WO2002062578A1

WO2002062578A1 - Opaquely tinted, antimicrobial, biaxially oriented, semi-crystalline film from a crystallizable thermoplastic

Info

Publication number: WO2002062578A1
Application number: PCT/EP2002/000854
Authority: WO
Inventors: Ursula Murschall; Ulrich Kern; Klaus Oberländer; Günther Crass
Original assignee: Mitsubishi Polyester Film Gmbh
Priority date: 2001-02-05
Filing date: 2002-01-28
Publication date: 2002-08-15

Abstract

The invention relates to an opaquely tinted, antimicrobially finished, biaxally oriented, semi-crystalline film whose thickness ranges from 1 to 500 ν. The inventive film contains as the main component an antimicrobial component and at least one color pigment in addition to a crystallizable thermoplastic. The antimicrobial component used is 2,4,4,'-trichloro-2'-hydroy-dipenylether ( triclosan ) alone or in admixture with other antimicrobial substances. Depending on the intended purpose, the film can be additionally functionalized, that is it can be UV-stabilized, flame-retardant, sealable, coated on one or both sides, or corona and/or flame-treated. The invention further relates to a method for producing said film and to the use thereof.

Description

COVERED COLORED, ANTIMICROBIAL, BIAXAL ORIENTED, PARTIAL CRYSTALLINE FILM FROM A CRYSTALLIZABLE THERMOPLASTIC

The invention relates to an opaque colored, antimicrobial, biaxially oriented, partially crystalline film made of a crystallizable thermoplastic, the thickness of which is in the range from 1 to 500 μm, and to a process for producing this film and its use. 5

Covered colored films made of crystallizable thermoplastics with a thickness between 1 and 500 μm are well known. These films have no antimicrobial effect.

DE-B 2346 787 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 emerged in the production of film with this claimed phospholane-modified raw material:

The raw material is very sensitive to hydrolysis and must be pre-dried 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, i.e. H. the mechanical properties decrease sharply due to the regular embrittlement, so that the film is unusable. This occurs after 48 hours of thermal stress

Embrittlement on.

GB-A 1 465 973 describes a coextruded, two-layer polyester film, one layer of which contains isophthalic acid and terephthalic acid-containing copolyesters and the other layer of polyethylene terephthalate consists. There is no usable information in the script about the sealing behavior of the film. Due to the lack of pigmentation, the film cannot be produced reliably (film cannot be wound) and can only be processed to a limited extent.

EP-A 0 035 835 describes a coextruded, sealable polyester film in which, in order to improve the winding and processing behavior, particles are added to the sealing layer, the average particle size of which exceeds the layer thickness of the sealing layer. The particulate additives form surface protrusions that prevent unwanted blocking and

Prevent sticking to rollers or guides. No further details regarding the incorporation of antiblocking agents are given about the other, non-sealable layer of the film. It remains open whether this layer contains antiblocking agents. The choice of particles with a larger diameter than the sealing layer and the concentrations given in the examples deteriorates the sealing behavior of the film. The script does not give any information on the sealing temperature range of the film. The seal seam strength is measured at 140 ° C and is in a range from 63 to 120 N / m (0.97 N / 15 mm to 1.8 N / 15 mm film width).

EP-A 0 432 886 describes a coextruded multilayer polyester film which has a first surface on which a sealable layer is arranged and a second surface on which an acrylate layer is arranged. The sealable cover layer can also consist of copolyesters containing isophthalic acid and terephthalic acid. The film on the back has improved processing properties. The script does not give any information about the sealing area of the film. The seal seam strength is measured at 140 ° C. A seal seam strength of 761.5 N / m (11.4 N / 15 mm) is specified for an 11 μm thick sealing layer. A disadvantage of the rear acrylic coating is that this side no longer seals against the sealable top layer. The film can therefore only be used to a very limited extent.

EP-A 0 515 096 describes a coextruded, multilayer sealable polyester film which has an additional layer on the sealable layer Additive contains. The additive can contain, for example, inorganic particles and is preferably applied to the film in an aqueous layer during its production. As a result, the film should maintain the good sealing properties and be easy to process. The back contains very few particles that get into this layer mainly through the regranulate. No information is given in this document on the sealing temperature range of the film. The seal seam strength is measured at 140 ° C and is more than 200 N / m (3 N / 15 mm). A seal seam strength of 275 N / m (4.125 N / 15 mm) is given for a 3 μm thick sealing layer.

WO 98/06575 describes a coextruded multilayer polyester film which contains a sealable cover layer and a non-sealable base layer. The base layer can be composed of one or more layers, the interior of the layer being in contact with the sealable layer. The other (outer) layer then forms the second non-sealable cover layer. Here too, the sealable top layer can consist of copolyesters containing isophthalic acid and terephthalic acid, which, however, contain no antiblocking particles. The film also contains at least one UV absorber, which is added to the base layer in a weight ratio of 0.1 to 10%. Are preferred as UV absorbers

Triazines, e.g.® Tinuvin 1577 from Ciba. The base layer is equipped with common antiblocking agents. The film is characterized by a good sealability, but does not have the desired processing behavior and also has deficits in the optical properties (gloss and cloudiness).

WO 99/31036 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. Furthermore, a process for the preparation of the diphenyl ether derivatives is described. 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 opaque colored, antimicrobial, biaxially oriented, partially crystalline film, the thickness of which ranges from 1 to

500 microns and containing, as a principal constituent, a crystallizable thermoplastic, wherein the film is characterized in that it contains as antimicrobial component 2,4,4 ^{'trichloro-2'-hydroxy-diphenyl} ether ( "triclosan") alone or a mixture of Triclosan with other antimicrobial substances and at least one coloring pigment.

The invention further relates to a method for producing this film and its use.

In addition to very good optical properties, the film according to the invention has above all an antimicrobial effect.

Antimicrobial activity means that the growth of gram-positive and gram-negative bacteria as well as mold and yeast is greatly reduced, i.e. that the antimicrobial film is at least not overgrown by the test culture and that the growth around the film is inhibited (Hemmhof).

Gram-negative bacteria are, for example, escherichia coli, klebsiella pneumoniae, proteus vulgaris or salmonella. Gram-positive bacteria are, for example, staphylococcus aureus, streptococcus faecalis, micrococcus luteus or corynebacterium minutissimum. Test organisms are pure, defined microorganisms such as pseudomonas aeruginosa, staphylococcus aureus, escherichia coli, aspergillus niger, penicillium funicolosum, chaetomium globosum, trichoderme virid or candida albicans used. If there is no active substance against the organism, the test organism will overgrow the film sample and thus the entire surface of the petri dish.

Depending on the intended use, the film can also be functionalized. The additional functionality is preferably that the film is UV stabilized, flame retardant, sealable, coated on one or both sides, corona and / or flame treated.

Good optical properties include, for example, homogeneous ones

Coloring, a high surface gloss (≥ 15), a low light transmission (<85%) and a low yellowness index (<30).

The good mechanical properties include a high modulus of elasticity (E _MD > 3200 N / mm ² ; E _TD > 3500 N / mm ² ) and good tensile strength values (in

MD> 100 N / mm ² ; in TD> 130 N / mm ² ).

Good stretchability includes the fact that the film can be oriented excellently and without tears in both its longitudinal and transverse directions.

Furthermore, it is very surprising that the film according to the invention can also be recycled, i.e. the regenerate can be used again without loss of the optical and mechanical properties, e.g. without negatively affecting the yellowness index of the film.

The main component of the film is a crystallizable thermoplastic. Suitable crystallizable or semi-crystalline thermoplastics are, for example polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), bibenzoyl-modified polyethylene terephthalate (PETBB), bibenzoyl-modified polybutylene terephthalate (PBTBB), bibenzoyl-modified polyethylene naphthalate (PENBB) or mixtures thereof, said polyethylene terephthalate , Polyethylene naphthalate and bibenzene-modified polyethylene terephthalate are preferred. In addition to the main monomers such as dimethyl terephthalate (DMT), ethylene glycol (EG), propylene glycol (PG), 1,4-butanediol, terephthalic acid (TA), benzenedicarboxylic acid, 2,6-naphthalene dicarboxylate (NDC) and / or 2,6-naphthalene dicarboxylic acid (NDA), also isophthalic acid (IPA), trans- and / or c / s-1, 4-cyclohexanedimethanol (c-CHDM, f-CHDM or c / f-CHDM) can be used.

According to the invention one understands crystallizable thermoplastics

- 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 by DSC (differential scanning calorimetry) with a heating rate of 20 ° C./min, from 180 ° C. to over 365 ° C., preferably from 180 ° C. to 310 ° C. C, a crystallization temperature range Tc of 75 ° C to 280 ° C, a glass transition temperature Tg of 65 ° C to 130 ° C, a density, measured according to DIN 53479, of 1, 10 to 1, 45 and a crystallinity of 5% up to 65%, preferably 20% to 65%.

The main constituent means that the amount of thermoplastic is between 50.0 and 99.5% by weight, preferably between 75.0 and 99.5% by weight. The remaining amount of 100% can, in addition to the inorganic pigment and triclosan, be other additives customary for biaxially oriented films.

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-bisphenoxarsin, N- (trihalogenmethylthio) phthalimide, diphenylantimony-2-ethylhexanoate, copper 8-hydroxyquinoline, tributyltin oxide and its derivatives and derivatives of halogenated diphenyl ether compounds are used. The amount is generally 0.005 to 10.0% by weight, preferred as 0.01 to 5.0 wt .-%, based on the weight of the crystallizable thermoplastic, the proportion of triclosan always outweighing.

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. Furthermore, it generally contains the antiblocking agents and lubricants customary for films for the purpose of economical production.

The triclosan can be added to both the base layer and one or both top layers. The extrusion process is suitable for this, preferably including the masterbatch process, i.e. in film production. If necessary, any intermediate layers that are present can also be antimicrobial.

It is important with the masterbatch technology that the grain size and the

Bulk weight of the masterbatch is similar to that of the thermoplastic, so that a homogeneous distribution and thus a correspondingly homogeneous finish can take place.

With masterbatch technology, the additives are initially in a fixed

Carrier material dispersed. 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 with the antimicrobial substance 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 amount used thermoplastics. 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 composed of at least one core layer and at least one cover layer, a three-layer A-B-A or A-B-C structure being 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 layer (s) which is adjacent to the core layer.

In a particular embodiment, the cover layers can consist of a polyethylene terephthalate, a bibenzene-modified polyethylene terephthalate polymer, a bibenzene-modified and / or unmodified polyethylene naphthalate polymer or a bibenzene-modified and / or unmodified polyethylene terephthalate-polyethylene naphthalate copolymer or compound.

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

The film according to the invention contains in the base layer and / or optionally the cover layers at least one coloring pigment in a concentration in the range from 0.2 to 40.0% by weight, preferably from 0.3 to 25.0% by weight , in particular 1.0 to 25.0% by weight, based on the weight of the thermoplastic in the layer in question. Inorganic white and black pigments as well as inorganic or organic colored pigments are used as color pigments.

The coloring pigment is preferably added using masterbatch technology, but can also be incorporated directly at the raw material manufacturer. Suitable white pigments are, for example, titanium dioxide, barium sulfate, calcium carbonate, kaolin, silicon dioxide, with titanium dioxide (anatase or rutile) and barium sulfate being preferred.

Titanium dioxide of the type described does not create any vacuoles in the polymer matrix during film production.

The titanium dioxide particles which may be used can have a coating of inorganic oxides, as is usually used as a coating for TiO ₂ white pigment in papers or paints to improve the light fastness.

As is well known, TiO ₂ is photoactive. When exposed to UV rays, free radicals form on the surface of the particles. These free radicals can migrate to the film-forming polymers, which leads to degradation reactions and yellowing.

The particularly suitable oxides include the oxides of aluminum, silicon, zinc or magnesium or mixtures of two or more of these compounds. Ti0 ₂ particles with a coating of several of these compounds, for. B. in EP-A-0 044 515 and EP-A-0 078 633. Furthermore, the coating can contain organic compounds with polar and non-polar groups.

The organic compounds must be sufficiently thermostable in the production of the film by extrusion of the polymer melt. Polar groups are for example -OH; -OR; --COOX; (X = R; H or Na, R = alkyl with 1 - 34 C atoms). Preferred organic compounds are alkanols and fatty acids with 8-30 C atoms in the alkyl group, especially fatty acids and primary n-

Alkanols with 12 - 24 carbon atoms, as well as polydiorganosiloxanes and / or polyorganohydrogensiloxanes such as polydimethylsiloxane and polymethylhydrogensiloxane.

The coating of titanium dioxide particles generally consists of 1.0 to 12.0, in particular 2.0 to 6.0 g of inorganic oxides and 0.5 to 3.0, in particular 0.7 to 1.5 g of organic compounds, based on 100.0 g of titanium dioxide particles. The coating is applied to the particles in aqueous suspension. The inorganic oxides are made from water-soluble compounds, e.g. B. alkali, in particular Sodium nitrate, sodium silicate (water glass) or silica precipitated in the aqueous suspension.

Among inorganic oxides such as Al ₂ O ₃ or SiO ₂ , the hydroxides or their various dewatering stages are, for. B. understand oxide hydrate without recognizing its exact composition and structure. On the Ti0 ₂ pigment, the oxide hydrates are z. B. of aluminum and / or silicon, the pigments are then washed and dried. This precipitation can thus take place directly in a suspension, as occurs in the manufacturing process after the annealing and the subsequent wet grinding. The oxides and / or oxide hydrates of the respective metals are precipitated from the water-soluble metal salts in the known pH range, for the aluminum, for example, aluminum sulfate is used in aqueous solution (pH less than 4) and by adding aqueous ammonia solution or sodium hydroxide solution in the pH range of 5 to 9, preferably from

7 to 8.5, the oxide hydrate precipitates. Assuming a water glass or alkali alumate solution, the pH of the TiO ₂ suspension presented should be in the strongly alkaline range (pH greater than 8). The precipitation then takes place by adding mineral acid such as sulfuric acid in the pH range from 5 to 8. After the precipitation of the metal oxides, the suspension is left for another 15 minutes to about 2

Stirred for hours, the precipitated layers undergo aging. The coated product is separated from the aqueous dispersion and, after washing, is dried at an elevated temperature, preferably at 70 to 100 ° C.

The film can optionally contain at least one optical brightener, which is used in amounts of from 10 ppm to 50,000 ppm, preferably from 20 ppm to 30,000 ppm, in particular from 50 ppm to 25,000 ppm, based on the weight of the crystallizable thermoplastic. The optical brightener is also preferably metered in directly during film production using the so-called masterbatch technology.

The optical brighteners used are able to absorb UV rays in the range of 360 to 380 nm and emit them again as longer-wave, visible blue-violet light. Suitable optical brighteners are bis-benzoxazoles, phenylcoumarins and bis-sterylbiphenyls, preferably phenylcoumarin, in particular triazine-phenylcoumarin (© Tinopal, Ciba-Geigy, Basel, Switzerland), © Hostalux KS (Clariant, Germany) and © Eastobrite OB-1 (Eastman ).

Typical inorganic black pigments are carbon black modifications, which can also be coated, carbon pigments which differ from the carbon black pigments in their higher ash content, and oxidic black pigments such as iron oxide black and copper, chromium and iron oxide mixtures. (Mixed-phase pigments).

Suitable inorganic colored pigments are oxidic colored pigments, hydroxyl-containing pigments, sulfidic pigments and chromates.

Examples of colored oxide pigments are iron oxide red, titanium oxide-nickel oxide-antimony oxide mixed-phase pigments, titanium dioxide-chromium oxide, antimony oxide mixed-phase pigments, mixtures of the oxides of iron, zinc and titanium, chromium oxide iron oxide brown, spinels of the cobalt-aluminum-titanium-nickel-zinc oxide system and mixed phase pigments based on other metal oxides. Typical hydroxyl-containing pigments are, for example, oxide hydroxides of trivalent iron, such as FeOOH. Examples of sulfidic pigments are cadmium sulfide selenides,

Cadmium zinc sulfide, sodium aluminum silicate with sulfur bound like polysulfide in the lattice. Examples of chromates are lead chromates, which can be monoclinic, rhombic and tetragonal in the crystal forms.

Like the white and black pigments, all colored pigments can be both uncoated and also inorganic and / or organically coated.

The organic colored pigments are generally divided into azo pigments and so-called non-azo pigments. The azo (--N = N -) group is characteristic of the azo pigments. Azo pigments can be monoazo pigments, diazo pigments, diazo condensation pigments, salts of azo color acids and mixtures of the azo pigments. 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, ie during the film production process, expediently after the extrusion. The is particularly preferred

Application by means of the "reverse gravure-roll coating" process, 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 volatilized. You lend the

Film surface an additional function, for example the film becomes sealable, printable, metallizable, sterilizable, antistatic or improves e.g. the aroma barrier or enables adhesion to materials that would otherwise not adhere to the film surface (e.g. photographic emulsions). Examples of substances / compositions that provide 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 polyesters (EP-A 0 144878 , US-A 4,252,885 or EP-A-0296620), vinyl acetate (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 which impart the additional functionality can contain the customary additives such as antiblocking agents, pH stabilizers in amounts in the range from 0.05 to 5.0% by weight, preferably from 0.1 to 3.0% by weight. % contain.

The substances / compositions mentioned are applied as described above as a dilute solution, emulsion or dispersion to one or both film surfaces and then the solvent is evaporated. If the coatings are applied in-line after the longitudinal stretching, the temperature treatment before the transverse stretching is usually sufficient to volatilize the solvent and to dry the coating. The dried coatings then have layer thicknesses of 5 to 100 nm, preferably 20 to 70 nm, in particular 30 to 50 nm. 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 does the visual appearance change due to color change or yellowing, but also has an extremely negative influence on the mechanical-physical properties of the films made of the thermoplastics.

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, start below 360 nm UV

To absorb light, its 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 there are mainly chain cleavages, but none

Networking observed. Carbon monoxide, carbon dioxide and carboxylic acids are the predominant quantities of photooxidation products. In addition to the direct photolysis of the ester groups, oxidation reactions must also be considered, 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 α-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 cause sun protection. 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 nm to 380 nm, preferably 280 to 360 nm. These are particularly suitable if they are in the temperature range of

260 to 300 ° C are thermally stable, i.e. do not decompose and do not lead to outgassing. Suitable UV stabilizers as light stabilizers are, for example, 2-hydroxybenzophenones, 2-hydroxybenzotriazoles, organic nickel compounds, salicylic acid esters, cinnamic acid ester derivatives, resorcinol monobenzoates, oxalic acid anilides, hydroxybenzoic acid esters, sterically hindered amines and

Triazines, with the 2-hydroxybenzotriazoles and the triazines being preferred.

The film according to the invention can contain 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% by weight, based on the weight of the layer of the 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- (hexyloxyphenol 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 0.1 to 5.0% by weight of 2,2 '- (1,4-phenylene) to [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, this leads to a color change 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 poor thermal stability and decomposes or outgasses at temperatures between 200 ° C and 240 ° C, Large amounts (approx. 10 to 15% by weight) of 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 index 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

Film has an excellent appearance and has an excellent profile and flatness, - the UV-stabilized film 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 fulfills the conditions according to DIN 4102 Part 2 and in particular the conditions according to DIN 4102 Part 1 and is classified in the construction class B 2 and in particular B1 of the flame retardant materials can. Furthermore, the optionally flame-retardant film should pass the UL test 94 "Horizontal Burning Test for Flammability of Plastic Material" so that it can be classified in 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 from 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 halide in the event of fire, is 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 make sense.

Phenolic stabilizers are generally used as hydrolysis stabilizers,

Alkali / alkaline earth stearates and / or alkali / alkaline earth carbonates in amounts of 0.01 to 1.0% by weight. Phenolic stabilizers are preferred 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. Pentaerythrityl tetrakis-3- (3,5-di-tert-butyl-4- Hydroxyphenyl) propionate or 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene are particularly advantageous.

In this embodiment, the flame-retardant film according to the invention contains, as the main constituent, 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 in addition to the antimicrobial substance. Bis- (5-ethyl-2-methyl-2-oxo-2λ ⁵ - [1, 3,2] dioxaphosphinan-5-ylmethyl ester) 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 required and with high fire protection requirements, the core layer can also be equipped with flame retardants, i.e. 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 10 -

350 μm the requirements of building material classes B2 and B1 according to DIN 4102 and UL test 94. The surface gloss of the films according to the invention, measured according to DIN 67530 (measuring angle 20 °), is ≥ 15, preferably> 20 and the light transmission L ^* , measured according to ASTM D 1003, is ≤ 85%, preferably <80%, which for the achieved antimicrobial effect in combination with muted coloring is surprisingly good.

Where a very good sealability is required and where this property cannot be achieved by means of an on-line coating, the film according to the invention has at least three layers and then in a particular embodiment comprises the base layer B, the sealable cover layer, as layers

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 consists essentially of copolyesters which are composed predominantly of isophthalic 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 top layer C

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

The seal initiation 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 the copolymer does not have any more

Additives, especially no inorganic or organic fillers, are added. 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.

In another embodiment, a layer of the multilayer film according to the invention can also be colored transparently. For this purpose, the film can contain at least one dye soluble in the thermoplastic, the concentration of the soluble dye preferably in the range from 0.01% by weight to 20.0% by weight, in particular in the range from 0.05 to 10.0% by weight .-%, 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), C.I. Solvent Yellow 16 (a fat-soluble azo dye), Fluorol Green Gold (a fluorescent polycyclic dye), C.I. Solvent red 1 (an azo dye), azo dyes such as Thermoplastrot BS, Sudanrot BB, C.I. Solvent Red

138 (an anthraquinone derivative), fluorescent benzopyran dyes such as Fluorolrot GK and Fluorolorange GK, C.I. Solvent blue 35 (an anthraquinone dye), C.I. Solvent blue 15: 1 (a phthalocyanine dye) and many others.

Mixtures of two or more of these soluble are also suitable

Dyes.

The soluble dye is preferably metered in using masterbatch technology, but can also be incorporated directly at the raw material manufacturer. The con- The concentration of the color additives is between 0.01% by weight and 40.0% by weight, preferably between 0.05% by weight and 25.0% 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.

The economic production includes that the raw materials or the raw material components that are required for the production of the film with commercially available

Industrial dryers, such as vacuum dryers i.e. can be dried under reduced pressure, fluidized bed dryer, fluid bed dryer or fixed bed dryer (shaft dryer). 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 above-mentioned dryer works in general at normal pressure with temperatures between 100 and 170 ° C.

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

It is favorable that the masterbatch, which contains the triclosan and optionally the flame retardant and the hydrolysis stabilizer, is pre-crystallized or pre-dried. This predrying involves gradual heating of the masterbatch under reduced pressure (20 to 80 mbar, preferably 30 to 60 mbar, in particular 40 to 50 mbar) and with stirring and optionally post-drying at constant, elevated temperature, likewise under reduced pressure

Print. The masterbatch is preferably batchwise at room temperature from a metering container in the desired mixture together with the polymers of the base and / or outer layers and possibly other raw material components in a vacuum dryer which is used in the course of the drying or Dwell time a temperature range of 10 ° C to 160 ° C, preferably 20 ° C to 150 ° C, in particular 30 ° C to 130 ° C passes. During the approximately 6-hour, preferably 5-hour, in particular 4-hour dwell time, the raw material mixture is stirred at 10 to 70 rpm, preferably 15 to 65 rpm, in particular 20 to 60 rpm. The raw material mixture pre-crystallized or pre-dried in this way is in a downstream likewise evacuated container at 90 ° to 180 ° C., preferably 100 ° C. to 170 ° C., in particular 110 ° C. to 160 ° C. for 2 to 8 hours, preferably 3 to 7 hours , especially after 4 to 6 hours.

In the production of the film according to the invention, it was found that the film can be produced in the dryer, for example, by means of masterbatch technology and a suitable predrying or pre-crystallization of the masterbatch. The film can also be oriented in the longitudinal and transverse directions without tears. Furthermore, no outgassing was found in the production process, which is essential to the invention.

The film according to the invention can be produced, for example, by an extrusion process in an extrusion line.

The foils can e.g. by known processes from a thermoplastic raw material, 0.005 to 10.0% by weight of triclosan, at least one coloring pigment and optionally with further raw materials and / or other customary 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 as well as multilayer, optionally coextruded films with the same or differently shaped surfaces can be produced, with at least one film optionally being pigmented. In addition, one or both surfaces of the film can be provided with a conventional functional coating by known methods.

In the preferred extrusion process for producing the film, the melted thermoplastic material is extruded through a slot die and quenched as a largely amorphous pre-film on a chill roll. This slide will then heated again and stretched in the longitudinal and transverse directions or in the transverse and in the longitudinal direction or in the longitudinal, in the transverse and again in the longitudinal direction and / or transverse direction. The stretching temperatures are generally from T _g +10 ° C. to T _g +60 ° C. (T _g = glass temperature), the stretching ratio of the longitudinal stretching is usually from 2 to 6, in particular from 3 to 4.5, that of

Transverse stretching at 2 to 5, in particular at 3 to 4.5, and that of the second longitudinal stretching which may have been carried out at 1, 1 to 3. The first longitudinal stretching can optionally be carried out simultaneously with the transverse stretching (simultaneous stretching). This is followed by the heat setting of the film at oven temperatures of 200 to 280 ° C, especially at 220 to 270 ° C. The film is then cooled and wound up.

Weathering tests have shown that, in the case of UV stabilization, the film according to the invention generally does not yellow, does not become brittle, and does not lose any gloss, even after an extrapolated 5 to 7 years of outdoor use

Surface, no cracking on the surface and no deterioration of the mechanical properties.

The standard viscosity SV (DCE) of the thermoplastic, measured in dichloroacetic acid according to DIN 53728, is in the range from 600 to 1000, preferably from

700 to 900.

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.

Due to the surprising combination of excellent properties and the antimicrobial effect, the film according to the invention is excellently suitable for a large number of different applications, for example in the interior, for example as a laminating medium, in the medical field, for protective glazing of machines and medical devices, as furniture films, as packaging film or as film in the disposal area and environmental protection. Since it has no environmental impact and can be easily recycled without loss of mechanical properties, it can be used, for example, for the production of short-lived articles and goods for the medical sector and in the packaging sector.

Due to the possibly good UV stability and / or flame stability, the film according to the invention is also suitable for outdoor applications, e.g. for greenhouses, roofing, external cladding, covers, furniture foils, applications in the construction sector and in the electrical industry, for applications in the refrigerator and freezer sector and for illuminated advertising profiles.

In the following exemplary embodiments, the individual properties were measured in accordance with the standards and methods described:

Hemmhof test In a shell test, the film according to the invention and a reference film which is not antimicrobially treated are examined. The film to be tested is placed on the nutrient agar in a petri dish and then very thinly covered with agar in which the test organisms are located. If there is no active substance against the organism, the test organism grows over the film pattern and thus the entire surface of the

Petri dish. A substance that inhibits growth is noticeable in that at least the film to be examined does not overgrow or, furthermore, the growth is still inhibited around the film (Hemmhof). Escherichia coli NCTC 8196 is used as the test culture.

Surface gloss, surface fields, surface tension The surface gloss is measured at a measuring angle of 20 ° according to DIN 67530. The surface defects are visual and the surface tension is determined using the so-called ink method (DIN 53364).

Light transmission (transparency)

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 is determined at an angle of less than 2.5 °.

Light transmission and haze are measured with the measuring device "© Hazegard plus" according to ASTM D 1003.

Mechanical properties The modulus of elasticity, the tensile strength and the elongation at break are measured in longitudinal and

Transverse direction measured according to ISO 527-1-2.

Standard viscosity (SV) and intrinsic viscosity (IV): The standard viscosity SV is measured based on DIN 53726 in dichloroacetic acid (DCE). The intrinsic viscosity (IV) is calculated as follows from the standard viscosity (SV) IV (DCE) = 6.67 ^■ 10 ^"4 SV (DCE) + 0.118.

Weathering (both sides), UV stability

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

Atlas Ci 65 Weather Ometer test device

Test conditions ISO 4892, i.e. H. artificial weathering

Irradiation time 1000 hours (per side)

Irradiation 0.5 W / m ² , 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.

yellowness

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

The fire behavior is according to DIN 4102 part 2, building material class B2 and according to DIN

4102 part 1, building material class B1 and determined according to UL test 94.

Determination of the sealing start temperature (minimum sealing temperature)

Heat-sealed samples (sealing seam 20 mm x 100 mm) are produced with the sealing device HSG / ET from Brugger, whereby the film is 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 s. Test strips 15 mm wide are cut from the sealed samples. The seal start temperature is the temperature at which a seal seam strength of at least 0.5 N / 15 mm is achieved.

Seal seam strength Two are used to determine the seal seam strength using the T-Peel method

15 mm wide film strips are placed on top of each other and sealed at 130 ° C, a sealing time of 0.5 s and a sealing pressure of 2 bar (device: Brugger type NDS, sealing jaw heated on one side).

Examples

The examples and comparative examples below are single-layer or multilayer, covered-colored films of different thicknesses, which were produced on the extrusion line described. The following stretching conditions were used: the stretch ratio was 4 for the longitudinal and transverse stretching, and the temperature was 120 ° C. and 125 ° C., respectively. The

Heat setting was carried out at 230 ° C.

All films of Examples 1 to 10 and those of Comparative Example 1 were weathered on both sides with the Atlas Ci 65 Weather Ometer from Atlas according to the test specification ISO 4892 on both sides per 1000 hours and then with regard to the mechanical properties, the discoloration, the surface defects and the haze and checked for gloss. In the examples, a PET was always used which had a standard viscosity SV (DCE) of 810, corresponding to an intrinsic viscosity IV of 0.658 dl / g, unless stated otherwise.

example 1

A 50 μm thick monofilm was produced, the main constituent being PET (type RT49, KoSa, Germany), 0.2% by weight of triclosan and 0.4% by weight of titanium dioxide (anatase type, particle diameter 0.2 μm) contained. The film also contained 30.0% by weight of the self-regenerate that is inherent in the film production.

The titanium dioxide used (Sachtleben, Germany) was added in the form of a masterbatch which, in addition to PET, contained 70,000 ppm of titanium dioxide.

The triclosan was added in the form of a masterbatch which, in addition to PET

Contained 10.0 wt .-% triclosan.

After the longitudinal stretching, the film was coated on both sides with an aqueous dispersion using the “reverse gravure-roll coating” method. In addition to water, the dispersion contained 4.2% by weight of hydrophilic polyester (5-Na-sulfoisophthalic acid-containing PET / I PA polyester, type SP41, Ticona, USA), 0.15% by weight of colloidal silicon dioxide (© Nalco 1060 , Deutsche Nalco Chemie, Germany) as an antiblocking agent and 0.15% by weight ammonium carbonate (Merck, Germany) as a pH buffer. The wet application weight is 2 g / m ² on the coated side. After the transverse stretching, the calculated thickness of the coating was 40 nm.

Example 2

Analogously to Example 1, a 50 μm thick monofilm was produced. In contrast to example 1, the film additionally contained 0.6% by weight of the UV stabilizer 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- (hexyl) oxyphenol ( ^® Tinuvin 1577 from Ciba

Geigy). The UV stabilizer was added in the form of a 20.0% by weight masterbatch. Tinuvin 1577 has a melting point of 149 ° C and is thermally stable up to approx. 330 ° C.

Example 3

A 50 μm thick coextruded A-B-A film was produced.

The main component of the 46 μm thick base layer B was PET according to Example 1, 7% by weight of titanium dioxide, 0.2% by weight of hydrolysis stabilizer and 4.0% by weight of flame retardant. The layer also contained 30.0% by weight of the self-regenerate that is inherent in the film production.

In addition to PET, the two 2 μm thick outer layers contained 0.7% by weight of triclosan and 0.1% by weight of © Sylobloc 44H (Grace, Germany) as anti-blocking agents.

The triclosan was added in the form of a masterbatch which, in addition to PET, contained 10.0% by weight of triclosan.

The titanium dioxide was metered in in the form of a masterbatch, in addition to PET

50.0% by weight of titanium dioxide (anatase type, particle size 0.2 μm, from Sachtleben, Germany) contained.

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 consists of 20.0% by weight of flame retardant (methanephosphonic acid bis- (5-ethyl-2-methyl-2-oxo-2λ ⁵ - [1, 3,2] - dioxaphosphinan-5-ylmethyl ester), 1 , 0 wt .-% hydrolysis stabilizer (pentaerythritol tetrakis-3- (3,5-di-tert-butyl-4 (hydroxylphenyl) propionate) and 79.0 wt .-% PET together. Example 4

Analogously to Example 3, a 50 μm thick A-B-A film was produced. In contrast to Example 3, the film was additionally coated on one side after the longitudinal stretching in accordance with the “reverse gravure-roll coating” method described in Example 1.

Example 5

A 12 μm thick, coextruded, sealable A-B-C film was produced.

The 10 μm thick base layer B contained PET as the main component according to the example

1, 0.5% by weight of titanium dioxide (rutile type, 0.2 μm particle diameter, from Kerr McGee), 0.2% by weight of triclosan and 30.0% by weight of the self-generated material that is inherent in the film production ,

The titanium dioxide was metered in directly from the raw material manufacturer for homogeneous distribution.

A copolyester composed of 78 mol% of ethylene terephthalate and 22 mol% of ethylene isophthalate was used as the thermoplastic for the 1 μm thick sealable cover layer A (produced by the transesterification process with Mn as 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 44 H (synthetic SiO ₂ from Grace) and 1.25% by weight of ^® Aerosil TT 600 (pyrogenic Si0 ₂ from Degussa)

The 1 μm thick, non-sealable top layer C contained, in addition to PET, 0.7% by weight of triclosan and 3.0% by weight of a masterbatch made 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.

The triclosan was added in each case in the form of a masterbatch which, in addition to PET, contained 10.0% by weight of triclosan. Example 6

A 12 μm thick A-B-C film was produced analogously to Example 5. In contrast to Example 5, this film was only coated on one side after the longitudinal stretching on the non-sealable top layer C by means of the “reverse gravure-roll coating” method as in Example 4.

Example 7

Analogously to Example 6, a 12 μm thick A-B-C film was produced which - as described - was coated on the top layer C with the SP41 adhesion promoter.

In contrast to Example 6, the coated film contained no titanium dioxide, but 1% by weight of Cl pigment blue 28 (CoAI ₂ 0 ₄ spinel, cobalt blue, Degussa, Germany), which was incorporated directly into the PET at the raw material manufacturer.

Example 8

Analogously to Example 7, a 12 μm thick A-B-C film was produced. In contrast to Example 7, 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 9

Analogously to Example 2, a 50 μm thick monofilm was produced which contained 0.4% by weight of titanium dioxide and which was antimicrobially treated with 0.2% by weight of triclosan, which was metered in in the form of a 10.0% by weight masterbatch has been.

The titanium dioxide used (anatase type, from Sachtleben, Germany) was added in the form of a masterbatch which, in addition to PET, contained 70,000 ppm of titanium dioxide.

The film also contained 0.6% by weight of the UV stabilizer according to the information from Example 2 and 0.2% by weight of hydrolysis stabilizer and 4.0% by weight of flame retardant according to the information from Example 3. After the longitudinal stretching, the film was coated on both sides using the “reverse gravure-roll coating” method analogous to Example 1.

Example 10 A 50 μm thick, coextruded film was produced. The recipe of the

47 μm thick base layer B corresponded to the formulation of the uncoated monofilm from example 9. It therefore contained, in addition to PET titanium dioxide, triclosan, a UV stabilizer, a flame retardant and a hydrolysis stabilizer.

The formulation of the 1.5 μm-thick cover layers A and C corresponded to that

Example 5. Analogously to Example 6, the film was coated on the top layer C with the SP41 adhesion promoter.

Comparative Example 1 A 50 μm thick monofilm was produced analogously to Example 1. In contrast to Example 1, the film did not contain triclosan, so it was not antimicrobial. The film was coated on both sides as in Example 1.

The properties of the films which were produced according to Examples 1 to 10 and Comparative Example 1 are shown in Table 1 below:

Table 1

Example 11

A 50 μm thick monofilm was produced with the following recipe:

38.0% by weight PET (type RT49) 2.0% by weight masterbatch, which in addition to PET 10.0% by weight triclosan (Ciba-Geigy,

Switzerland) contained 10.0% by weight of masterbatch, which in addition to PET contains 70,000 ppm of titanium dioxide (anatase type,

Sachtleben, Germany) contained 50.0% by weight of regrind (inherent in the film production, contained not only PET but also titanium dioxide and triclosan)

Example f2

A coherently colored, three-layer A-B-A film with a total thickness of 50 μm was produced by coextrusion and subsequent stepwise orientation in the longitudinal and transverse directions with the following recipe:

Base layer B (44 μm thick): mixture of 43.0% by weight PET (type 4020)

7.0% by weight of masterbatch which, in addition to PET, contained 50.0% by weight of titanium dioxide (anatase type, from Sachtieben, Germany)

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

Cover layers A (each 3 μm thick): mixture of

83.0% by weight of PET (type 4020, KoSa, Germany) 10.0% by weight of masterbatch which, in addition to PET, contained 10.0% by weight of triclosan, 7.0% by weight of masterbatch, which in addition to PET 10,000 ppm © Sylobloc 44H (Grace, Germany) contained

The PET from which the opaque colored film was produced had a standard viscosity SV (DCE) of 770, which corresponds to an intrinsic viscosity IV (DCE) of 0.632 dl / g. Example 13

Analogously to Example 12, a 50 μm thick A-B-A film was produced. In contrast to Example 12, the base layer B was also equipped with triclosan.

Base layer B: mixture of

41.0% by weight PET (type 4020)

7.0% by weight of masterbatch which, in addition to PET, contains 50.0% by weight of titanium dioxide (anatase type, from Sachtleben, Germany), 2.0% by weight of masterbatch which, in addition to PET, contains 10.0% by weight of % Triclosan contained 50.0% by weight of regenerate (inherent in the film production, in addition to PET also contained small amounts of pigment and triclosan)

Cover layers A: mixture of 90.0% by weight of PET (type 4020), 3.0% by weight of masterbatch which, in addition to PET, contained 10.0% by weight of triclosan

7.0% by weight of masterbatch which, in addition to PET, contained 10,000 ppm of Sylobloc 44H

After the longitudinal stretching, the film was coated on one side in accordance with Example 1, but only using the “reverse gravure-roll coating” method.

Example 14

Example 11 was repeated with the difference that the coated film contained no titanium dioxide, but 1.0% by weight of Cl pigment blue 28 (CoAI ₂ 0 ₄ spinel, cobalt blue, Degussa, Germany), which was incorporated directly into the PET at the raw material manufacturer ,

Comparative Example 2

Example 12 was repeated with the difference that this film was not antimicrobially treated with triclosan.

The properties of the films which were produced according to Examples 11 to 14 and Comparative Example 2 are shown in Table 2 below: Table 2

+ improved adhesion no coating

Claims

claims

1. Dyed, antimicrobial, biaxially oriented, partially crystalline film made of a crystallizable thermoplastic, whose thickness is in the range of 1 to 500 microns, characterized in that it is 2,4,4 ^' -Trichlor-2'-hydroxy as an antimicrobial component -diphenyl ether ("Triclosan") alone or a mixture of Triclosan with other antimicrobial

Contains substances and at least one coloring pigment.

2. Film according to claim 1, characterized in that the crystallized thermoplastic is a polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, bibenzene-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 is in the range from 0.005 to 10.0% by weight, preferably 0.01 to 5% 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- (trihalogenomethylthio) phthalimide, diphenylantimony-2-ethylhexanoate, copper-8-hydroxyquinoline, Tributyltin oxide and its derivatives as well as derivatives of halogenated diphenyl ether compounds.

5. Film according to one or more of claims 1 to 4, characterized in that the coloring pigment in a concentration in the range from 0.2 to 40.0% by weight, preferably from 0.3 to 25.0% by weight. %, in particular 1.0 to 25.0% by weight, based on the weight of the thermoplastic, is present.

6. A film according to one or more of claims 1 to 5, characterized in that inorganic white and black pigments and inorganic or organic colored pigments are contained as color pigments.

7. Film according to one or more of claims 1 to 6, 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 colored with a soluble dye and / or sealable and / or is coated on one or both surfaces and / or is corona treated on one or both sides.

8. Film according to claim 7, characterized in that the concentration of the UV stabilizer in the range of 0.01 to 5.0 wt .-%, preferably 0.1 to 3 wt .-%, the concentration of the flame retardant in the range of

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 wt .-%, based on the weight of the crystallizable thermoplastic, is.

9. Film according to claim 7 or 8, characterized in that the UV stabilizers as 2-hydroxybenzophenones, 2-hydroxybenzotriazoles, organo-nickel compounds, salicylic acid esters, cinnamic acid ester derivatives, resorcinol monobenzoates, oxalic acid anilides, hydroxybenzoic acid esters, sterically hindered amines and triazines, preferably 2-hydroxy - benzotriazoles and triazines and especially 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) -tetramethyl-propyl) -phenol are present.

10. Film according to one or more of claims 7 to 9, characterized in that the organic phosphorus compounds carboxyphosphinic acids, their anhydrides and alkanephosphonic acid esters are contained as flame retardants.

11. Film according to one or more of claims 7 to 10, 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.

12. Film according to one or more of claims 1 to 11, characterized in that the film contains regrind.

13. A process for the preparation of a colored, antimicrobial, biaxially oriented, partially crystalline film made of a crystallizable thermoplastic with a thickness in the range from 1 to 500 μm, characterized in that a crystallizable thermoplastic with an antimicrobial substance, at least one coloring pigment in the presence or the absence of further functionality-imparting substances, formed into a flat melt film by an extrusion process, quenched with the aid of a cooling roll to form a largely amorphous pre-film, this film then heated again and stretched at least once in the longitudinal and transverse directions, then at temperatures from 200 to 280 ° C heat set and finally cooled and wound up.

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

15. The method according to claim 13 or 14, 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 other substances at Foil production can be metered into the extruder, the addition via the masterbatch technology being preferred.

16. The method according to one or more of claims 13 to 15, 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 components always being 100% by weight.

17. Use of the film according to one or more claims 1 to 12 for the

Indoor and outdoor use.

18. Use according to claim 17 as laminating medium, in the medical field, as packaging film, in the disposal area and environmental protection.