WO2002057349A1

WO2002057349A1 - Amorphous, antimicrobial, transparent film consisting of a thermoplastic that can be crystallised, method for the production and use thereof

Info

Publication number: WO2002057349A1
Application number: PCT/EP2002/000085
Authority: WO
Inventors: Ursula Murschall; Ulrich Kern; Günther Crass
Original assignee: Mitsubishi Polyester Film Gmbh
Priority date: 2001-01-17
Filing date: 2002-01-08
Publication date: 2002-07-25

Abstract

The invention relates to an amorphous, antimicrobial, transparent film consisting of a thermoplastic that can be crystallised, whose thickness ranges between 30 and 1000 νm. Said film contains the thermoplastic as the main component and in addition 2,4,4'-trichloro-2'-hydroxy diphenyl ether ('triclosan') as the antimicrobial component, either on its own or as part of a mixture with other antimicrobial substances. The film is characterised by cost-effective thermoforming properties, excellent optical characteristics and by an antimicrobial action. It can also exhibit UV stability, resistance to discoloration, photo-oxidative stability and flame-retardant properties and is heat-sealable. The invention also relates to a method for producing said film and to the use thereof.

Description

Amorphous, antimicrobial, transparent film made of a crystallizable thermoplastic, process for its production and its use

The invention relates to an amorphous, antimicrobial, transparent film made of a crystallizable thermoplastic, the thickness of which ranges from 30 to

1000 μm. As the main constituent it contains the thermoplastic and additional antimicrobial component as 2,4,4 ^{'trichloro-2'-hydroκy-diphenyiether} ( "triclosan") alone or a mixture of triclosan and other antimicrobial substances. The film is characterized by economic thermoformability, very good optical properties and an antimicrobial effect and can also have UV stability, yellowing resistance, photooxidative stability, flame retardant finish and sealability. The invention further relates to a method for producing this film and its use.

Transparent films made of crystallizable thermoplastics with a thickness of 30 to

1000 μm are well known. These films have no antimicrobial effect. Furthermore, these films are not UV-stable, so that neither the films nor the articles made from them are suitable for outdoor use. In outdoor applications, these films show yellowing and deterioration of the mechanical properties after a short time due to photooxidative degradation by sunlight. The foils are also not flame retardant, which makes them unsuitable for areas where high flame retardancy is required. The foils are not sufficiently sealable.

WO99 / 31036 describes derivatives of halogenated diphenyl ether compounds which have antimicrobial properties in combination with improved migration behavior. The diphenyl ether derivatives described are thermally stable, show low volatility with a low tendency to migrate and are preferably suitable for the antimicrobial finishing of polymeric compounds, for example for the antimicrobial finishing of plastics, rubbers, paints and fibers. Despite all these properties, it has been found that the antimicrobial activity of the substituted compounds is reduced compared to the known compounds. Furthermore, a process for the preparation of the diphenyl ether derivatives is described, the starting material being the 2,4,4 'trichloro-2'-hydroxy-diphenyl ether (triclosan).

WO 99/42650 discloses the use of esterified triclosan for the production of antimicrobial finished textile fibers, the compounds used in the dispersed state e.g. diffuse into the fibers under dyeing conditions. As a textile substrate, i.a. also called polyester. Triclosan, the basic substance of the compounds used, is said to be unsuitable because of its easy solubility in water at high pH and its property of volatilizing at high temperatures. The volatilizing substance would also cause health problems.

DE-A 19823 991 discloses 0.1 to 20 mm thick amorphous, i.e. Non-crystalline, undrawn and unoriented plates are known which contain a bibenzene-modified polyalkylene terephthalate and / or a bibenzene-modified polyalkylene naphthalate as the main component. The plates are characterized by good mechanical properties in a wide temperature range. A note on transparencies that include have no antimicrobial properties.

DE-B 2346787 describes a flame-retardant raw material. In addition to the raw material, the use of the raw material for films and fibers is also claimed. The following deficits were found in the production of film with this claimed phospholane-modified raw material: The raw material is very sensitive to hydrolysis and must be predried very well. When drying the raw material with dryers which correspond to the prior art, the raw material sticks together, so that a film can only be produced under the most difficult conditions. The films produced under extreme, uneconomical conditions become brittle when exposed to temperature, ie the mechanical properties are lost the normal embrittlement, so that the film is unusable. This embrittlement occurs after 48 hours of thermal stress.

Amorphous, transparent films made of a crystallizable thermoplastic are also known. These films can have various functionalities such as sealability, flame retardant effect and UV stability. However, none of the known films has antimicrobial properties.

None of the references teach or point to a thermoplastic film containing triclosan, and furthermore that triclosan can be incorporated into a crystallizable thermoplastic, with all antimicrobial properties being retained during the processing and use phase.

The object of the present invention is to avoid the disadvantages of the prior art described.

The invention therefore relates to an amorphous, antimicrobially finished, transparent film with a thickness in the range from 30 to 1000 μm, which contains a crystallizable thermoplastic as the main component, which is characterized in that the film is additionally used as an antimicrobial component 2,4,4 ^' -

Contains trichloro-2'-hydroxy-diphenyl ether ("triclosan") alone or a mixture of triclosan and other antimicrobial substances. The invention further relates to a method for producing this film and its use.

In addition to economic thermoformability and good optical properties, the film according to the invention has above all an antimicrobial effect. Care must be taken that the triclosan. is incorporated into the crystallizable thermoplastics in a short time at sufficiently high temperatures, the effective antimicrobial concentration of the substance being retained and health risks being excluded. It is surprising that this incorporation is possible. Antimicrobial effect means that the growth of gram-positive and gram-negative bacteria as well as mold and yeast is greatly reduced. Gram-negative bacteria are, for example, escherichia coli, klebsiella pneumoniae, proteus vulga s or salmonella. Gram-positive bacteria are, for example, staphylococcus aureus, streptococcus faecalis, micrococcus luteus or corynebacterium minutissimum. Pure, defined microorganisms such as pseudomonas aeruginosa, staphylococcus aureus, escherichia coli, aspergillus niger, peniciliium funicolosum, chaetomium globosum, trichoderme viride or candida albicans are used as test organisms. Significantly reduced means that in the Hemmhof test, the antimicrobial film is at least not overgrown by the test culture and the growth around the film is also inhibited. The non-vegetated zone that forms around the film sample is called the inhibition zone.

Good optical properties include, for example, high light transmission, i.e. Transparency (> 64%), a high surface gloss (> 100), a low haze (<30%) and a low yellowness index (YID <10).

Thermoformability means that the film can be thermoformed or thermoformed on commercially available thermoforming machines without complex pre-drying to form complex and large-area shaped articles.

In addition, the film can have other functionalities. This includes UV stability, yellowing resistance, photooxidative stability, flame retardant finish and sealability, further that it is coated on one or both surfaces and / or is corona treated on one or both sides. Such a film can have one or more of the functional properties.

Furthermore, it is very surprising that the film according to the invention can also be recycled, ie the regrind can be used again without loss of the optical and mechanical properties, for example without adversely affecting the yellowness index of the film. The main component of the transparent film is a crystallizable thermoplastic. Suitable crystallizable or semi-crystalline thermoplastics are, for example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), bibenzol-modified polyethylene terephthalate (PETBB), bibenzene-modified polybutylene terephthalate (PBTBB), bibenzol-modified polyethylenenaphthalate, and mixtures of these with polyethylene, naphthalenate, and polyethylene-naphthalate (PEN), and polyethylene-naphthalate-modified (polyethylene-en-naphthalate) Polyethylene terephthalate are preferred.

In addition to the main monomers such as

Dimethyl terephthalate (DMT), ethylene glycol (EG), propylene glycol (PG), 1,4-butanediol, jerephthalic acid (TA), benzenedicarboxylic acid, 2,6-naphthalene dicarboxylate (NDC) and / or 2,6-naphthalene dicarboxylic acid (NDA), isophthalic acid (IPA), trans- and / or cis-1,4-cyclohexanedimethanol (c-CHDM, t-CHDM or c / t-CHDM) can also be used.

According to the invention, crystallizable thermoplastics are understood to be crystallizable homopolymers, crystallizable copolymers, crystallizable compounds, crystallizable recyclate and other variations of crystallizable thermoplastics.

Preferred starting materials for the production of the film are crystallizable thermoplastics, which have a crystallite melting point Tm, measured with DSC (differential

Scanning calorimetry) with a heating rate of 20 ° C / min, from 180 to over 365 ° C, preferably from 180 to 310 ° C, a crystallization temperature range Tc from 75 to 280 ° C, a glass transition temperature Tg from 65 to 130 ° C, a Density, measured according to DIN 53479, from 1.10 to 1.45 and a crystallinity of 5 to 65%, preferably 20 to 65%. For thermoformability, it is important that the crystallizable thermoplastic have a diethylene glycol content of ≥ 1.0% by weight, preferably> 1.2% by weight, in particular ≥1.3% by weight and / or a polyethylene glycol content of ≥1 .0% by weight, preferably ≥1.2% by weight, in particular ≥1.3% by weight and / or an isophthalic acid content of 3.0 to 10.0% by weight.

The antimicrobial substance according to the invention is 2,4,4'-trichloro-2-hydroxy-diphenyl ether (triclosan) alone or in a mixture with other antimicrobial substances such as 10,10'-oxy-bisphenoxarsine, N- (trihalomethylthio) phthalimide, Diphenylantimon-2-ethylhexanoate, copper 8-hydroxyquinoline, tributyltin oxide and its derivatives and derivatives of halogenated diphenyl ether compounds. The amount is generally 0.005 to 10.0% by weight, preferably 0.01 to 5.0% by weight, based on the weight of the crystallizable thermoplastic, the proportion of triclosan always predominating.

For the purposes of the present invention, amorphous film means films which, although the crystallizable thermoplastic has a crystallinity of 10 to 65%, preferably 20 to 65%, are not crystalline. Not crystalline, i.e. H. essentially amorphous, means that the degree of crystallinity is generally below 3%, preferably below 1%. Such a film is essentially in the unoriented state.

The film according to the invention can be either single-layer or multi-layer. It can also be coated with various copolyesters or adhesion promoters. For the purpose of economical production, it generally contains the antiblocking and lubricants that are customary for films.

The triclosan can be added to both the base layer and one or both outer layers. The extrusion process is suitable for this, preferably including the masterbatch process. If necessary, any intermediate layers that are present can also be antimicrobial. The triclosan is preferably metered in directly during film production using the so-called masterbatch technology, the concentration of the triciosan being in the range from 0.005 to 10.0% by weight, preferably from 0.01 to 5.0% by weight, based on the weight of the finished layer of the crystallizable thermoplastic is.

It is important with the masterbatch technology that the grain size and the bulk density of the masterbatch are similar to those of the thermoplastic, so that a homogeneous distribution and thus a homogeneous antimicrobial treatment can take place.

In masterbatch technology, the additives are first dispersed in a solid carrier material. The thermoplastic itself comes as a carrier material, e.g. polyethylene terephthalate or other polymers that are sufficiently compatible with the thermoplastic, in question. For the production of films, the masterbatch is mixed with the thermoplastic provided as the film raw material and treated together in an extruder, the components fusing together and thus being dissolved in the thermoplastic. In the production of the masterbatch in the present invention, the amount of antimicrobial active ingredient is generally 0.4 to 30.0% by weight, preferably 0.8 to 15.0% by weight, based on the thermoplastics used. When producing masterbatches, care must be taken that the volatility of the triclosan is taken into account by suitable measures.

In the multilayer embodiment, the film is made of at least one

Core layer and at least one top layer, a three-layer A-B-A or A-B-C structure is preferred in particular.

For this embodiment, it is essential that the thermoplastic of the core layer has a standard viscosity similar to that of the thermoplastic of the cover layers) which adjoins (adjoins) the core layer. In a particular embodiment, the cover layers can be made from a polyethylene terephthalate, from a bibenzene-modified polyethylene terephthalate polymer, from a bibenzene-modified and / or unmodified polyethylene naphthalate polymer or from a bibenzene-modified and / or unmodified polyethylene terephthalate-polyethylene naphthalate copolymer or

-Compound exist. In this embodiment, the thermoplastics of the cover layers also have similar standard viscosities as the thermoplastic of the core layer.

According to the invention, the film can be coated on at least one of its surfaces, so that the coating on the finished film has a thickness of

5 to 100 nm, preferably 20 to 70 nm, in particular 30 to 50 nm. The coating is preferably applied in-line, i.e. during the film production process, expediently after extrusion. Application by means of the "reverse gravure-roll coating" method is particularly preferred, in which the coatings can be applied extremely homogeneously in the layer thicknesses mentioned. The coatings are applied as a dilute solution, emulsion or dispersion, preferably in aqueous form, to at least one surface of the film and then the solvent is evaporated. They give the film surface an additional function, for example making the film sealable, printable, metallizable, sterilizable, antistatic or improve e.g. the aroma barrier or enable adhesion to materials that would otherwise not adhere to the film surface (e.g. photographic emulsions). Examples of substances / compositions which give additional functionality are: acrylates (WO 94/13476), ethyl vinyl alcohols, polyvinylidene dichloride,

Water glass (Na ₂ SiO ₄ ), hydrophilic polyesters such as 5-Na-sulfoisophthalic acid-containing PET / IPA polyester (EP-A 0 144878, US-A 4252885 or EP-A 0296620), vinyl acetates (WO 94/13481), polyvinyl acetates, polyurethanes , Alkali or alkaline earth metal salts of C ₁₀ -C ₁₈ fatty acids, butadiene copolymers with acrylonitrile or methyl methacrylate, methacrylic acid, acrylic acid or their esters. The substances / compositions that give the additional functionality can usual additives such as antiblocking agents, pH stabilizers in amounts in the range of 0.05 to 5.0 wt .-%, preferably from 0.1 to 3.0 wt .-%.

The film can also be corona-treated on at least one side and / or coated on at least one side with a scratch-resistant coating, with a copolyester or with an adhesion promoter and / or vapor-coated with ethylene-vinyl alcohol copolymer, ethyl-vinyl alcohol, polyvinyl alcohol or polyvinylidene dichloride.

Furthermore, the films can be coated with metals such as aluminum or ceramic materials such as SiO _x or Al _x O _y , preferably in an off-line process. This improves their gas barrier properties in particular.

The thermoforming process usually includes the steps of predrying, heating, molding, cooling, demolding, tempering. During the thermoforming process, it was found that the films according to the invention can surprisingly be thermoformed without prior predrying. This advantage compared to thermoformable polycarbonate or polymethyl methacrylate films, which require pre-drying times of 10 to 15 hours, depending on the thickness, at temperatures of 100 to 120 ° C, drastically reduces the costs of the forming process. In addition, it was very surprising that the detail reproduction of the molded body is excellent. The film can also be fed to the thermoforming process, for example as a roll.

It was more than surprising that the films according to the invention with a higher diethylene glycol content and / or polyethylene glycol content and / or I PA content compared to the standard thermoplastic can be thermoformed economically on commercially available thermoforming systems and provide excellent detail reproduction.

The following process parameters have generally proven to be suitable for the thermoforming process: Process step film according to the invention

Predrying is not necessary

Mold temperature 100 to 140 ° C

Heating time per 10 μm film thickness <5 sec per 10 μm film thickness film temperature during shaping 100 to 160 ° C

Possible stretch factor 1, 5 to 4.0

Excellent detail reproduction

Shrinkage (shrinkage) <1.5%

In a special embodiment, the film according to the invention can be provided with UV stability.

Light, especially the ultraviolet portion of solar radiation, i.e. H. the wavelength range from 280 to 400 nm induces degradation processes in thermoplastics, as a result of which not only the visual appearance is caused by entering

Color change or yellowing changes, but by which the mechanical-physical properties of the films made of thermoplastics are extremely negatively affected.

The prevention of these photooxidative degradation processes is of considerable technical and economic importance, since otherwise the application possibilities of numerous thermoplastics are drastically restricted.

Polyethylene terephthalates, for example, begin to absorb UV light below 360 nm, their absorption increases considerably below 320 nm and is very pronounced below 300 nm. The maximum absorption is in the range between 280 and 300 nm.

In the presence of oxygen, mainly chain cleavages are observed, but no cross-links. Carbon monoxide, carbon dioxide and carboxylic acids are the predominant quantities of photooxidation products Direct photolysis of the ester groups must still be considered oxidation reactions, which also result in the formation of carbon dioxide via peroxide radicals.

The photooxidation of polyethylene terephthalates can also lead to hydroperoxides and their decomposition products and to associated chain cleavages via hydrogen elimination in the a-position of the ester groups (H. Day, D. M. Wiles: J. Appl. Polym. Sei 16, 1972, page 203).

UV stabilizers (also called UV absorbers) as light stabilizers are chemical compounds that can intervene in the physical and chemical processes of light-induced degradation. Soot and other pigments can partially protect against light. However, these substances are unsuitable for films according to the invention, since they lead to discoloration or color change. Only organic and organometallic compounds are suitable for these foils, which give the thermoplastic to be stabilized no or only an extremely slight color or color change.

Suitable UV stabilizers as light stabilizers are compounds which absorb at least 70%, preferably 80%, particularly preferably 90%, of UV light in the wavelength range from 180 to 380 nm, preferably 280 to 360 nm. These are particularly suitable if they are thermally stable in the temperature range from 260 to 300 ° C, i.e. do not decompose and do not lead to outgassing. Suitable UV stabilizers as light stabilizers are, for example, 2-hydroxybenzophenones, 2-hydroxybenzotriazoles, organo-nickel

Compounds, salicylic acid esters, cinnamic acid ester derivatives, resorcinol monobenzates, oxalic acid anilides, hydroxybenzoic acid esters, sterically hindered amines and triazines, the 2-hydroxybenzotriazoles and the triazines being preferred. The film according to the invention contains at least one UV stabilizer as light stabilizer, the concentration of the UV stabilizer preferably in the range from 0.01 to 5.0% by weight, in particular in the range from 0.1 to 3.0%. -%, based on the weight of the layer of crystallizable thermoplastic.

In a very particularly preferred embodiment, the film contains 0.01 to 5.0% by weight of 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- (hexyl) oxyphenol of the formula

or 0.01 to 5.0% by weight of 2,2-methylene-bis (6- (2H-benzotriazol-2-yl) -4- (1, 1, 2,2-tetramethylpropyl) phenol of the formula

or 0.01 to 5.0% by weight of 2,2 '- (1,4-phenylene) bis [4H-3,1-benzoxazin-4-one] of the formula

It is completely surprising that the use of the above-mentioned UV stabilizers in films in combination with an antimicrobial finish leads to the desired result. If an attempt is made to achieve a certain UV stability via an antioxidant, the film quickly turns yellow after weathering.

If commercially available UV stabilizers are used which absorb the UV light and thus generally offer protection, it is found that

the UV stabilizer has a poor thermal stability and decomposes or outgasses at temperatures between 200 ° C and 240 ° C, large amounts (approx. 10 to 15% by weight) of the UV stabilizer have to be incorporated so that the UV light is absorbed and the film is not damaged.

At these high concentrations, the film shows strong color changes even after production. The mechanical properties are also adversely affected. Et al occur:

Nozzle deposits, which leads to profile fluctuations; Roller deposits from the UV stabilizer, which leads to impairment of the optical properties (poor cloudiness, adhesive defect, inhomogeneous surface); - Deposits in the production process. It was therefore more than surprising that excellent UV protection was achieved even at low concentrations of the UV stabilizer used according to the invention. It was very surprising that this excellent UV protection - the yellowness of the film compared to a non-stabilized film in the

Setting the measuring accuracy does not change, no outgassing, no nozzle deposits, which means that the

Foil exhibits excellent optics and has an excellent profile and flatness, - the UV-stabilized foil is characterized by excellent running reliability, so that it can be manufactured reliably. This means that the film is also economically viable.

A flame-retardant effect means that the film according to the invention in a so-called fire protection test meets the conditions according to DIN 4102 part 2 and in particular the conditions according to DIN 4102 part 1 and can be classified in building material class B 2 and in particular B1 of the flame retardant materials.

Furthermore, the possibly flame-retardant film should meet the UL

Test 94 "Horizontal Burning Test for Flammability of Plastic Material" passed, so that it can be classified in the class 94 VTM-0.

The film according to the invention can contain at least one flame retardant which is metered in directly during film production using the so-called masterbatch technology, the concentration of the flame retardant being in the range from 0.5 to 30.0% by weight, preferably 1.0 up to 20.0% by weight, based on the weight of the layer of the crystallizable thermoplastic. The concentration of the flame retardant in the masterbatch is generally in the range from 5.0 to 60.0% by weight. Typical flame retardants include bromine compounds, chlorinated paraffins and other chlorine compounds, antimony trioxide, aluminum hydroxide, the halogen compounds being disadvantageous on account of the halogen-containing by-products formed. Furthermore, the low light resistance of a film equipped with it, in addition to the development of hydrogen halides in the

Fire extremely disadvantageous.

Suitable flame retardants which are used according to the invention are, for example, organic phosphorus compounds such as carboxyphosphinic acids, their anhydrides and alkanephosphonic acid esters, preferably methanephosphonic acid esters. It is essential that the organic phosphorus compound is soluble in the thermoplastic, since otherwise the required optical properties will not be met.

Since the flame retardants generally have a certain sensitivity to hydrolysis, the additional use of a hydrolysis stabilizer can be expedient.

Phenolic stabilizers, alkali / alkaline earth stearates and / or alkali / alkaline earth carbonates are generally used as hydrolysis stabilizers in amounts of 0.01 to 1.0% by weight. Phenolic stabilizers are used in an amount of

0.05 to 0.6% by weight, in particular 0.15 to 0.3% by weight, and with a molar mass of more than 500 g / mol is preferred. Pentaerythrityl tetrakis-3- (3,5-di-te / τ.-butyl-4-hydroxyphenyl) propionate or 1,3,5-trimethyl-2,4,6-tris (3,5-di- te / t-butyl-4-hydroxybenzyl) benzene.

In this embodiment, the flame-retardant film according to the invention contains, as the main component, a crystallizable PET, 1.0 to 20.0% by weight of an organic phosphorus compound soluble in the thermoplastic as a flame retardant and 0.1 to 1.0% by weight of a hydrolysis stabilizer next to the antimicrobial substance. Bis- (5-ethyl-2-methyl-2-oxo-2λ ⁵ - [1,3,2] dioxaphosphinan-5-ylmethyl ester) methanephosphonic acid is preferred as the flame retardant.

This information regarding flame retardant and hydrolysis stabilizer also applies to other thermoplastics to be used according to the invention.

Surprisingly, fire protection tests according to DIN 4102 and the UL test have shown that in the case of a three-layer film, it is quite sufficient to equip the 0.5 to 2.0 mm thick top layers with flame retardants in order to achieve improved flame retardancy. If necessary and at high

Fire protection requirements can also include flame retardants in the core layer. H. include so-called basic equipment.

In addition, measurements showed that the film does not become brittle at a temperature of 60 ° C. over a longer period of time. This result is attributed to the synergistic effect of suitable pre-crystallization, predrying, masterbatch technology and hydrolysis stabilizer.

No embrittlement after thermal stress means that the film has no embrittlement and no disadvantageous mechanical properties after 100 hours of annealing at 60 ° C. in a forced air oven.

Surprisingly, films according to the invention in the thickness range 30-1000 μm meet the requirements of building material classes B2 and B1 according to DIN 4102 and UL Test 94.

Where a very good sealability is required and where this property cannot be achieved via an on-line coating, the film is in accordance with the

Invention constructed at least three layers and then in a particular embodiment comprises as layers the base layer B, the sealable cover layer A and the top layer C, which may or may not be sealable. In the embodiment in which the cover layer C is sealable, the cover layers A and C are identical.

Sealable top layer A

The sealable cover layer A applied to the base layer B by coextrusion is based on polyester copolymers and essentially consists of copolyesters which are composed predominantly of isophthalic acid and terephthalic acid units and of ethylene glycol units. The remaining monomer units come from other aliphatic, cycloaliphatic or aromatic diols or dicarboxylic acids, as can also occur in the base layer. The preferred copolyesters which provide the desired sealing properties are those which are composed of ethylene terephthalate and ethylene isophthalate units and of ethylene glycol units. The proportion of ethylene terephthalate is 40 to 95 mol% and the corresponding proportion of ethylene isophthalate is 60 to 5 mol%. Preferred are copolyesters in which the proportion of ethylene terephthalate is 50 to 90 mol% and the corresponding proportion of ethylene isophthalate is 50 to 10 mol%, and in particular copolyesters in which the proportion of ethylene terephthalate is 60 to 85 mol% and the corresponding proportion Ethylene isophthalate is 40 to 15 mol%.

Non-sealable uecKscnicnt u

In principle, the same polymers can be used for the other, non-sealable top layer C or for any intermediate layers present, as was described above for the base layer.

The desired sealing and processing properties of the

Films according to the invention are made from the combination of the properties of the copolyester used for the sealable top layer and the topographies the sealable cover layer A and the sealable or non-sealable cover layer C.

The seal start temperature of 130 ° C and the seal seam strength of at least 0.6 N / 15 mm is achieved if the copolymers described in more detail above are used for the sealable cover layer A. The best sealing properties of the film are obtained if no further additives, in particular no inorganic or organic fillers, are added to the copolymer. In this case, the lowest seal starting temperature and the highest seal seam strengths are obtained for a given copolyester. However, the handling of the film is poor in this case, since the surface of the sealable cover layer A tends to block. The film can hardly be wrapped and is not suitable for further processing on high-speed packaging machines. In order to improve the handling of the film and the processability, it is necessary to modify the sealable cover layer A.

This is best done with the aid of suitable antiblocking agents of a selected size, which are added to the sealing layer in a specific concentration in such a way that, on the one hand, blocking is minimized and, on the other hand, the sealing properties are only insignificantly deteriorated.

The film is furthermore suitable as a composite film, the composite consisting of the film according to the invention, optionally with an ethylene-vinyl alcohol copolymer, ethyl-vinyl alcohol, polyvinyl alcohol or polyvinylidene dichloride coating and a second film. This second film can e.g. can also be an antimicrobial thermoplastic film, a standard thermoplastic film or a polyolefin film.

The second film can have one or more layers and, like the first film, can be amorphous, ie non-oriented, and can have at least one sealing layer. The second film may be bonded to the first film with or without adhesive. The thickness of this second film is preferably in the range from 30 to 500 μm.

The composite film is generally obtained by laminating or laminating the two films to one another, with or without an intermediate adhesive layer, by passing them between rollers heated to 30 to 90 ° C.

However, it is also possible, for example, to apply the second, possibly transparent colored layer to the first, coated layer by in-line coating (melt extrusion onto an existing layer).

If adhesives are used, they are applied to a film surface by known methods, in particular by application from solutions or dispersions in water or organic solvents. The solutions usually have an adhesive concentration of 5.0 to 40.0% by weight in order to give an amount of adhesive on the film of 1.0 to 10.0 g / m ² .

Adhesives made from thermoplastic resins, such as cellulose esters and ethers, alkyl and acrylic esters, polyamides, polyurethanes or polyesters, or from thermosetting resins such as

Epoxy resins, urea / formaldehyde, phenyl / formaldehyde or melamine / formaldehyde resins, or consist of synthetic rubbers.

Suitable solvents for the adhesive are e.g. Hydrocarbons, such as ligroin and toluene, esters, such as ethyl acetate, or ketones, such as acetone and methyl ethyl ketone.

In another embodiment, the film according to the invention can also be colored transparently. For this purpose, the film can contain at least one dye which is soluble in the thermoplastic, the concentration of the soluble dye preferably being in the range from 0.01% by weight to 20.0% by weight, in particular in the range from Range from 0.05 to 10.0 wt .-%, based on the weight of the crystallizable thermoplastic.

Soluble dye is understood to mean substances that are molecularly dissolved in the polymer (DIN 55949).

The color change of the film is based on the wavelength-dependent absorption and / or scattering of the light. Dyes can only absorb light, but cannot scatter it, because a certain particle size is the physical prerequisite for scattering.

Coloring with dye is a solution process. As a result of this solution process, the dye is molecularly dissolved, for example, in the crystallizable thermoplastic. Such coloring is referred to as transparent, translucent, translucent or opal.

Of the various classes of soluble dyes, the fat and aromatic soluble dyes are particularly preferred. These are, for example, azo and anthraquinone dyes. They are particularly suitable e.g. for coloring PET, because the migration of the dye is restricted due to the high glass transition temperatures of PET. (Literature J. Koerner: Soluble dyes in the plastics industry in "VDI-Gesellschaft Kunststofftechnik:": Coloring plastics, VDI-Verlag, Düsseldorf 1975).

Suitable soluble dyes are, for example: C.I. Solvent Yellow 93 (a

Pyrazolone derivative), Cl solvent yellow 16 (a fat-soluble azo dye), fluorol green gold (a fluorescent polycyclic dye), CISolvent red 1 (an azo dye), azo dyes such as thermoplastic red BS, Sudan red BB, CISolvent red 138 (an anthraquinone derivative), fluorescent dyes such as fluoropyran GK and Fluorolorange GK, CI Solvent Blue 35 (an anthraquinone dye), Cl Solvent Blue 15: 1 (a phthalocyanine dye) and many others.

Mixtures of two or more of these soluble dyes are also suitable.

The soluble dye is preferably metered in using masterbatch technology, but can also be incorporated directly at the raw material manufacturer. The concentration of the color additives is between 0.01% by weight and 40% by weight, preferably between 0.05% by weight and 25% by weight, based on the weight of the crystallizable thermoplastic.

To set further desired properties, the film can also be corona or flame treated. The treatment intensity is chosen so that the surface tension of the film is generally above 45 mN / m.

Economic production includes the fact that the raw materials or the raw material components required for producing the film can be dried using commercially available industrial dryers, such as vacuum dryers, fluidized bed dryers, fluid bed dryers or fixed bed dryers (shaft dryers). It is essential that the antimicrobial and flame-retardant active substances and the other active substances do not outgas or form wall coverings in the dryers, that the raw materials do not stick together and are not thermally degraded. The dryers mentioned generally work at temperatures between 100 and 170 ° C. at normal pressure.

In a vacuum dryer that allows the gentlest drying conditions, the raw material goes through a temperature range of approx. 30 to 130 ° C at a reduced pressure of 50 mbar. Then a so-called post-drying is in a hopper at temperatures of 100 to 130 ° C and a residence time of 3 to 6 hours is required.

The surface gloss, measured according to DIN 67530 (measuring angle 20 °), is ≥100, preferably ≥110, the light transmission L *, measured according to ASTM D 1003, is ≥64%, preferably> 66% and the haze of the film, measured according to ASTM D 1003 is <30%, preferably <25%.

The standard viscosity SV (DCE) of the thermoplastic, measured in dichloroacetic acid according to DIN 53728, is in the range from 600 to 1400, preferably from

700 to 1200.

The bulk density, measured according to DIN 53466, is in the range from 0.75 to 1.0 kg / dm ³ , preferably from 0.80 to 0.90 kg / dm ³ .

The polydispersity of the thermoplastic Mw / Mn measured by means of GPC is in the range from 1.5 to 4.0, preferably from 2.0 to 3.5.

In the production of the film according to the invention, it was found that the film can be produced in the dryer in a process-reliable manner, for example by means of masterbatch technology and a suitable predrying or pre-crystallization of the masterbatch. Furthermore, no outgassing was found in the production process, which is essential to the invention.

Weathering tests have shown that the films according to the invention themselves

Weathering tests after an extrapolated 5 to 7 years for outdoor applications generally show no yellowing, no embrittlement, no loss of gloss on the surface, no cracking on the surface and no deterioration in the mechanical properties. Furthermore, the film according to the invention can be easily recycled without environmental pollution and without loss of mechanical properties, which makes it suitable, for example, for use as short-lived articles and goods for the medical field.

This film can be produced, for example, by an extrusion process in an extrusion line.

The foils can e.g. According to known processes from a thermoplastic raw material, 0.005 to 10.0% by weight of triclosan and with optionally further raw materials and / or other conventional additives in a customary amount of 0.1 to a maximum of 10.0% by weight, the sum of crystallized Thermoplastic and the additives is always 100%, both as monofilms and as multilayer, optionally coextruded films with the same or differently formed surfaces, one surface being pigmented, for example, and the other surface containing no pigment. Likewise, one or both surfaces of the film can be provided with a conventional functional coating by known methods.

The polymers or raw material mixtures are fed to an extruder or, in the case of multilayer films, to a plurality of extruders. Any foreign bodies or impurities that may be present can be filtered off from the polymer melt before extrusion. The melt (s) are then formed into flat melt films in a mono nozzle or, in the multilayer case, in a multilayer nozzle, and in the multilayer case are layered one on top of the other. Then the

Monofilm or the multilayer film quenched with the help of a cooling roller and solidified as a largely amorphous, ie unoriented film. The cooled, amorphous film is then hemmed and wound up. Due to the surprising combination of excellent properties and the antimicrobial effect, the film according to the invention is outstandingly suitable for a large number of different applications, for example in the interior, for example as a laminating medium, in the medical field, as packaging film or as a film in the disposal area and environmental protection. Since it can be easily recycled without polluting the environment and without losing its mechanical properties, it can be used, for example, to manufacture short-lived articles and goods for the medical sector.

In the following exemplary embodiments, the individual are measured

Properties according to the following standards or procedures.

measurement methods

DEG content / PEG content / IPA content

The DEG / PEG / I PA content is determined by gas chromatography after saponification in methanolic KOH and neutralization with aqueous hydrochloric acid.

Hemmhof test In a shell test, the film according to the invention and a non-antimicrobial reference film were examined. The film to be tested was placed on the nutrient agar in a petri dish and then very thinly overlaid with agar in which the test organisms were located. If there was no active substance against the organism, the test organism grew on the film sample and thus the entire surface of the petri dish. A substance that inhibited growth was noticeable in that at least the film to be examined was not overgrown or, furthermore, the growth was still inhibited around the film (Hemmhof). Escherichia coli NCTC 8196 was used as the test culture. The evaluation of the test was carried out by a visual assessment. Surface gloss, surface defects, surface tension The surface gloss was measured at a measuring angle of 20 ° according to DIN 67530. The surface defects were determined visually and the surface tension using the so-called ink method (DIN 53364).

light transmission

Under the light transmission is the ratio of the total let through

To understand light to the incident amount of light.

cloudiness

Haze is the percentage of the transmitted light that deviates by more than 2.5 ° on average from the incident light beam. The image sharpness was determined at an angle of less than 2.5 °.

Light transmission and haze were measured using the "© Hazegard plus" measuring device in accordance with ASTM D 1003.

SV (DCE), IV (DCE)

The standard viscosity SV (DCE) was measured in accordance with DIN 53726 in dichloroacetic acid. The intrinsic viscosity (IV) was calculated as follows from the standard viscosity (SV): IV (DCE) = 6.67 • 10-4 SV (DCE) + 0.118.

yellowness

The yellowness index (YID) is the deviation from the colorlessness in the "yellow" direction and was measured in accordance with DIN 6167.

Weathering (both sides), UV stability

The UV stability was tested according to the test specification ISO 4892 as follows:

Test device: Atlas Ci 65 Weather Ometer

Test conditions: ISO 4892, ie artificial weathering Irradiation time 1000 hours (per side)

Irradiation 0.5 W / m2, 340 nm

Temperature 63 ° C

Relative humidity: 50%

Xenon lamp inner and outer filter made of borosilicate

Irradiation cycles 102 minutes of UV light, then 18 minutes of UV light with water spraying of the samples, then again 102 minutes of UV light, etc.

fire behavior

The fire behavior was determined according to DIN 4102 part 2, building material class B2 and according to DIN 4102 part 1, building material class B1 and according to UL test 94.

Determination of the sealing start temperature (minimum sealing temperature) With the sealing device HSG / ET from Brugger, heat-sealed samples were obtained

(Sealing seam 20 mm x 100 mm), whereby the film was sealed at different temperatures with the help of two heated sealing jaws at a sealing pressure of 2 bar and a sealing time of 0.5 seconds. Test strips 15 mm wide were cut from the sealed samples. The seal starting temperature is the temperature at which a seal seam strength of at least 0.5 N / 15 mm is achieved.

Seal strength

To determine the seal seam strength using the T-Peel method, two 15 mm wide film strips were placed on top of one another and sealed at 130 ° C, a sealing time of 0.5 seconds and a sealing pressure of 2 bar (device: Brugger type NDS, one-sided heated sealing jaw). Examples

The examples and comparative examples below are each amorphous, undrawn, single-layer or multilayer, transparent films of different thicknesses, which were produced on the extrusion line described.

All films of Examples 4 to 13 and those of Comparative Example 2 were weathered on both sides for 1000 hours per side according to the test specification ISO 4892 with the Atlas Ci 65 Weather Ometer from Atlas and then tested for thermoformability, discoloration, surface defects and gloss ,

example 1

A 250 μm thick monofilm was produced using the following recipe:

48.0% by weight PET (type T94W, KoSa, Germany)

2.0% by weight of masterbatch which, in addition to PET (type T94W), contained 10.0% by weight of triclosan

50.0% by weight of regrind (inherent in film production, contained small amounts of triclosan in addition to PET)

The PET (type T94W) from which the film according to the invention was produced had a standard viscosity SV (DCE) of 1080. The IPA content was 4.8% by weight and the crystallinity of the PET was 48%.

Example 2

A three-layer ABA film with a total thickness of 250 μm was produced by coextrusion with the following recipe: Base layer B (240 μm thick): mixture of 50.0% by weight PET (type T94W)

50.0% by weight of regrind (inherent in film production, in addition to PET also contained small amounts of pigment and triclosan from the outer layers)

Cover layers A and C (each 5 μm thick): mixture of 83.0% by weight PET (type T94W)

10.0% by weight of masterbatch which, in addition to PET (type T94W), contained 10.0% by weight of triclosan

7.0% by weight of masterbatch which, in addition to PET (type T94W), contained 10,000 ppm © Sylobloc 44H (from Grace, Germany)

Example 3 Analogously to Example 2, a 250 μm thick A-B-A film was produced. In contrast to example 2, the base film was also equipped with triclosan. The film was also coated.

Base layer B: mixture of 48.0% by weight PET (type T94W)

2.0% by weight of masterbatch, which, in addition to PET (type T94W), contained 10.0% by weight of triclosan, 50.0% by weight of regenerate (inherent in film production, also contained small amounts of pigment and triclosan in addition to PET)

Cover layers A: mixture of 90.0% by weight PET (type T94W)

3.0% by weight of masterbatch which, in addition to PET (type T94W), contained 10.0% by weight of triclosan, 7.0% by weight of masterbatch, which, in addition to PET (type T94W), contained 10,000 ppm © Sylobloc

44H contained After the extrusion, the film was coated on one side with an aqueous dispersion using the “reverse gravure-roll coating” method. In addition to water, the dispersion contained 3.0% by weight of hydrophilic polyester (5-Na-sulfoisophthalic acid-containing PET / I PA polyester under the name SP41, Ticona, USA), 0.10% by weight of colloidal silicon dioxide (© Nalco 1060, Deutsche Nalco Chemie, Germany) as an antiblocking agent and 0.10% by weight ammonium carbonate (Merck, Germany) as a pH buffer. The wet application weight was 1.5 g / m ² on the coated side. After drying, the calculated thickness of the coating was 50 nm.

Comparative Example 1

Example 2 was repeated. In contrast to Example 2, the film was not antimicrobially treated with triclosan.

The properties of those according to Examples 1 to 3 and the comparative example

1 films produced are shown in Table 2 below.

Table 1

Example 4

A 150 μm thick monofilm was produced, the main constituent being PET (type T94W, KoSa, Germany), 0.2% by weight of triclosan and 0.1% by weight © Sylobloc 44H (from Grace, Germany) and 30 , 0% by weight of the intrinsic regenerate produced during film production.

The Sylobloc 44H used was added in the form of a masterbatch which, in addition to PET, contained 10,000 ppm of Sylobloc. The triclosan was also added in the form of a masterbatch, which in addition to PET contained 10.0% by weight of triclosan. The PET from which the transparent film and the respective masterbatch were produced had a standard viscosity SV (DCE) of 1050 and the DEG content was 1.8% by weight.

After the extrusion, the film was coated on one side as described in Example 3.

Example 5

Analogously to Example 4, a 150 μm thick monofilm was produced. In contrast to Example 4, the film additionally contained 0.6% by weight of the UV stabilizer 2- (4.6-

Geigy). The UV stabilizer was added in the form of a 20% by weight masterbatch (Tinuvin has a melting point of 149 ° C and is thermally stable up to approx. 330 ° C).

Example 6

A 150 μm thick coextruded A-B-A film was produced.

The main constituent of the 130 μm thick base layer B was PET according to Example 4, furthermore 0.1% by weight of hydrolysis stabilizer, 2.0% by weight of flame retardant and, in addition, 30.0% by weight of the self-regenerated material inherent in film production.

In addition to PET, the two 10 μm thick outer layers contained 0.7% by weight of triclosan and 0.1% by weight of Sylobloc 44H as antiblocking agents.

The triclosan was added in the form of a masterbatch which, in addition to PET, contained 10.0% by weight of triclosan. For the purpose of homogeneous distribution, the sylobloc, which is not soluble in PET, was incorporated into the PET by the raw material manufacturer.

The hydrolysis stabilizer and the flame retardant were metered in in the form of a master batch. The masterbatch was composed of 20.0% by weight of flame retardant, 1.0% by weight of hydrolysis stabilizer and 79.0% by weight of PET.

Pentaer thrityl-tetrakis-3- (3,5-di-tet. -Butyl-4-hydroxylphenyl) propionate was used as the hydrolysis stabilizer and the organic phosphorus compound methanephosphonic acid bis- (5 ~ ethyl-2-methyl- 2-oxo-2λ ⁵ - [1,3,2] dioxaphosphinan-5-ylmethyl ester) (© Amgard P1045 from Albright & Wilson).

Example 7

Analogously to Example 6, a 150 μm thick A-B-A film was produced with the difference that it was additionally coated on one side after the extrusion as in Example 3.

Example 8

A 150 μm thick, coextruded, sealable A-B-C film was produced.

The main constituent of the 130 μm thick base layer B was PET according to Example 4, furthermore 0.2% by weight of triclosan and 30.0% by weight of the self-regenerate that is inherent in the film production.

The triclosan was added in the form of a masterbatch which, in addition to PET, contained 10.0% by weight of triclosan. For the 10 μm thick sealable cover layer A, a copolyester of 78 mol% ethylene terephthalate and 22 mol% ethylene isophthalate was used as the thermoplastic (produced by the transesterification process with Mn as the transesterification catalyst, Mn concentration: 100 ppm).

It also contained 3.0% by weight of a masterbatch composed of 97.75% by weight of copolyester and 1.0% by weight of Sylobloc 44H and 1.25% by weight of © Aerosil TT 600 (pyrogenic SiO ₂ from Fa. Degussa)

The 10 μm thick, non-sealable top layer C contained 0.7 in addition to PET

% By weight of triclosan 3.0% by weight of a masterbatch composed of 97.75% by weight of PET and 1.0% by weight of Sylobloc 44H and 1.25% by weight of Aerosil TT 600 as an antiblocking agent.

Example 9 Analogously to Example 8, a 150 μm thick, coextruded, sealable

A-B-C film made. In contrast to Example 8, after extrusion, this film was coated on one side on the non-sealable top layer C as described in Example 3.

Example 10

Analogously to Example 9, a 150 μm thick, coextruded, sealable A-B-C film was produced, which - as described - was coated with the adhesion promoter SP41 on the top layer C.

In contrast to the film from Example 9, the base layer B additionally contained

1.5% Cl solvent blue 35 (fat-soluble anthraquinone dye, © Sudanblau 2, BASF, Germany). The colorant was metered in in the form of a masterbatch which, in addition to PET, contained 20.0% by weight of blue colorant. Example 11

Analogously to Example 10, a 150 μm thick, coextruded, sealable, colored was

A-B-C film made. In contrast to Example 10, the film was uncoated.

The film was corona treated on top layer C. The intensity was chosen so that the surface tension was> 45 mN / m.

Example 12

Analogously to Example 5, a 150 μm thick monofilm was produced which was antimicrobially treated with 0.2% by weight of triclosan, which in the form of a

10.0 wt .-% masterbatch was metered. It also contained 0.6% by weight of the UV stabilizer according to the information from Example 5 and 0.1% by weight of hydrolysis stabilizer and 2.0% by weight of flame retardant according to the information from Example 6.

Furthermore, the film contained 1.5% C.I. Solvent blue 35 (fat-soluble anthraquinone dye, © Sudanblau 2, BASF, Germany). The colorant was metered in in the form of a masterbatch which, in addition to PET, contained 20.0% by weight of blue colorant.

After the extrusion, the film was coated on one side as in Example 3.

Example 13

A 150 μm thick, coextruded, sealable A-B-C film was produced.

The formulation of the 130 μm thick base layer B corresponded to the formulation of the uncoated monofilm from Example 12, so in addition to PET triclosan, it contained a UV stabilizer, a flame retardant, a hydrolysis stabilizer and a soluble dye. The formulations of the 10 μm thick cover layers A and C corresponded to the formulations from Example 8.

Analogously to Example 9, the film was coated on the top layer C with the SP41 adhesion promoter.

Comparative Example 2

Analogously to Example 4, a 150 μm thick monofilm was produced which, in contrast to Example 4, did not contain any triclosan and was therefore not antimicrobially treated. The film was coated on one side as in Example 4.

The properties of the films produced according to Examples 4 to 13 and Comparative Example 2 are shown in Table 2 below.

Table 2

Claims

claims

1. Amorphous, antimicrobially finished, transparent film with a thickness in the range from 30 to 1000 μm, which contains a crystallizable thermoplastic as the main component, characterized in that the film is additionally used as an antimicrobial component 2,4,4 ^' -Trichlor-2 ^' - contains hydroxy-diphenyl ether ("tri-closan") alone or a mixture of triclosan and other antimicrobial substances.

2. Film according to claim 1, characterized in that the crystallizable thermoplastic is a polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, bibenzol-modified polyethylene terephthalate or mixtures thereof, preferably polyethylene terephthalate, polyethylene naphthalate or bibenzene-modified polyethylene terephthalate.

3. Film according to claim 1 or 2, characterized in that the concentration of triclosan in the range of 0.005 to 10.0 wt .-%, preferably

0.01 to 5.0% by weight, based on the weight of the crystallizable thermoplastic.

4. Film according to one or more of claims 1 to 3, characterized in that the other antimicrobial substances 10,10 ^' oxy-bisphenoxarsin, N- (trihalomethylthio) phthalimide, diphenylantimony-2-ethylhexanoate, copper 8- hydroxyquinoline, tributyltin oxide and its derivatives and derivatives of halogenated diphenyl ether compounds.

5. Film according to one or more of claims 1 to 4, characterized in that the film is equipped with a flame retardant and / or with UV stabilizers to achieve at least one further functionality and / or is colored with a soluble dye and / or is sealable and / or is coated on one or both surfaces and / or is corona-treated on one or both sides.

6. Film according to claim 5, characterized in that the concentration of the UV stabilizer in the range of 0.01 to 5.0 wt .-% preferably 0.1 to

3% by weight, the concentration of the flame retardant in the range from 0.5 to 30.0% by weight, preferably from 1.0 to 20.0% by weight and the concentration of the soluble dye in the range from 0.01 to 20.0% by weight, preferably in the range from 0.05 to 10.0% by weight, based on the weight of the crystallizable thermoplastic.

7. Film according to one of claims 5 or 6, characterized in that the UV stabilizers as 2-hydroxybenzophenones, 2-hydroxybenzotriazoles, organochlorine compounds, salicylic acid esters, cinnamic acid ester derivatives, resorcinol monobenzoates, oxalic acid anilides, hydroxybenzoic acid esters, sterically hindered amines and triazines, preferably 2-hydroxybenzotriazoles and triazines and in particular 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- (hexyl) oxyphenol or 2,2'-methylene-bis (6- (2H-Benzotriazol-2-yl) -4- (1, 1, 2,2-tetra-methylpropyl) phenol are present.

8. Film according to one or more of claims 5 to 7, characterized in that the organic phosphorus compounds carboxyphosphinic acids, their anhydrides or alkanephosphonic acid esters are contained as flame retardants.

9. Film according to one or more of claims 5 to 8, characterized in that in addition to the flame retardant, a hydrolysis stabilizer in the form of phenolic stabilizers, alkali / alkaline earth stearates and / or alkali / alkaline earth carbonates in an amount of 0.01 to 1.0 % By weight, preferably phenolic stabilizers in an amount of 0.05 to 0.6 % By weight, in particular 0.15 to 0.3% by weight and with a molecular weight of more than 500 g / mol, is contained.

10. Film according to one or more of claims 1 to 9, characterized in that regenerate is contained in the film.

11. A method for producing an amorphous, antimicrobially equipped, transparent film made of a crystallizable thermoplastic with a thickness in the range from 30 to 1000 microns, characterized in that a crystallizable thermoplastic with an antimicrobial substance in the presence or absence of further substances imparting functionality formed into a flat melt film by an extrusion process, quenched with the aid of a cooling roll and solidified as a largely amorphous film.

12. The method according to claim 11, characterized in that the antimicrobial substance in the form of 2,4,4 ^' -Trichlor-2 ^' -hydroxy-diphenyl ether ("triclosan") alone or a mixture of triclosan and other antimicrobial substances and the others Substances in the film production is metered into the extruder, the addition via the

Masterbatch technology is preferred.

13. The method according to claim 11 or 12, characterized in that the antimicrobial substance in addition to the thermoplastic in a masterbatch in amounts of 0.4 to 30.0 wt .-%, preferably 0.8 to 15.0 wt .-%, is used, the sum of the constituents always being 100% by weight.

14. The method according to one or more of claims 11 to 13, characterized in that the film with a flame retardant and / or with UV stabilizers and / or colored with a soluble dye and coated and / or equipped with at least one sealing layer and / or corona treated.

15. Use of the film according to one or more claims 1 to 10 for use indoors and outdoors.

16. Use according to claim 15 as a lamination medium, in the medical field, as packaging film, in the disposal area and environmental protection.

000