DE10105110A1 - Opaquely-tinted, biaxially-oriented partly-crystallised film with antimicrobial properties, e.g. for packaging and laminating, comprises crystallisable polyester containing the antimicrobial Triclosan and color pigments - Google Patents

Abstract

Opaquely tinted, biaxially-oriented, partly crystalline film with a thickness of 1-500 microns based on a crystallisable thermoplastic (I) contains 2,4,4'-trichloro-2'-hydroxy-diphenyl ether (Triclosan) and optionally other antimicrobial substances as antimicrobial components together with at least one color pigment. An Independent claim is also included for a method for the production of this film by extruding a mixture of (I) with additives as above, with or without other functional substances to form a flat melt film, quenching on a cooling roll, reheating and stretching at least once in the machine direction and the cross direction, heat fixing at 200-280 deg C, cooling and winding on a reel.

Description

The invention relates to further embodiments of DE 101 in the main application. , , , , (internal No. 01 / 013MFE) described, opaque colored, antimicro Biologically equipped, biaxially oriented, partially crystalline film made of a crystallized ed thermoplastic, whose thickness is in the range of 1 to 500 microns and which as antimicrobial component 2,4,4'-trichloro-2'-hydroxy-diphenyl ether ("triclosan") alone or a mixture of triclosan with other antimicrobial substances and contains at least one coloring pigment. These slides in their out leadership forms have at least one additional functionality besides the antimicrobial equipment. The term "additional functionality" includes the UV stability, yellowing resistance, photooxidative stability, flame retardant Equipment and sealability. Such a film can be one or more of the have functional properties. All such foils are characterized by economic thermoformability, due to very good optical properties, through an antimocrobial effect and moreover through one or more other functionalities. The invention further relates to a method for Production of this film and its use.

Covered colored films made of crystallizable thermoplastics with a thickness between 1 and 500 µm are well known. These foils have none antimicrobial effect.

DE-B 23 46 787 describes a flame-retardant raw material. Next The raw material is also the use of the raw material for films and fibers 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 become. When drying the raw material with dryers that are state of the art Technique correspond, the raw material glues, so that only under the most difficult Conditions a film can be produced.
• - The films produced under extreme, uneconomical conditions become brittle when exposed to temperature, d. H. the mechanical property due to the regular embrittlement, so 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 described, the one layer of isophthalic and terephthalic acid containing copolyesters and their other layer made of polyethylene terephthalate consists. There is nothing in the script about the sealing behavior of the film usable information. Due to the lack of pigmentation, the film is not Can be produced reliably (film cannot be wound) and only with restrictions further processed.

EP-A 0 035 835 describes a coextruded, sealable polyester film described, to improve the winding and processing behavior particles are placed in the sealing layer, the average particle size of which Layer thickness of the sealing layer exceeds. Through the particulate additives surface protrusions are formed which prevent unwanted blocking and Prevent sticking to rollers or guides. Over the other, not sealable Layer of the film, no further details on the incorporation of antiblock made average. It remains open whether this layer contains antiblocking agents. By Choice of particles with a larger diameter than the sealing layer and in the The sealing behavior of the film is shown in the examples deteriorated. Information on the sealing temperature range of the film is given in the Scripture not made. 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 described, which has a first surface on which a sealable layer is arranged and has a second surface on which an acrylate layer is arranged. The sealable top layer can also be made of isophthalic acid term and terephthalic acid copolyesters exist. Through the back Coating gives the film improved processing properties. information the script does not refer to the sealing area of the film. The sealed seam strength is measured at 140 ° C. For an 11 µm thick sealing layer, one Seal seam strength of 761.5 N / m (11.4 N / 15 mm) stated. Disadvantage of the back acrylic coating is that this side against the sealable Top layer no longer seals. The film is therefore only very limited use.

EP-A 0 515 096 describes a coextruded, multi-layer sealable Described polyester film that an additional on the sealable layer Additive contains. The additive can e.g. B. contain and will contain inorganic particles preferably in an aqueous layer on the film during its manufacture plotted. In this way, the film should maintain the good sealing properties and be easy to work with. The back contains very few particles that get into this layer mainly via the regranulate. Details of the The sealing temperature range of the film is also not mentioned in this document. The Seal seam strength is measured at 140 ° C and is more than 200 N / m (3 N / 15 mm). A sealing seam strength of 275 N / m is required for a 3 µm thick sealing layer (4.125 N / 15 mm).

WO 98/06575 describes a coextruded multilayer polyester film described that a sealable top layer and a non-sealable Contains base layer. The base layer can consist of one or more Layers are built up, the inner of the layer with the sealable Layer is in contact. The other (outer) layer then does not form the second sealable top layer. The sealable cover layer can also be made here copolyesters containing isophthalic acid and terephthalic acid, which  but do not contain antiblock particles. The slide also contains at least one UV absorber, the base layer in a weight ratio from 0.1 to 10% is added. Are preferred as UV absorbers Triazines, e.g. B. ®Tinuvin 1577 from Ciba. The base layer is with usual antiblocking agents. The film is characterized by a good one Sealability, but does not have the desired processing behavior and also shows deficits in the optical properties (gloss and cloudiness).

WO 99/31036 contains derivatives of halogenated diphenyl ether compounds described the antimicrobial properties in combination with improved Have migration behavior. The diphenyl ether derivatives described are thermally stable, show low volatility with low migration tendency and are preferred for the antimicrobial finishing of polymeric compounds such as for example for the antimicrobial finishing of plastics, rubbers, paints and fibers. Furthermore, there is a process for producing the dipheny lether derivatives described.

None of the references teach or point to a triclosan containing Thermoplastic film out, further that Triclosan in a crystallizable Thermo plasters can be incorporated, with all antimicrobial properties during the Processing and use phase are maintained.

The object of the present invention is to overcome the disadvantages of Avoid prior art.

The invention therefore relates to an opaque colored, antimicrobial armored, biaxially oriented, partially crystalline film, the thickness of which ranges from 1 to 500 µm, according to the main application DE 101. , , , , (internal no. 01 / 013MFE), which as a main component a crystallizable thermoplastic and additionally as antimicrobial component 2,4,4'-trichloro-2'-hydroxy-diphenyl ether ("triclosan") alone or a mixture of triclosan with other antimicrobial substances  and contains at least one coloring pigment, characterized in that it is provided with at least one additional functionality.

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

The expression "further or additional functionality" includes the 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 possess one or more of the functional properties. All such foils are characterized by economic thermoformability, by very good optical properties, through an antimocrobial effect and beyond through one or more additional functionalities.

An additional functionality means that the film, for example, with a flame retardant and / or equipped with UV stabilizers and / or is sealable and / or is coated on one or both surfaces and / or is corona treated on one or both sides.

Antimicrobial effect means that the growth of gram-positive and gram-negative bacteria and mold and yeast are greatly reduced, d. H. that the antimicrobial-treated film at least not from the test culture is overgrown and the growth around the film is also inhibited is (Hemmhof).

Gram-negative bacteria are, for example, escherichia coli, klebstella pneumo niae, proteus vulgaris or salmonella. Gram-positive bacteria are for example staphylococcus aureus, streptococcus faecalis, micrococcus luteus or coryne bacterium minutissimum. Pure, defined micro are used as test organisms organisms such as pseudomonas aeruginosa, staphylococcus aureus, escherichia coli, aspergillus niger, penicillium funicolosum, chaetomium globosum, trichoderme  virid or candida aibicans used. Unless against the organism effective substance is present, the test organism is the film sample and thus overgrown the entire surface of the Petri dish.

Good optical properties include, for example, homogeneous ones Coloring, high surface gloss (≧ 15), 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 ).

The good stretchability means that the film is both in its manufacture can be oriented in the longitudinal as well as in the transverse direction excellently and without tears.

Furthermore, it is very surprising that the film according to the invention also recyclable, d. H. the regenerate can be used again without losing the optical and mechanical properties, e.g. B. without the yellowness index of the film influence.

The main component of the film is a crystallizable thermoplastic. Suitable crystallizable or partially crystalline thermoplastics are, for example Polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate halat (PBT), bibenzol-modified polyethylene terephthalate (PETBB), bibenzolmodifi Ornamental polybutylene terephthalate (PBTBB), bibenzene-modified polyethylene naphthalate (PENBB) or mixtures thereof, with polyethylene terephthalate, Polyethylene naphthalate and bibenzene-modified polyethylene terephthalate are preferred are.

In addition to the main monomers such as Dimethyl terephthalate (DMT), ethylene glycol (EG), propylene glycol (PG), 1,4-butane diol, terephthalic acid (TA), benzene dicarboxylic acid, 2,6-naphthalene dicarboxylate (NDC)  and / or 2,6-naphthalene dicarboxylic acid (NDA), also isophthalic acid (IPA), trans and / or cis-1,4-cyclohexanedimethanol (c-CHDM, t-CHDM or c / t-CHDM) 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 with DSC (differential Scanning Calorimetry) with a heating rate of 20 ° C / min. of 180 ° C to over 365 ° C, preferably from 180 ° C to 310 ° C, a crystallization temperature range Tc from 75 ° C to 280 ° C, a glass transition temperature Tg from 65 ° C to 130 ° C, a density, measured according to DIN 53479, from 1.10 to 1.45 and have a crystallinity of 5% to 65%, preferably 20% to 65%.

The main component 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 100% can in addition to the inorganic pigment and triclosan for Biaxially oriented films can be common additives.

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- (trihalomethylthio) phthalimide, Diphenylantimon-2-ethylhexanoate, copper 8-hydroxyquinoline, tributyltin oxide and its derivatives and derivatives of halogenated diphenyl ether compounds used. The amount is generally 0.005 to 10.0% by weight, preferably as 0.01 to 5.0 wt .-%, based on the weight of the crystallizable Thermoplastics, the proportion of triclosan always predominating.  

The film according to the invention can be either single-layer or multi-layer his. It can also be coated with various copolyesters or adhesion promoters his. Furthermore, it generally contains the for economic production Foils usual antiblocking and lubricants.

The triclosan can cover both the base layer and one or both layers are added. The extrusion process is ideal for this wise including the master batch process, d. H. in film production, on. If necessary, any intermediate layers that are present can also be anti be microbially equipped.

It is important with the masterbatch technology that the grain size and the Bulk density of the masterbatch is similar to that of the thermoplastic, so that a homogeneous distribution and thus a correspondingly homogeneous equipment can be done.

With masterbatch technology, the additives are initially in a fixed Carrier material dispersed. The thermoplastic itself, z. B. the polyethylene terephthalate or other polymers with the Thermopla are sufficiently well tolerated. This is used for film production Masterbatch mixed with the thermoplastic intended as film raw material and treated together in an extruder, the ingredients being together merge and thus be dissolved in the thermoplastic.

When preparing the masterbatch with the antimicrobial substance in the present amount of antimicrobial agent in the generally 0.4 to 30.0% by weight, preferably 0.8 to 15.0% by weight on the thermoplastics used.

When producing masterbatches, care must be taken that the volatility of the Triclosan is taken into account through appropriate measures.  

In the multilayer embodiment, the film is made of at least one Core layer and at least one top layer, with a particular three-layer A-B-A or A-B-C structure is preferred.

For this embodiment it is essential that the thermoplastic of the core layer has a similar standard viscosity as the thermoplastic of the top layer (s), that adjoins the core layer.

In a special embodiment, the cover layers can be made from one Polyethylene terephthalate, from a bibenzene-modified polyethylene terephthalate Polymers, from a bibenzol-modified and / or unmodified polyethylene naphthalate polymers or from a bibenzene-modified and / or unmodified polyethylene terephthalate-polyethylene naphthalate copolymers or compound consist.

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

The film according to the invention contains and / or optionally in the base layer the top 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 relevant layer. Inorganic whites are used as coloring pigments - and black pigments as well as inorganic or organic colored pigments used.

The coloring pigment is preferred over the masterbatch technology added, 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, whereby titanium dioxide (anatase or rutile) and Barium sulfate are preferred.  

Titanium dioxide of the type described produces within the polymer matrix no vacuoles 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. TiO ₂ particles with a coating of several of these compounds are used, 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 carbon atoms in the alkyl group, in particular fatty acids and primary n-alkanols with 12-24 carbon atoms, and also 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 up 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 on Organic oxides are made from water-soluble compounds, e.g. B. alkali, especially sodium nitrate, sodium silicate (water glass) or silica in the aqueous suspension precipitated.  

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 TiO ₂ pigment after the glow and grinding in aqueous suspension, the oxide hydrates such. 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 from 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 stirred for a further 15 minutes to about 2 hours, the precipitated layers undergoing 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, wherein the optical brightener in amounts 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 is used. Also the Optical brightener is preferably via the so-called masterbatch technology dosed directly during film production.

The optical brighteners used are able to withstand UV rays in the range of Absorb 360 to 380 nm and as a longer-wave, visible blue-violet To give off light again.  

Suitable optical brighteners are bis-benzoxazoles, phenylcoumarins and bis- sterylbiphenyls, preferably phenylcoumarin, especially triazine-phenylcoumarin (®Tinopal, Ciba-Geigy, Basel, Switzerland), ®Hostalux KS (Clariant, Germany) and ®Eastobrite OB-1 (Eastman).

Typical inorganic black pigments are soot modifications, which are also cocoa tet can be carbon pigments, which differ from the carbon black pigments by a distinguish higher ash content, and oxidic black pigments such as iron oxide black and copper, chrome, iron oxide mixtures. (Mixed-phase pigments).

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

Examples of oxidic colored pigments are iron oxide red, titanium oxide-nickel oxide anti monoxide mixed phase pigments, titanium dioxide-chromium oxide, antimony oxide mixed pha Senpigmente, mixtures of the oxides of iron, zinc and titanium, chromium oxide Iron oxide brown, spinels of the cobalt-aluminum-titanium-nickel-zinc oxide and system Mixed phase pigments based on other metal oxides.

Typical hydroxyl-containing pigments are, for example, oxide hydroxides trivalent iron, such as FeOOH.

Examples of sulfidic pigments are cadmium sulfide selenides, cadmium Zinc sulfides, sodium aluminum silicate with sulfur bound in polysulfide form Grid.

Examples of chromates are lead chromates, which in the crystal forms are monoclinic, rhombic and tetragonal.

Like the white and black pigments, all colored pigments can both be uncoated as well as inorganic and / or organic coated.  

The organic colored pigments are usually divided into azo pigments and such called non-azo pigments. The azo pigment is characteristic of the azo pigments. (-N = N -) - group. Azo pigments can be monoazo pigments, diazo pigments, diazo condensation pigments, salts of azo dyes 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, advantageously after the 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 volatilized. They give the film surface an additional function, for example the film is thereby sealable, printable, metallizable, sterilizable, antistatic or improve z. B. the aroma barrier or allow adhesion to materials that would otherwise not adhere to the film surface (z. B. photographic emulsions). Examples of substances / compositions that 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 polyesters (EP-A 0 144 878, US-A 4,252,885 or EP-A-0 296 620), 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 its 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 as described above as dilute solution, emulsion or dispersion on one or both film surfaces applied and then the solvent evaporated. Will the Coatings applied in-line after longitudinal stretching are usually sufficient Heat treatment prior to transverse stretching to remove the solvent volatilize and dry the coating. The dried coatings then have layer thicknesses of 5 to 100 nm, preferably 20 to 70 nm, ins special 30 to 50 nm.

In a special embodiment, the film according to the invention can be UV- be stably equipped.

Light, especially the ultraviolet portion of solar radiation, i.e. H. of the waves length range from 280 to 400 nm, induces degradation processes with thermoplastics, as a result, not only the visual appearance through entering Color change or yellowing changes, but by the mechanical physical properties of the films from the thermoplastics extremely negative to be influenced.

The prevention of these photooxidative degradation processes is of considerable importance technical and economic importance, 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 Range between 280 and 300 nm.

In the presence of oxygen there are mainly chain cleavages, but none Networking observed. Provide carbon monoxide, carbon dioxide and carboxylic acids the quantitatively predominant photo-oxidation products. In addition to the Direct photolysis of the ester groups still need to be carried out in oxidation reactions  The formation of peroxide radicals should also be considered Cause carbon dioxide.

The photooxidation of polyethylene terephthalates can also be done via hydrogen cleavage in the α-position of the ester groups to form hydroperoxides and their decomposition products as well as the associated chain splitting (H. Day, D. M. Wiles: J. Appl. Polym. Sci 16, 1972, page 203).

UV stabilizers or UV absorbers as light stabilizers are chemical Compounds that are involved in the physical and chemical processes of the light indu graced dismantling can intervene. Soot and other pigments can partially cause sun protection. However, these substances are for films according to the Invention unsuitable because they lead to discoloration or color change. For this Films are only suitable organic and organometallic compounds that the thermoplastics to be stabilized no or only an extremely low color or Give color change.

Suitable UV stabilizers as light stabilizers are compounds that 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 absorb. These are particularly suitable if they are in the temperature range of 260 to 300 ° C are thermally stable, d. H. do not decompose and not to Outgassing. Suitable UV stabilizers are light stabilizers for example 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, with the 2-hydroxybenzotriazoles and the triazines being preferred.

The film according to the invention can have at least one UV stabilizer as light contain protective agents, 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 wt .-%, based on the weight of the layer of crystallizable thermo plastic, lies.

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 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 UV stabilizers mentioned above in films in combination with an antimicrobial finish to the desired result. When trying to achieve some UV stability via an anti To achieve oxidans, this leads to a color change after weathering.

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

• - The UV stabilizer has a lack of thermal stability and at Temperatures decomposed or outgassed between 200 ° C and 240 ° C,
• - Large quantities (approx. 10 to 15% by weight) UV stabilizer incorporated must be so that the UV light is absorbed and the film does not is damaged.

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

• - nozzle deposits, which leads to profile fluctuations;
• - Roller deposits from the UV stabilizer, which affects the optical properties (poor cloudiness, adhesive defect, inhomogeneous Surface) leads;
• - 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 accuracy of the measurement does not change,
• - No outgassing, no nozzle deposits, which means that Film has an excellent appearance and an excellent profile and has excellent flatness,
• - The UV-stabilized film has excellent running safety distinguished so that it can be manufactured in a reliable manner. In order to 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 the conditions according to DIN 4102 part 2 and in particular the conditions according to DIN 4102 part 1 are fulfilled and in the Building material class B2 and especially B1 of the flame retardant materials can be classified.

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 94 VTM-0 class.

The film according to the invention can contain at least one flame retardant, using the so-called masterbatch technology directly in film production is metered in, 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, based on the Weight of the layer of crystallizable thermoplastic, is. The concentration of the flame retardant in the masterbatch is generally in the range of 5.0 up to 60.0% by weight.

Typical flame retardants include bromine compounds, chlorinated paraffins and other chlorine compounds, antimony trioxide, aluminum hydroxide, the Halogen compounds due to the resulting halogen-containing by-products are disadvantageous. Furthermore, the low light resistance is one of them  equipped film next to the development of hydrogen halide on fire case 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 dimethyl methylphosphonate. It is essential to the invention that the organic phosphorus compound is soluble in the thermoplastic, otherwise the required optical properties are not met.

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

Phenolic stabilizers are generally used as hydrolysis stabilizers, Alkali / alkaline earth stearates and / or alkali / alkaline earth carbonates in amounts of 0.01 up to 1.0 wt .-% used. Phenolic stabilizers are used in an amount of 0.05 to 0.6 wt .-%, in particular 0.15 to 0.3 wt .-% and with a molecular weight of more than 500 g / mol is preferred. 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-hydro xybenzyl) benzene are particularly advantageous.

In this embodiment, the flame retardant film contains according to the Invention as main component a crystallizable PET, 1.0 to 20.0% by weight an organic phosphorus compound soluble in thermoplastic as a flame preservative and 0.1 to 1.0 wt .-% of a hydrolysis stabilizer in addition to antimicrobial substance. Dimethyl methylphosphonate is a flame retardant prefers.

This information regarding flame retardants and hydrolysis stabilizers also applies in With regard to other thermoplastics to be used according to the invention.

Surprisingly, fire protection tests according to DIN 4102 and the UL Test showed 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 to achieve improved flame retardancy. If necessary and at high Fire protection requirements can also include the core layer with flame retardants be equipped, d. H. include so-called basic equipment.

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

No embrittlement after exposure to temperature means that the film after 100 hours of annealing at 60 ° C in a forced air oven, no embrittlement and has no adverse mechanical properties.

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 achieved antimicrobial effect in combination with muted coloring is surprisingly good.

Where a very good sealability is required and where this property is not can be achieved via an online coating, the film is in accordance with Invention constructed at least three layers and then includes a special one Embodiment 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 Embodiments in which the cover layer C is sealable are the cover layers A and C identical.  

Sealable top layer A

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

Non-sealable top layer C

For the other, non-sealable top layer C or for any existing one In principle, the same polymers can be used between the intermediate layers. as previously described for the base layer.

The desired sealing and processing properties of the Film according to the invention are made from the combination of the properties of the used copolyesters for the sealable top layer and the topographies the sealable cover layer A and the sealable or non-sealable Obtain top layer C.

The seal starting temperature of 130 ° C and the seal seam strength of at least 0.6 N / 15 mm is achieved if for the sealable outer layer A the Copolymers described in more detail above can be used. The best sealing properties  the film is obtained when the copolymer has no further Additives, especially no inorganic or organic fillers added become. In this case, the lowest is obtained for a given copolyester Seal starting temperature and the highest seal seam strengths. However in this case the handling of the film is bad because the surface of the sealable top layer A tends to block. The film can hardly be and is for further processing on high-speed packaging machines not suitable. 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 help of suitable antiblocking agents selected size in a certain concentration of the sealing layer be added in such a way that on the one hand the blocking is minimized and on the other hand, the sealing properties are only slightly deteriorated.

In another embodiment, one layer of the multilayer film can also be colored transparently according to the invention. The slide can do this contain at least one dye soluble in the thermoplastic, the Concentration of the soluble dye, preferably in the range of 0.01% by weight and 20.0% by weight, in particular in the range from 0.05 to 10.0% by weight on the weight of the crystallizable thermoplastic.

Soluble dye means substances that are molecular in the polymer are solved (DIN 55949).

The color change of the film is based on the wavelength-dependent Absorption and / or scattering of light. Dyes can only absorb light but do not scatter as a certain particle size is the physical Spreading is a prerequisite.

Coloring with dye is a solution process. As The result of this solution process is the dye, for example in  solved the crystallizable thermoplastic. Such colorations are called labeled transparent, translucent, translucent or opal.

Of the different classes of soluble dyes, especially those fat and aromatic soluble dyes preferred. This is for example wise around azo and anthraquinone dyes. They are particularly suitable for. B. for Coloring of PET because of the high glass transition temperatures of PET the migration of the dye is restricted. (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 (a Azo dye), azo dyes such as Thermoplastic Red BS, Sudan Red BB, C.I. Solvent Red 138 (an anthraquinone derivative), fluorescent benzopyran dyes such as fluorol red GK and fluorine orange 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, can also be incorporated directly at the raw material manufacturer. The con concentration of the color additives is between 0.01% by weight and 40.0% by weight, preferably between 0.05% and 25.0% by weight, based on the Weight of the crystallizable thermoplastic.

To set other desired properties, the film can also be corona- or be flame treated. The treatment intensity is chosen so that the Surface tension of the film is generally over 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 d. H. under reduced pressure, Fluidized bed dryer, fluid bed dryer or fixed bed dryer (shaft dryer), can be dried. It is essential that the antimocrobial and flame-retardant active substances and the other active substances do not outgas or Wall coverings in the dryers ensure that the raw materials do not stick together be thermally degraded. The dryers mentioned generally work normal pressure with temperatures between 100 and 170 ° C.

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

It is essential to the invention that the masterbatch which contains the triclosan and that the masterbatch which may contain the flame retardant and optionally contains the hydrolysis stabilizer, pre-crystallized or pre-dried is not. 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 a After drying at constant, elevated temperature also under reduced Print. The masterbatch is preferably made from one at room temperature Dosing container in the desired mixture together with the polymers the base and / or cover layers and possibly other raw material components in batches in a vacuum dryer, which during the drying or Dwell time a temperature range from 10 ° C to 160 ° C, preferably 20 ° C to 150 ° C, especially 30 ° C to 130 ° C passes. During the approx. 6- hours, preferably 5 hours, in particular 4 hours the raw material mixture at 10 to 70 rpm, preferably 15 to 65 rpm, ins stirred particularly 20 to 60 rpm. The so pre-crystallized or pre-dried  Raw material mixture is in a downstream, also 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 4 to 6 hours dried.

When producing the film according to the invention it was found that using masterbatch technology and a suitable predrying or Precrystallization of the masterbatch the film without gluing in the dryer can be made. The film can also be used lengthways and crossways Orientate direction without breaks. Furthermore, no outgassing in the Production process found, which is essential to the invention.

The production of the film according to the invention can, for example, according to a Extrusion processes take place in an extrusion line.

The films can e.g. B. by known methods from a thermoplastic raw material, 0.005 to 10.0% by weight of triclosan, at least one coloring pigment and with possibly further raw materials and / or further conventional additives in usual amount of 0.1 to a maximum of 10.0 wt .-%, the sum of crystallized thermoplastic and the additives is always 100%, both as Monofilms as well as multi-layer, optionally co-extruded films same or differently designed surfaces are produced, where appropriate, at least one film is pigmented. You can also one or both surfaces of the film by known methods with one usual functional coating.

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 film is 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 T _g + 10 ° C to T _g + 60 ° C (T _g = glass temperature), the stretching ratio of the longitudinal stretching is usually 2 to 6, in particular 3 to 4.5, that of the transverse stretching 2 to 5, in particular in the case of 3 to 4.5, and that of the second longitudinal stretching which may be 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 even after a projected 5 to 7 years of outdoor use generally no yellowing, no embrittlement, no loss of gloss Surface, no cracking on the surface and no deterioration of the has mechanical properties.

The standard viscosity SV (DCE) of the thermoplastic, measured in dichloro acetic 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 GPC is in Range from 1.5 to 4.0, preferably from 2.0 to 3.5.

When producing the film according to the invention it was found that the Process film can be produced reliably. Furthermore, there were no outgassings found in the production process, which is essential to the invention.

Due to the surprising combination of excellent properties and antimicrobial effect, the film according to the invention is extremely suitable for a variety of different applications e.g. B. indoors, for example  as a lamination medium, in the medical field, for protective glazing from Machines and medical devices, as furniture films, as packaging films or as a film in the disposal area and environmental protection. Since it has no environmental impact and is easily recyclable without loss of mechanical properties, can, for example, for the production of short-lived articles and goods for used in the medical field and in the packaging sector.

Suitable due to the possibly good UV stability and / or flame stability the film according to the invention also for outdoor applications such. B. for Greenhouses, canopies, exterior claddings, covers, furniture foils, applications in the construction sector and in the electrical industry, for applications in the cooling and freezing area and for illuminated advertising profiles.

The invention is explained in more detail below on the basis of exemplary embodiments explained without being limited to this. The individual properties were checked as follows:

Antimicrobial effect

In a shell test, the film according to the invention and one were not antimicrobial reference film examined. It was the one to be checked Place the film on the nutrient agar in a petri dish and apply it finally very thinly overlaid with agar, in which can be used as a test culture escherichia coli NCTC 8196. Unless against the organism active substance was present, the test organism grew on the film ster and therefore the entire surface of the petri dish. The antimicrobial The film was not overgrown by the test culture and the growth around the film inhibited around.

surface gloss

The surface gloss was measured at a measuring angle of 20 ° according to DIN 67530 measured.  

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 light that passes through the radiated light beam deviates by more than 2.5 ° on average. 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 ASTM D 1003 measured.

surface defects

The surface defects were determined visually.

surface tension

The surface tension was measured using the so-called ink method (DIN 53364).

Mechanical properties

The modulus of elasticity, the tensile strength and the elongation at break were measured in longitudinal and Transverse direction measured according to ISO 527-1-2.

Standard viscosity (SV) and intrinsic viscosity (IV)

The standard viscosity SV - based on DIN 53726 - was measured as a 1% solution in dichloroacetic acid (DCE) at 25 ° C. SV (DCE) = (η _rel - 1) × 1000. 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 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 / 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 the samples, then again 102 minutes of UV light, etc.

Yellow value

The yellowness index (YID) is the deviation from the colorlessness in the direction of "yellow" and was measured according to DIN 6167. Yellowness indexes (YID) of <5 are not visual visible.

fire behavior

The fire behavior was 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 were used with the sealing device HSG / ET from Brugger (Sealing seam 20 mm × 100 mm) made, the film 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 was sealed. From the sealed Samples were cut test strips 15 mm wide. The T-seal seam strength was measured as in the determination of the seal strength. The Seal start temperature is the temperature at which a seal seam strength of at least 0.5 N / 15 mm is reached.  

Seal strength

Two 15 mm wide film strips were used to determine the seal seam strength superimposed and at 130 ° C, a sealing time of 0.5 s and a seal pressure of 2 bar (device: Brugger type NDS, one-sided heated sealing jaw) sealed. The seal seam strength was determined by the T-Peel method.

Examples

The examples below and the comparative example are each around single-layer or multi-layer, colored films of different thicknesses, which were produced on the extrusion line described.

All foils were tested on both sides according to the ISO 4892 test specification weathered on each side with the Atlas Ci 65 Weather Ometer from Atlas and then regarding the mechanical properties, the discoloration, the Surface defects, turbidity and gloss checked.

In the examples, a PET was always used that has a standard viscosity SV (DCE) of 810, corresponding to an intrinsic viscosity IV of 0.658 dl / g unless otherwise noted.

example 1

A 50 µm thick monofilm was produced, the main component being PET (Type RT49, KoSa, Germany), 0.2% by weight of triclosan and 0.4% by weight of titanium contained dioxide (anatase type, particle diameter 0.2 microns). The film contained further 30.0% by weight of the intrinsically occurring in the film production Eigenregenerates.

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

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 / IPA polyester, type SP41, Ticona, USA), 0.15% by weight of colloidal silicon dioxide (®Nalco 1060, German 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 per 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. The difference for 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 in the form of a 20.0% by weight masterbatch added. Tinuvin 1577 has a melting point of 149 ° C and is up to approx. 330 ° C thermally stable.

Example 3

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

The 46 μm thick base layer B contained the main constituent PET according to Bei 1.7% by weight of titanium dioxide, 0.2% by weight of hydrolysis stabilizer and 4.0% by weight Flame retardants. The layer also contained 30.0% by weight of the immanent of the self-generated regenerative film.

The two 2 µm thick top layers contained 0.7% by weight of PET Triclosan and 0.1% by weight ®Sylobloc 44H (from Grace, Germany) as anti block agents.  

The triclosan was added in the form of a masterbatch which, in addition to PET Contained 10.0 wt .-% 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) included.

For the purpose of homogeneous distribution, the Sylobloc, which is not soluble in PET, was incorporated into the PET at the raw material manufacturer.

The hydrolysis stabilizer and the flame retardant were in the form of a Masterbatches added. The masterbatch consists of 20.0% by weight flame preservative (dimethyl methylphosphonate), 1.0% by weight hydrolysis stabilizer (Pentaerylthrityl-tetrakis-3- (3,5-di-tert-butyl-4 (hydroxylphenyl) propionate) and 79.0% by weight of PET together.

Example 4

Analogously to example 3, a 50 μm thick ABA film was produced. In contrast to Example 3, the film was coated on one side with an aqueous dispersion after the longitudinal stretching 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 / IPA 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 was 2 g / m ² per coated side. After the transverse stretching, the calculated thickness of the coating was 40 nm.

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 wt .-% titanium dioxide (rutile type, 0.2 µm particle diameter, Kerr McGee), 0.2% by weight of triclosan and 30.0% by weight of the inherent in the Self-generated film production.

The titanium dioxide was directly from the raw material manufacturer for a homogeneous distribution dosed.

For the 1 µm thick sealable cover layer A was used as a thermoplastic Copolyester of 78 mol% ethylene terephthalate and 22 mol% ethylene isophthalate used (produced via 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 (synthetic SiO ₂ from Grace) and 1.25% by weight of ®Aerosil TT 600 (pyrogenic SiO ₂ from Degussa)

In addition to PET, the 1 μm thick top layer C contained 0.7% by weight of triclosan and 3.0% by weight a master batch 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 the form of a masterbatch, which next to PET contained 10.0% by weight of triclosan.

Example 6

A 12 μm thick ABC film was produced analogously to Example 5. In contrast to Example 5, the non-sealable top layer C was coated on one side with an aqueous dispersion after the longitudinal stretching by means of 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 / IPA polyester, type SP41, Ticona, USA), 0.15% by weight of colloidal silicon dioxide (Nalco 1060) as an antiblocking agent and 0.15% by weight ammonium carbonate (Merck, Germany) as a pH buffer. The wet application weight was 2 g / m ² per coated side. After the transverse stretching, the calculated thickness of the coating was 40 nm.

Example 7

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

In contrast to Example 6, the coated film contained no titanium dioxide, but 1% by weight of CI pigment blue 28 (CoAl ₂ O 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 for example 7 the film was uncoated.

The film was corona treated on top layer C. The intensity became like this chosen that the surface tension was <45 mN / m.

Example 9

Analogously to Example 2, a 50 μm thick monofilm was produced which had 0.4% by weight Contained titanium dioxide and equipped with 0.2 wt .-% triclosan antimicrobial was that was metered in in the form of a 10.0 wt .-% masterbatch.

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

Analogously to example 2, the film to improve the UV stability contained 0.6% by weight. of the UV stabilizer Tinuvin 1577. The UV stabilizer was in shape of a 20.0% by weight master batch.  

The film also contained 0.2% by weight of hydrolysis stabilizer and 4.0% by weight. Flame retardant according to example 3.

After the longitudinal stretching, the film was coated on both sides with an aqueous dispersion using the “reverse gravure-roll coating” method. The dispersion corresponds to the information in Example 4. The wet application weight was 2 g / m ² per coated side. After the transverse stretching, the calculated thickness of the coating was 40 nm.

Example 10

A 50 μm thick, coextruded film was produced.

The formulation of the 47 µm thick base layer B corresponded to the formulation of Monofilm from Example 9, so it contained one in addition to PET titanium dioxide, triclosan UV stabilizer, a flame retardant and a hydrolysis stabilizer.

The formulation of the 2.5 µm thick cover layers A and C corresponded to the formulation from example 5. Analogous to example 9, the cover layer C with the adhesion promoter was SP41 coated.

Comparative Example 1

Analogously to Example 1, a 50 µm thick, monochrome, colored film was used manufactured. In contrast to Example 1, the film did not contain triclosan, so it was not antimicrobial. The film became analogous to Example 1 on both sides coated.

The properties of the films produced are shown in the table below refer to.  

Claims (18)

1. Colored, antimicrobial, biaxially oriented, partially crystalline film, the thickness of which is in the range from 1 to 500 μm, according to main application DE 101. , , , , (internal no. 01 / 013MFE), which contains a crystallizable thermoplastic as the main component and additionally as an antimicrobial component 2,4,4'-trichloro-2'-hydroxy-diphenyl ether ("Triclosan") alone or a mixture of Triclosan with other anti-microbial Contains substances and at least one coloring pigment, characterized in that it is provided with at least one additional functionality. 2. Film according to claim 1, characterized in that the crystallized Thermoplastic a polyethylene terephthalate, polybutylene terephthalate, poly ethylene naphthalate, bibenzene-modified polyethylene terephthalate or Mixtures thereof, preferably polyethylene terephthalate, polyethylene is naphthalate or bibenzene-modified polyethylene terephthalate. 3. Film according to claim 1 or 2, characterized in that the conc triclosan in the range of 0.005 to 10.0 wt .-%, preferably 0.01 to 5.0 wt -.%, Based on the weight of the crystallizable Thermoplastics. 4. Film according to one or more of claims 1 to 3, characterized records that the other antimicrobial substances 10,10'-oxy-bis- phenoxarsin, N- (trihalomethylthio) phthalimide, diphenylantimon-2- ethylhexanoate, copper 8-hydroxyquinoline, tributyltin oxide and the like Derivatives and derivatives of halogenated diphenyl ether compounds are. 5. Film according to one or more of claims 1 to 4, characterized characterized in that the coloring pigment in a concentration in Range from 0.2 to 40.0% by weight, preferably from 0.3 to 25.0% by weight,  particularly 1.0 to 25.0% by weight, based on the weight of the thermo plastic, is included. 6. Film according to one or more of claims 1 to 5, characterized characterized in that inorganic pigments as white and Black pigments as well as inorganic or organic colored pigments are included. 7. Film according to one or more of claims 1 to 6, characterized characterized in that the film is flame retardant with a flame retardant and / or equipped with UV stabilizers and / or with a soluble Dye is colored and / or is sealable and / or on one or is coated on both surfaces and / or on one or both sides is corona treated. 8. Film according to one or more of claims 1 to 7, characterized characterized in that the concentration of the UV absorber in the range of 0.01 to 5.0% by weight, preferably 0.1 to 3.0% by weight, the concentration of the flame retardant in the range of 0.5 to 30.0 wt .-%, 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 thermo plastic, lies. 9. Film according to one or more of claims 1 to 8, characterized records that the UV absorber as 2-hydroxybenzophenones, 2-hydroxy benzotriazoles, nickel-organic compounds, salicylic acid esters, cinnamic acid ester derivatives, resorcinol monobenzoates, oxalic acid anilides, hydroxybenzoe acid esters, sterically hindered amines and triazines, preferably 2- Hydroxybenzotriazoles and triazines and especially 2- (4,6-diphenyl-1,3,5- triazin-2-yl) -5- (hexyloxy) phenol or 2,2'-methylene-bis (6- (2H-benzotriazol- 2-yl) -4- (1,1,2,2, -tetramethylpropyl) phenol are present.   10. Film according to one or more of claims 1 to 9, characterized characterized in that the flame retardant organic phosphorus compound dungen, preferably carboxyphosphinic acids, their anhydrides and Contains dimethyl methyl phosphonate. 11. Film according to one or more of claims 1 to 10, characterized records that a hydrolysis stabilizer in the form of phenolic Stabili catalysts, alkali / alkaline earth stearates and / or alkali / alkaline earth carbonates in an amount of 0.01 to 1.0 wt .-%, preferably phenolic Stabilisa toren in an amount of 0.05 to 0.6 wt .-%, in particular 0.15 to 0.3 wt .-% and with a molecular weight of more than 500 g / mol, is included. 12. Film according to one or more of claims 1 to 11, characterized records that the regenerate is used. 13. Process for the production of a colored, antimicrobial color prepared, biaxially oriented, partially crystalline film according to the main anmel EN 101. , , , , (internal no. 01 / 013MFE) with further functionalities from a crystallizable thermoplastic with a thickness in the range of 1 to 500 µm, characterized in that a crystallizable thermo plast with an antimicrobial substance, at least one color Pigment and other substances that confer functionality an extrusion process into a flat melt film, with Quenched into a largely amorphous pre-film with the help of a cooling roll, this film is then heated again and at least once in longitudinal and stretched in the transverse direction, then at temperatures of 200 to 280 ° C is heat set and finally cooled and wound up. Film solidified becomes. 14. The method according to claim 13, characterized in that the film be layers and / or equipped with at least one sealing layer and / or is corona treated.   15. The method according to claim 13 or 14, characterized in that the antimicrobial substance in the form of 2,4,4'-trichloro-2'-hydroxy-diphenyl ether ("triclosan") alone or a mixture of triclosan and others antimicrobial substances and the other substances in the Foil production are metered into the extruder, the addition over masterbatch technology is preferred. 16. The method according to one or more of claims 13 to 15, characterized characterized in that in the masterbatch in addition to the thermoplastic 0.4 to 30.0 wt .-%, preferably 0.8 to 15.0% by weight of the antimicrobial substance is contained, the sum of the constituents 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 a lamination medium, in medical Area, as packaging film, in the disposal area and environmental protection.