschiedlichen Grundmaterialien (einschließlich Fugenmaterial, Tapeten, Beton, Wand- und Deckenfarben, Teppichböden) eignen sich die Mikropartikel.
• 4) Nutztierhaltung: Bakterien in Rindern, Schweinen und Geflügel sind meinst gegen mindestens ein Antibiotikum resistent. Die mikrobielle Belastung in Ställen ist hoch, Oberflächen, welche das erfindungsgemäße Material enthalten, können durch ihre permanente Wirksamkeit das Keimniveau senken und dadurch Übertragung verhindern.
• 5) Gastgewerbe: Hotels sind traditionell Infektionsherde; die mikrobielle Belastung in Hotelbetten muss als sehr hoch bezeichnet werden. Materialien, die mit dem erfindungsgemäßen Material ausgerüstet wurden und daher eine permanent dekontaminierende Eigenschaft haben, ermöglichen eine dauerhafte, wartungsfreie, antimikrobielle Wirkung für das gesamte Bett mit Matratzen, Auflagen und Bettwäsche.
• 6) Personenbeförderung: Überall wo sich Menschen bewegen, hinterlassen sie durch Ausatmen, Berührung und Ablagerungen von ihrer Bekleidung mikrobielle Spuren. Durch Dauerdekontaminierung mit Hilfe des erfindungsgemäßen Materials werden Griff- und Sitzflächen in öffentlichen Verkehrsmitteln ohne zusätzliche Hygienemaßnahmen ihres gefährlichen Potentials beraubt. Entsprechend ausgerüstete Lüftungs- und Klimaanlagen ermöglichen eine Abtötung luftgetragener Bakterien und Pilze.
• 7) Dekubitus: Ein Druckgeschwür ist die Folge einer Nekrose der Haut und der darunter liegenden Gewebe aufgrund anhaltender Druckbelastung. Die im Stuhl und Urin befindlichen Bakterien wirken permanent auf die Haut ein. Hautschäden sind die Folge. Die Feuchtigkeit aus Urin lässt die obere Hautschicht aufquellen. Bakterien und Pilze nisten sich ein und vermehren sich. Infektionen durch pathogene Bakterien und Pilze verursachen zusätzliche Belastungen (Windeldermatitis) und reduzieren die Widerstandskraft der Haut. Ein erfindungsgemäßes Schutzsystem setzt sich zusammen aus (a) einem antimikrobiellen Liege-Entlastungssystem aus Technogel, Schäumen und anderen Materialien, (b) antimikrobiellen Inkontinenzartikeln, (c) Hautpflege, und (d) Spezial-Bett- und Leibwäsche.
• 8) Windeldermatitis: entsteht durch das Zusammenwirken dreier Faktoren: gestaute Feuchtigkeit (Aufweichen der Haut), Bakterien und Pilze (Infektionen) und okklusives Milieu (Wärmestau). Feuchte Haut begünstigt die Windeldermatitis, denn sie begünstigt die Vermehrung von Bakterien und Pilzen aus Stuhl und Urin. Wird Urin zersetzt, entsteht Ammoniak, das Hautmilieu wird alkalisch. Der Säureschutzmantel bricht zusammen. Dann finden der Hefepilz Candida albicans oder andere Erreger, wie Staphylokokken und Streptokokken, ideale Voraussetzungen vor und die Haut reagiert mit Entzündungen. Durch die erfindungsgemäße antimikrobielle Ausrüstung von Baby- und Erwachsenen-Windeln wird das Keimniveau gesenkt und Infektionen vermieden. Der Einsatz bei akuter Windeldermatitis lässt Infektionen, Rötungen und Schmerzen abklingen. Diese Aussagen wurden in einem Heilversuch bei Dermatest^® bestätigt.
• 9) Tinea pedis (Fußpilz), Fußgeruch und diabetisches Fußsyndrom (DFS): In Schuhen finden Bakterien und Pilze hervorragende Lebensbedingungen. 90% aller Sportler, 60% der Allgemeinbevölkerung haben Fußpilz. Trotz sehr wirkungsstarker Antimykotika konnte dieser Anstieg der Infektionsrate nicht aufgehalten werden. Grund ist das Fehlen sicherer Prophylaxemaßnahmen, die das Infektions- und das Reinfektionspotential bannen könnten. Durch Verwendung des erfindungsgemäßen Materials kann ein Fußumfeld geschaffen werden, in dem die Tendenz zu Neu-Infektionen oder Re-Infektionen minimiert wird. Geeignete Fertigprodukte enthaltend das Material sind: Schuhe, Arbeitsschuhe, Sportschuhe, Badeschuhe, Hausschuhe, Einwegschlappen, Socken, Füßlinge, Waschhandschuhe, Abtrockentücher, Einlegesohlen, Schuhspanner, Zehenstöpsel, und Hautpflegecremes.
• 10) Wundversorgung: Wunden entwickeln meist Infektionstendenzen durch Keime. Mit dem erfindungemäßen Material ausgerüstete Wundauflagen ermöglichen eine permanente Keimreduzierung. Von besonderer Bedeutung ist dabei die Wirksamkeit gegen MRSA und andere pathogene Bakterien, die für lokale Wundinfektionen und nosokomiale Infektionen verantwortlich sind.
• 11) Neurodermitis: Bei Neurodermitis entwickeln sich meist auf der Haut Superinfektionen mit Staphylokokken. Diese können durch Einsatz des erfindungsgemäßen Materials in Kleidung und in Zubereitungen zum Auftragen auf die Hautvermieden werden.
• 12) Infektionskrankheiten einschließlich Vogelgrippe und SARS: SARS und viele weitere Infektionskrankheiten werden durch Einatmen von kontaminierter Luft und Aerosolen verursacht, Vogelgrippe und weitere Infektionskrankheiten durch engen Kontakt mit infizierten Tieren und wahrscheinlich auch durch engen Kontakt mit infizierten Menschen. Schutzbekleidung und Mundschutze mit dem erfindungsgemäßen Material stellen eine Möglichkeit dar, Infektionsketten zu unterbrechen.
• 13) Intiminfektionen: Durch Oberflächen mit dem erfindungsgemäßen Material werden Geruchsentwicklung und Infektionsrisiken minimiert.

The products are preferably used in the following application areas:

• 1) Hospital and nursing home: By means of spatial / personal barrier zones, microbial colonization, contamination, sources of infection and transmission risks can be limited, infections and reinfections are prevented and eradication processes are shortened. Among other things, this shortens the isolation phase in MRSA patients (infected with antibiotic resistant S. aureus), reduces nosocomial infections and reduces the risk of uncontrolled spread of pathogens. The center is the patient and his bed with the following products: patient clothing (eg shirt, slipper, gloves, napkin, mouth mask), hygiene articles: (eg incontinence products, towels, washcloths), bedding (disposable bed linen, textile Bed linen, mattresses, mattress pads). The bed is enclosed by antimicrobial surfaces in the room (floor, walls, air conditioning, furniture, curtains, cleaning cloths). In addition to the spatial antimicrobial equipment, protective clothing for other people next to the patient especially personnel and visitor clothing, surgical clothing, masks, drapes, shoes, head protection and cleaning cloths.
• 2) home care: avoid unnecessary or additional risks of infection through bedding, mattresses and underwear, incontinence products, protective pads and skin-stabilizing skin care containing the material of the invention.
• 3) House and construction: The focus of microbial burdens in the house is the fungus Aspergillus niger. Mushrooms find excellent living conditions in potential damp locations and in rooms that are poorly ventilated or air-conditioned. In addition to the optical inconvenience, the spores of the molds have a high allergenic and ill-making potential. For a precautionary anti-mold in different basic materials (including joint material, wallpaper, concrete, wall and ceiling colors, carpets) are the microparticles.
• 4) livestock: Bacteria in cattle, pigs and poultry are most resistant to at least one antibiotic. The microbial load in stables is high, surfaces containing the material according to the invention can lower the germ level by their permanent effectiveness and thereby prevent transmission.
• 5) Hospitality: hotels are traditionally foci of infection; The microbial load in hotel beds must be described as very high. Materials that have been equipped with the material of the present invention and therefore have a permanent decontaminating property, provide a durable, maintenance-free, antimicrobial effect for the entire bed with mattresses, pads and bedding.
• 6) Passenger Transportation: Everywhere where people move, they leave microbial traces by exhaling, touching and depositing their clothing. By Dauerdekontaminierung using the material according to the invention grip and seats are deprived of public transport without additional hygiene measures of their dangerous potential. Appropriately equipped ventilation and air conditioning systems allow the killing of airborne bacteria and fungi.
• 7) Pressure Ulcer: Pressure ulcer is the result of necrosis of the skin and underlying tissues due to sustained pressure. The bacteria in the stool and urine permanently affect the skin. Skin damage is the result. The moisture from urine causes the upper skin layer to swell. Bacteria and fungi nest and multiply. Infections caused by pathogenic bacteria and fungi cause additional stress (diaper dermatitis) and reduce the resistance of the skin. A protection system according to the invention is composed of (a) an antimicrobial bedding relief system of technogel, foams and other materials, (b) antimicrobial incontinence articles, (c) skin care, and (d) special bed and underwear.
• 8) Diaper dermatitis: caused by the interaction of three factors: dammed up moisture (softening of the skin), bacteria and fungi (infections) and occlusive environment (heat accumulation). Moist skin favors diaper dermatitis because it promotes the proliferation of bacteria and fungi from stool and urine. If urine is decomposed, ammonia is formed, the skin's environment becomes alkaline. The acid mantle breaks down. Then the yeast Candida albicans or other pathogens, such as staphylococci and streptococci, find ideal conditions and the skin reacts with inflammation. The antimicrobial finish of baby and adult diapers according to the invention reduces the germ level and avoids infections. Use in acute diaper dermatitis subsides infections, redness and pain. These statements were confirmed in a healing trial with Dermatest ^® .
• 9) Tinea pedis (foot fungus), foot odor and diabetic foot syndrome (DFS): In shoes bacteria and fungi find excellent living conditions. 90% of all athletes, 60% of the general population have athlete's foot. Despite very potent antimycotics, this increase in the infection rate could not be stopped. The reason is the lack of safe prophylactic measures that could ban the infection and the reinfection potential. By using the material of the present invention, a foot environment can be created in which the tendency for new infections or re-infections is minimized. Suitable finished products containing the material include: shoes, work shoes, sports shoes, bathing shoes, slippers, disposable slippers, socks, booties, wash mitts, tea towels, insoles, shoe trees, toe caps, and skin care creams.
• 10) Wound care: Wounds usually develop infection tendencies by germs. Dressings equipped with the material according to the invention enable a permanent reduction of germs. Of particular importance is the activity against MRSA and other pathogenic bacteria, which are responsible for local wound infections and nosocomial infections.
• 11) Atopic dermatitis: In eczema, superinfections with staphylococci usually develop on the skin. These can be avoided by using the material according to the invention in clothing and in preparations for application to the skin.
• 12) Infectious diseases including bird flu and SARS: SARS and many other infectious diseases are caused by inhalation of contaminated air and aerosols, bird flu and other infectious diseases due to close contact with infected animals and probably also through narrow ones Contact with infected people. Protective clothing and mouthguards with the material according to the invention represent a possibility of interrupting chains of infection.
• 13) Intiminfections: Odors and risks of infection are minimized by surfaces with the material according to the invention.

The Material according to the invention can be used both in disposable products as well as in multiply used products. This especially applies to the use in textiles, the material So can be used in disposable or reusable textiles.

A further preferred use of the invention Material is its use in disposable household articles. This includes filters (for exhaust hoods, vacuum cleaners, taps, Water filter), containers (such as garbage and vacuum bags, Brotzeitittüten), disposable textiles (such as wipes), Slides, etc.

Use in biologically active compositions

In pharmaceutical, veterinary or cosmetic Compositions is the composition for topical application suitable. The topical application closes the application of other active ingredients in the same composition. The Application can be achieved by applying a textile as described above, in particular a non-woven or cloth containing the inventive Material, or by applying a pharmaceutical preparation such as a cream, gel or solution (e.g., tonic for rubbing in). Also, the application of a powder or Powder containing the material according to the invention in particle form is one aspect. In particular, the composition in non-solid preparation, a cream, a gel, a powder, a Colloid or a foam, in solid form a dressing material, a wound dressing, a mask, a stocking or underwear.

The Composition contains in addition to the invention Material optionally one or more other active ingredients (eg. B. for the treatment of inflammation or improvement the skin structure) as well as for the respective application form usual pharmaceutical, cosmetic or veterinary carrier materials and additives.

The Selection and composition of the appropriate form of administration and the applied dose depends on the planned application and the severity of microbial infestation.

The Composition can in addition to the invention Material still other antimicrobial or other active substances contain. A preferred aspect is that the composition no further antimicrobial agents in addition to the invention Contains material.

The Compositions are for the treatment and prevention of all Species of microbial infestation suitable, especially for therapy and Prevention of infestation of skin (including the scalp) and hair, especially for the treatment of infections, Tinea capitis (fungal diseases of the scalp), tinea pedis, acne, Diaper rash eczema, erysipelas, mycoses, or infected infection-prone wounds, especially open contaminated wounds Wounds, intertrigo ("soreness"), abrasions and burns, chronic wounds and open areas, microbially populated areas of skin, especially MRSA-populated skin areas.

The material according to the invention can in a preferred Aspect also for the treatment of itching, cuts and minor Wounds and for treatment or prevention and palliation be used by skin diseases in humans and animals. The middle is in this case preferably a solid, so a powder, Tissue or nonwoven (fleece / felt), which is the inventive Contains material. This powder can be applied directly to the skin (Wound) applied or on a suitable carrier material (i.e., a cloth or fabric, but also a topical one Application form such as a cream or a gel) are applied.

The Inventive material is suitable to perishable Products such as cosmetics, process aids, etc., to stabilize. In addition, it can be perishable to increase durability 15 foods are used by these foods in a container (foil, container, box or similar) are kept, which is the inventive Contains material.

Finally, the material is also suitable for preparing compositions containing inactivated bacteria. Such compositions are useful as pharmaceuticals, food additives or the like. The composition may or may not contain the material of the present invention contain, preferably it does not contain the material anymore.

The The present invention is described by embodiments in FIG Form of a preparation example, application examples and a comparative example explained in more detail

Comparative Example 1

The filaments were carried out on a high-temperature trial spinning machine from Fourné. This is a spinning machine known to those skilled in the art, as described, for. B. is described in Ullmann's Encyclopedia of Industrial Chemistry, Vol. 10, Fibers 3, General Production Technology p. 535 , The spinneret used was a multifilament nozzle with 12 holes and a hole diameter of 400 .mu.m, the take-off speed was between 150 and 1500 m / min. The stretching was carried out in a second stage on a room stretching device, the godet 2 was heated to 60 to 80 ° C and the actual stretching between this galette and the godet 3 over a heating rail at temperatures of 100-120 ° C was carried out. A polyester having a solution viscosity (IV) of 1.07 dl / g was dried to a residual moisture content of 0.004%, filled into a 5 liter hopper and placed on the spinning extruder. At a melt temperature of 290 ° C, the filaments were cooled by blowing and the yarn passed through a cold godet duo with a take-off speed of 1000 m / min and then wound up. The preparation used was a commercial product. The spinning pressure after 30 minutes spin time was 50 bar. The bobbins were after 24 hours storage in a normal climate on a room stretching device at 1000 m / min stretching speed and a preheating on Galette 2 of 80 ° C over a heated to 100 ° C heating rail with a stretch ratio of 1: 4.20 stretched. During this process, reel spools were run for 10 minutes.

The following textile test values were determined for the filaments: titers: 20.1 dtex fineness of tear: 60.3 cN / tex Elongation at break: 7.35%

Production Example 1: (Production of a Compounds of polyethylene terephthalate (PET) and 0.2% copper (II) oxide powder and 3 parts Disperplast 1148 from copper (II) powder

In a co-rotating twin-screw extruder (Rheomex PWT16 / 25p from Thermo Electron Corporation (Karlsruhe) GmbH) at a throughput of 1.5 kg / h and at one temperature in all 4 heating zones of 270 ° C 0.2 parts of a copper (II) oxide powder (Grain size: 3 microns) in a melt of 99.8 parts of a PET RT20 polyethylene terephthalate (Invista Resins and Fibers GmbH Gersthofen), the additional 0.006 Parts of Disperplast 1148 (Byk Chemie) contained at one screw revolution number from 80 rpm. introduced, extruded and granulated. In connection This was the compound in a convection dryer for 2 h at 130 ° C and then in a vacuum dryer at 0.5 mbar Dried at 130 ° C for 8 h.

The rheological properties were determined in a laboratory kneader (Rheomix 600p of Thermo Electron Corporation (Karlsruhe) GmbH), adding 50 g of the compound to the kneader, the kneading tests at 285 ° C with a residence time of 30 minutes. The evaluation by the sensors and the Uniformity of torque showed that no Reactions that led to an increase in melt viscosity and blockage of the melt systems of the spinning apparatus. A spinning temperature of 285 ° C is therefore possible.

Application examples:

Application example 1

One Sample according to Preparation Example 1 was used in the laboratory for chemical and physical tests on textiles, Leather and commodities of the company Hansecontrol in Hamburg according to the eluate method on the delivery of copper to ISO 105 E04, DIN EN ISO 17294-2, wherein the PET Cu (II) containing composition in fiber form at 40 ° C in acidic welding solution was extracted for 30 min, using as formulation for acidic sweat solution a saliva solution used in baby clothing. The dissolved metal components were determined by ICP-MS or OES at a tolerance of +/- 10%. A value of 8.6 mg / kg was measured, which was within the tolerance range from 0-50 mg / kg for such products according to Ökotex certification lies. It was a migration test. By the low Migration of copper can be concluded that the product too after 50 washes still has the same effectiveness.

Application example 2 (molding composition as fiber with antimicrobial effect)

The Investigation was carried out according to ASTM E 2149-1 (Dynamic shake flask test).

The Sample material was chopped and placed in an Erlenmeyer flask given with phosphate buffer. After adding the test germ were to taken at the indicated times aliquots and the germ count of the test germ. The testing approaches were shaking incubated (dynamic contact conditions).

In each case 0.5 g of filament were used in the test. There was no steam sterilization of the samples.
Contact temperature: 36 ° C
Incubation temperature: 36 ° C
Nutrient medium: Nutrient medium: CASO agar
Incubation: 2 days at 36 ° C Test germs: Escherichia coli DSM 10233 Staphylococcus aureus DSM 799

The following tables show the following:
The killing kinetics of E. coli during a contact time with the product of the invention over a period of up to 6 hours. It is found that the product found according to Preparation Example 1 shows marked antimicrobial effects against E. coli.

The Absterbekinetik of S. Aureus during a contact time with the product according to the invention over a period of up to 6 hours. It is found that the product obtained according to Preparation Example 1 shows pronounced antimicrobial effects against S. aureus. Use Example 2.1: (Action against E. coli) sample name comment Contact time [h] Result Ser. No. CFU / DUT log KbE / examinee Diff. log. T (x) -T (0) %-Reduction Rebac effect 1 KH2P04 buffer reference 0 1.60E + 07 7.20 0.0 0,000 - reference 1 2,10E + 07 7.32 0.1 -31.250 - reference 2 1,40E + 07 7.15 -0.1 12,500 - reference 6 1,70E + 07 7.23 0.0 -6.250 - 2 Production example (rebac-fiber 0.2% MT100, PBT) + Active substance 0 1,80E + 07 7.26 0.0 0,000 0.0 + Active substance 1 1,00E + 07 7.00 -0.3 44.444 -0.4 + Active substance 2 1,20E + 07 7.08 -0.2 33,333 -0.1 + Active substance 6 8,10E + 06 6.91 -0.3 55,000 -0.4 Application Example 2.2: (Effect on S. aureaus) sample name comment Contact time [h] Result Ser. No. CFU / test) ing log KbE / examinee Diff. log. T (x) -T (0) %-Reduction Rebac effect 1 KH2PO4 buffer reference 0 9.50E + 06 6.98 0.0 0,000 - reference 1 1,50E + 07 7.18 0.2 -57.895 - reference 2 1.60E + 07 7.20 0.2 -68.421 - reference 6 1,20E + 07 7.08 0.1 -26.316 - 2 Production example (rebac-fiber 0.2% MT100, PBT) + Active substance 0 4,60E + 06 6.66 0.0 0,000 0.0 + Active substance 1 5,60E + 06 6.75 0.1 -21.739 -0.1 + Active substance 2 5,90E + 06 6.77 0.1 -28.261 -0.1 + Active substance 6 4,30E + 04 4.63 -2.0 99.065 -2.1 bold numbers: <50 cps / examinee, ie there are <and> signs for the related calculations

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• - DE 60102291 T2 [0002]
• - EP 1272037 B1 [0002]
• WO 01/74166 [0002]
• - US 020040247653 A1 [0002]
• US 3651014A [0026]
• - DE 3334782 [0034]
• - DE 2842005 [0035]
• - DE 3506472 A [0035]
• - EP 711810 A [0036]
• - EP 365916A [0037]
• WO 94/14870 [0044]

Cited non-patent literature

• - Ullmanns Encyclopadie der technischen Chemie, Volume 15, 4th ed. 1978, pp. 253-271 and Franck, Kunststoffkompendium, 6th ed. Würzburg 2006, p. 154f [0056]
• - Ullmanns Encyclopadie der technischen Chemie, Volume 15, 4th ed. 1978, pp. 282-288 [0061]
• - Ullmann's Encyclopedia of Industrial Chemistry, Vol. 10, Fibers 3, General Production Technology p. 535 [0101]

Claims (16)

Copper (II) containing molding composition of polyester, containing i. 0.001% by weight to 10% by weight, preferably 0.05% by weight to 10% by weight, based on the total weight of components i) to iii) copper (II), ii. 0.001 wt .-% to 99.999 wt .-%, preferably 0.01 wt .-% to 99.95 wt .-% of at least one polyester based on aromatic dicarboxylic acids and an aliphatic or aromatic dihydroxy compound and / or iii. 0 wt .-% to 99.999 wt .-%, at least one polyester composed of A) an aliphatic or at least one cycloaliphatic dicarboxylic acid or its ester-forming derivatives or mixtures thereof, B) a diol component of at least one C _{2 to} C ₁₂ alkanediol or a C ₅ -C ₁₀ -cycloalkanediol or mixtures thereof and optionally C) at least one hydroxycarboxylic acid of the formula Ia or Ib

in which p is an integer from 1 to 1500 and r is an integer from 1 to 4, and G is a radical selected from the group consisting of phenylene, - (CH ₂ ) q-, where q is an integer Number of 1 to 5 means -C (R) H- and -C (R) HCH ₂ , wherein R is methyl or ethyl, and wherein ii and iii together make up at least 0.001. iv. beyond 0 wt .-% to 300 wt .-%, preferably 0 wt .-% to 80 wt .-%, based on the weight of components i) to iii), conventional auxiliaries and additives. Molding composition according to claim 1, characterized that component ii) at least one polyethylene terephthalate and / or polybutylene terephthalate. Molding composition of polyester, containing i. 0.1% by weight to 5 wt .-% based on the total weight of components i) to ii) copper (II), ii. 99.9 wt .-% to 95 wt .-% polyethylene terephthalate iii. 0 wt .-% to 10 wt .-%, based on component i), of a dispersant iv. beyond 0 wt .-% to 300 wt .-%, preferably 0 % By weight to 80% by weight, based on the weight of component i) to iii), common auxiliaries and additives. Process for the preparation of molding compositions according to Claims 1 to 3, characterized in that the components i) to iii) or i) to iv) are mixed. Process for the preparation of molding compositions according to Claims 1 to 3, characterized in that component i) is mixed in the preparation of component ii) or iii). Blends, micropowders, moldings, films or fibers or products made therefrom, obtainable from the Molding compositions according to claims 1 to Third Fiber obtainable according to claims 1 to 3, with a filament fineness of at least 0.5 dtex per single filament, preferably at least 0.5 dtex per single filament. Use of the molding compositions according to any of claims 1 to 3 for the preparation of blends, micropowder, Moldings, films, spunbonded nonwovens or fibers and articles made therefrom Products. 9 Use of the molding composition according to any of claims 1 to 3 or obtained via the method according to claims 4 or 5 for the reduction or preventing the colonization / spread of microorganisms, in particular of pathogenic fungi, bacteria and / or mold. Use of the molding composition according to any of claims 1 to 3 or obtained via the method according to claims 4 to 5 as a component of textile fabrics and non-textile products. Use of the composition according to claim 9 or 10 for the production of textile fabrics form, optionally in combination with other fibers. Use of the composition according to claim 11, as nonwovens, felt, woven, knitted or knitted fabrics. Use of the molding composition in the form of fibers or Micropowder as a constituent of dressings, preferably absorbent and padding materials, in particular absorbent aids in Form of suction diapers and incontinence pads or surgical Sutures and medical devices, preferably aids for collecting excretions. Use of the molding compound in the form of micropowder as a coating on / in a porous or non-porous Support material. Use of the molding compound in the form of micropowder as a component of dispersions, colloids, gels and sols. Use of the molding compound in the form of micropowder as equipment for disposable articles in bandages, Medical products, packaging in the form of containers, Paperboard based on paper and cardboard. Use according to claim 10, characterized that the non-textile products are selected from plastics, Foams, rubber, paints, lacquer, ceramics, latex, glue, glue.