DE10100703A1 - Multilayer, biaxially oriented and thermofixed polyester film with a matt finish, e.g. for packaging, decorative or medical applications, includes triclosan as an antimicrobial agent - Google Patents

Abstract

Multilayer, biaxially oriented and thermofixed film comprising a crystallized thermoplastic base layer and at least one matt polyester covering layer includes triclosan in at least one layer. Multilayer, biaxially oriented and thermofixed film comprising a crystallized thermoplastic base layer and at least one matt polyester covering layer includes triclosan (2,4,4'-trichloro-2'-hydroxy diphenyl ether) in at least one layer, where the polyester is a blend of a polyethylene terephthalate homo- or copolymer and a copolyester in which the diol units are derived from aliphatic or alicyclic diols with 2-11 carbon atoms and the dicarboxylic acid units comprise 65-95 mole% isophthalic acid units, 5-15 mole% units derived from a sulfo-substituted aromatic dicarboxylic acid and 0-20 mole% units derived from an aliphatic dicarboxylic acid of formula (I): HOOC(CH2)nCOOH (I) n = 1-11. An Independent claim is also included for production of the film by coextruding the base and covering layers and then biaxially stretching and thermofixing the film.

Description

The invention relates to further developments of the main application DE 101. , , (internal no. 01 / 002MFE) described multilayer, biaxially oriented and heat-set film with a base layer made of a crystallizable thermoplastic and at least one cover layer with a matt surface, the cover layer comprising a mixture or a blend consisting of a) a polyethylene terephthalate Homopolymer and / or copolymer and b) a polyethylene terephthalate copolymer, the dicarboxylic acid units of which are 65 to 95 mol% from isophthalic acid units and 1 to 20 mol% of units of aliphatic dicarboxylic acids of the formula HO ₂ C- [ CH ₂ ] _n -CO ₂ H, where n is an integer from 1 to 11, and 4 to 15 mol% of units of aromatic dicarboxylic acids which - bound to the aromatic part - have at least one sulfonate group and its diol -Units are units of aliphatic or cycloaliphatic diols with 2 to 11 carbon atoms and at least one layer of the film is an antimicrobial ante has 2,4,4'-trichloro-2'-hydroxy-diphenyl ether (triclosan). It also relates to a method for producing this film and its use.

Polyester films with a matt top layer have already been described. So is in US-A 4 399 179 a polyester film laminate with a biaxially stretched transparent base layer and at least one at least monoaxially ver stretched, matte top layer disclosed, the matte layer essentially from a polyethylene terephthalate copolymer with units of oligo- or Polyethylene glycol and inert particles. The particles (preferably from Silicic acid, kaolin, talc, zinc oxide, aluminum oxide, calcium carbonate or Barium sulfate) usually have a diameter of 0.3 to 20 µm. Your share in the Cover layer is generally 3 to 40 wt .-%. Base and / or top layer can also contain antioxidants, UV absorbers, pigments or dyes  contain. The surface of the cover layer roughened by the particles is writable.

The prior art also includes polyester films that are applied to one or the other are functionalized in other ways. A multilayer, biaxially oriented and Heat-set polyester film is the subject of GB-A 1 465 973, for example. The film comprises a layer of transparent PET and a layer of a transparent copolyester. The surface of the copolyester layer can be embossed with the help of rollers, so that the slide is writable.

EP-A 035 835 describes a biaxially stretched and heat-set, more Layered polyester film described, which is a layer of a highly crystalline Polyester and with it a sealable layer made of an im comprises essentially amorphous, linear polyester. The latter layer contains finely divided particles whose average diameter is larger than that Layer thickness. Surface protrusions are formed by the particles Prevent unwanted blocking and sticking to rollers or guides. The This makes it easier to wind up and process the film. By choosing Particles with a larger diameter than the sealing layer and in the The sealing behavior of the film is shown in the examples deteriorated. The sealed seam strength of the sealed film at 140 ° C 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 film with a polyester Base layer, a cover layer of a sealable polyester and a described on the back polyacrylate coating. The sealable top layer can be made from a copolyester with units of isophthalic acid and tere phthalic acid exist. The film can be coated on the back better processing. For an 11 µm thick sealing layer, a sealing seam strength becomes  of 761.5 N / m (11.4 N / 15 mm) at a temperature of 140 ° C specified. A disadvantage of the back acrylic coating is that it Side no longer seals against the sealable top layer. The film is there to be used only to a very limited extent.

A coextruded, multilayer, sealable polyester film is also in the EP-A 515 096. The sealable layer also contains pigments tion particles, preferably silica gel particles. The particles can also on the already extruded film are applied, for example by coating with an aqueous silica gel dispersion. This should make the film the good seal Maintain properties and be easy to process. The back only contains very few particles, mainly over the regranulate in this layer reach. The seal seam strength is measured at 140 ° C and is more than 200 N / m (3 N / 15 mm). For a 3 µm thick sealing layer one Seal seam strength of 275 N / m (4.125 N / 15 mm) specified.

The coextruded, multilayer polyester film known from WO 98/06575 comprises a sealable cover layer and a non-sealable base layer. The base layer can be made up of one or more layers, the inner layer being in contact with the sealable layer. The other The (outer) layer then forms the second, non-sealable top layer. The sealable cover layer can also consist of copolyesters with units Isophthalic acid and terephthalic acid exist. However, the top layer contains no antiblock particles. The film also contains at least one UV Absorber in the base layer in a weight ratio of 0.1 to 10% is included. As UV absorbers are preferably triazines, for. B. ®Tinuvin 1577 from Ciba. The base layer is with common antiblocking agents fitted. The film is characterized by a good sealability however not the desired processing behavior and also shows deficits in the optical properties.  

Layers of copolyester can also be removed by applying an ent produce talking aqueous dispersion. So is in EP-A 144 878 Described polyester film that has a continuous on at least one side Coating from the copolyester carries. The dispersion is placed on the film the stretching or applied before the last stretching step. The Polyester coating consists of a condensation product from various those monomers capable of forming polyesters, such as Iso phthalic acid, aliphatic dicarboxylic acids, sulfomonomers and aliphatic or cycloaliphatic glycols.

DE-A 23 46 787 contains, among other things, flame-retardant films linear polyesters modified with carboxyphosphinic acids. However, the manufacture of these films has a number of problems prevented. So the raw material is very sensitive to hydrolysis and has to be done very well be dried. When drying the raw material with dryers that stand correspond to the technology, he glued, so that only under the most difficult conditions a film can be produced. The under extreme, uneconomical conditions The foils produced also become brittle when exposed to high temperatures. The mechanical properties decrease so much that the film becomes unusable. This embrittlement occurs after 48 hours of thermal stress on.

In the prior art there is no evidence of how a film at least on one side a low gloss with high transparency can be awarded, at the same time the film is antimicrobial and shows no embrittlement after temperature exposure. Therefore it exists there is still a need for transparent, antimicrobial-treated films for whom at least one side appears matt.  

The object of the present invention was therefore that in the main application DE 101. , , described antimicrobially equipped, transparent poly ester film, which has at least one matt surface, with special Equip functionalities.

The present invention accordingly relates to a multilayer, biaxially oriented and heat-set film according to main application DE 101 with a base layer made of a crystallizable thermoplastic and at least one cover layer with a matt surface, the cover layer comprising a mixture or a blend consisting of

• a) a polyethylene terephthalate homopolymer and / or copolymer and
• b) a polyethylene terephthalate copolymer, the dicarboxylic acid units
  65 to 95 mol% from isophthalic acid units,
  0 to 20 mol% of units of aliphatic dicarboxylic acids of the formula HO ₂ C- [CH ₂ ] _n -CO ₂ H, where n is an integer from 1 to 11, and
  5 to 15 mol% of units of aromatic dicarboxylic acids which - bound to the aromatic part - have at least one sulfonate group,
  and whose diol units are units made from aliphatic or cyclo aliphatic diols having 2 to 11 carbon atoms,

and at least one layer of the film has an antimicrobial effect 2,4,4'-trichloro-2'-hydroxy-diphenyl ether (triclosan), characterized thereby records that the film is provided with at least one other functionality.  

The proportion of triclosan is generally 0.01 to 10% by weight, preferably 0.1 up to 5% by weight, based in each case on the weight of the layer equipped with it.

Under the name "polyethylene terephthalate homopolymer" polymers are understood, in addition to ethylene glycol and terephthalic acid units contain no further monomer units. "Polyethylene terephthalate copoly mere "accordingly also contain units from other diols and / or dicarboxylic acids.

The additional functionality is preferably that the film against UV radiation stabilized, flame retardant, on one side or on coated on both sides, sealable and / or corona or flame treated.

The cover layer of the film according to the invention is characterized by a characteristic matt surface or optics. Their good mechanical properties include a high modulus of elasticity (in the longitudinal direction = machine direction (MD) more than 3,200 N / mm ² ; in the transverse direction (TD) more than 3,500 N / mm ² ) and good tensile strength values (in MD more than 100 N / mm ² ; in TD more than 130 N / mm ² ). The film can be stretched excellently in both its longitudinal and transverse directions and without tears.

For the purposes of the present invention, mixtures are mechanical To understand mixtures that are made from the individual components. in the In general, the individual components are molded parts small size, e.g. B. lenticular or spherical granules, poured together and mixed mechanically with a suitable vibrator. Another way to create a mix is to use the Components a) and b) in granular form, each separately for the extruder for the top layer according to the invention and the mixture in  Extruder, or carried out in the subsequent melt-carrying systems becomes.

A blend in the sense of the present invention is an alloy-like composite of the individual components a) and b), which are no longer in the original Components can be disassembled. It has properties like a homogeneous one Substance and can be characterized by appropriate parameters.

The film according to the invention has at least two layers. It then includes one Base layer B and a cover layer A. In a preferred embodiment According to the invention, the film is constructed in three layers and has on one side Layer B has a top layer A and another on the other side Top layer C. According to the invention, the antimicrobial agent in the top layer (s) and / or the base layer.

The base layer B of the film preferably consists of at least 70% by weight of a thermoplastic polyester. Polyesters made from ethylene glycol and terephthalic acid (= polyethylene terephthalate, PET), from ethylene glycol and naphthalene-2,6-dicarboxylic acid (= polyethylene-2,6-naphthalate, PEN), from 1,4-bis hydroxymethyl-cyclohexane and terephthalic acid (= Poly-1,4-cyclohexanedimethylene lerephthalate, PCDT) and from ethylene glycol, naphthalene-2,6-dicarboxylic acid and biphenyl-4,4'-dicarboxylic acid (= polyethylene-2,6-naphthalate bibenzoate, PENBB). Particularly preferred are polyesters which consist of at least 90 mol%, preferably at least 95 mol%, of ethylene glycol and terephthalic acid units or of ethylene glycol and naphthalene-2,6-dicarboxylic acid units. The remaining monomer units come from other aliphatic, cycloaliphatic or aromatic diols or dicarboxylic acids. Suitable other aliphatic diols are, for example, diethylene glycol, triethylene glycol, aliphatic glycols of the general formula HO- (CH ₂ ) _n -OH, where n represents an integer from 3 to 6 (in particular propane-1,3-diol, butane-1,4) diol, pentane-1,5-diol and hexane-1,6-diol) or branched aliphatic glycols with up to 6 carbon atoms. Of the cycloaliphatic diols, cyclohexanediols (in particular cyclohexane-1,4-diol) may be mentioned. Suitable other aromatic diols correspond, for example, to the formula HO-C ₆ H ₄ -XC ₆ H ₄ -OH, where X is -CH ₂ -, -C (CH ₃ ) ₂ -, -C (CF ₃ ) ₂ -, -O -, -S- or -SO ₂ - stands. In addition, bisphenols of the formula HO-C ₆ H ₄ -C ₆ H ₄ -OH are also very suitable.

Other aromatic dicarboxylic acids are preferably benzenedicarboxylic acids, naphthalenedicarboxylic acids (for example naphthalene-1,4- or -1,6-dicarboxylic acid), biphenyl-x, x'-dicarboxylic acids (in particular biphenyl-4,4'-dicarboxylic acid), diphenylacetylene-x, x'-dicarboxylic acids (especially diphenylacetylene-4,4'-dicarboxylic acid) or stilbene-x, x'-dicarboxylic acids. Of the cycloaliphatic dicarboxylic acids, cyclohexanedicarboxylic acids (in particular cyclohexane-1,4-dicarboxylic acid) should be mentioned. Of the aliphatic dicarboxylic acids, the (C ₃ -C ₁₉ ) alkanedioic acids are particularly suitable, the alkane fraction being straight-chain or branched.

The polyester can be produced, for example, after the transesterification proceed. It is based on dicarboxylic acid esters and diols, which with the usual transesterification catalysts, such as zinc, calcium, lithium, Magnesium and manganese salts are implemented. The intermediates are then in the presence of common polycondensation catalysts, such as antimony trioxide or titanium salts, polycondensed. The manufacture can just as well by the direct esterification process in the presence of poly condensation catalysts. You go directly from the Dicarbon acids and the diols.

Contains at least one cover layer of the multilayer film according to the invention a mixture or a blend with the two described in more detail below Components a) and b) and optionally additives.  

Component a) of the cover layer preferably consists essentially of a polyethylene terephthalate homo- or copolymer, especially one those as already described for the base layer. For the Generating high levels of matting has proven to be beneficial if the Component a) making up polyester has a comparatively low viscosity having. A is used to describe the viscosities of the melts modified solvent viscosity (SV value) used. For standard ones Polyethylene terephthalate, which is used for the production of biaxially oriented films are suitable, the SV values are in the range from 500 to 1200. To a high mattness to get the film in the sense of the present invention, it has proven to be proved to be favorable if the SV value of the polyethylene terephthalate or copolymers a) in the range from 500 to 800, preferably in the range from 500 to 750, particularly preferably in the range from 500 to 700.

Aliphatic dicarboxylic acids for the preparation of the copolyester b) are especially malon, adipine, azelaine, glutar, sebacin, cork, amber and brassylic acid and mixtures of these acids or their for the formation of Derivatives capable of polyesters. Of the acids mentioned, sebacic acid prefers.

The aromatic dicarboxylic acid, which, bound to the aromatic part, has at least one sulfonate group, preferably corresponds to the formula

wherein
Z is a 3-valent aromatic residue and
M is an alkali metal cation, preferably Na ⁺ , K ⁺ or Li ⁺ .

Monomers of this type are known and in US-A 3,563,942 and US-A 3,779,993 described. Examples of such monomers are sodium sulphere phthalic acid, sodium 5-sulfoisophthalic acid, sodium sulfophthalic acid, 5-para Sodium sulfophenoxy-isophthalic acid, 5-sodium sulfopropoxy-isophthalic acid and Similar monomers and their derivatives capable of forming polyesters, z. B. dimethyl ester. The trivalent aromatic radical Z in the formula mentioned is therefore preferably a trivalent benzene radical. Under the term "for Derivatives capable of forming polyesters are compounds with groups to understand the condensation reactions, especially transesterification reactions capable of forming ester bonds. These include Carboxyl groups and their lower alkyl esters, e.g. B. dimethyl terephthalate, Diethyl terephthalate and numerous other esters, halides or salts. before the acid monomers are used as dimethyl esters because of this Way the condensation reaction can be better controlled.

The diol units in the copolyester b) are in particular units of Ethylene glycol, 1,5-pentadiol, 1,6-hexanediol, neopentyl glycol, 1,10-decanediol and / or cyclohexanedimethanol. Ethylene glycol is preferably used. The Diol component is present in a stoichiometric amount.

The copolyesters can be made by known polymerization techniques become. In general, the procedure is such that the acid components with glycol brought together and heated in the presence of an esterification catalyst are and then a polycondensation catalyst is added.

It has been shown that the proportions of the individual components for the copolyester b) are decisive for achieving the matt top layer. So that is Proportion of isophthalic acid units at least 65 mol%, preferably 70 to 95 mol%, each based on the total of the dicarboxylic acid units.  

For aliphatic dicarboxylic acid, it applies that any acid with the formula mentioned brings satisfactory results, being adipic acid, azelaic acid, sebacin acid, malonic acid, succinic acid, glutaric acid and mixtures of these acids are preferred. The proportion of units from aliphatic dicarboxylic acids is up to 20 mol%, preferably 1 to 15 mol%, in each case based on the Acid component of the copolyester b).

The copolyesters suitable for the purposes of the invention continue to stand out characterized in that they have an acid number of less than 10, preferably from 0 to 3, an average molecular weight of less than about 50,000 and an SV value in the range of about 30 to 700, preferably about 350 to 650.

The weight ratio of component a) to component b) can be within further limits vary and depends on the intended application the multilayer film. The ratio of component a) to component b) is generally in the range from 10:90 to 95: 5, preferably from 20:80 to 95: 5, particularly preferably from 30:70 to 95: 5.

The antimicrobial agent triclosan is preferably the so-called Masterbatch technology metered in directly during film production. As a carrier materials for the masterbatch come from the thermoplastic itself (especially Polyethylene terephthalate) or other polymers with the thermoplastic are sufficiently tolerated. It is important that grain size and Bulk weight of the masterbatch is the same or at least similar to the grain size and the bulk density of the thermoplastic are therefore homogeneous Distribution is achieved. The proportion of antimicrobial agent in the masterbatch is generally 0.4 to 30% by weight, preferably 0.8 to 15% by weight, each based on the weight of the carrier material.  

In addition to triclosan, the film can also have other antimicrobial compounds included. These are, for example, 10,10'-oxy-bisphenox-arsine, N- Trihalomethylthio-phthalimide, diphenylantimon-2-ethylhexanoate, copper-8- hydroxy-quinoline, tributyltin oxide and its derivatives and derivatives of halogenated diphenyl ether compounds, the above derivatives of 2,4,4'-trichloro-2-hydroxy-diphenyl ether are particularly preferred. This Derivatives (especially esters and ethers) of triclosan are, for example, in WO 99/31036 described. They are thermally stable and show a low level Volatility with little tendency to migrate. The other antimicrobial active compounds are preferably also used as a masterbatch added.

A further development of the film described in the main application is that it is coated on at least one side. The coating on the finished film generally has a thickness of 5 to 100 nm, preferably 20 to 70 nm, in particular 30 to 50 nm. It is preferably applied in-line, ie during the film production process, expediently before transverse stretching. Application by means of the "reverse gravure-roll coating" method is particularly preferred, in which the coating can be applied extremely homogeneously in the layer thickness mentioned. The coatings are applied - preferably in water - as solutions, suspensions or dispersions. The coatings mentioned give the film surface additional functionality. For example, this makes the film sealable, printable, metallizable, sterilizable, antistatic, shows an improved aroma barrier or an improved adhesion of materials which would otherwise not adhere to the film surface (e.g. photographic emulsions). Examples of substances or compositions which give additional functionality are acrylates (see WO 94/13476), ethyl vinyl alcohols, PVDC, water glass (Na ₂ SiO ₄ ), hydrophilic polyesters (5-Na-sulfoisophthalic acid-containing PET / IPA polyesters as in EP-A 144 878 or US Pat. No. 4,252,885), copolymers with vinyl acetate units (see WO 94/13481), polyvinyl acetates, polyurethanes, alkali metal or alkaline earth metal salts of (C ₁₀ -C ₁₈ ) fatty acids, copolymers with units from butadiene and Acrylonitrile, methyl methacrylate, methacrylic acid and / or acrylic acid and / or their esters. The substances or compositions which impart the additional functionality can contain the customary additives, such as antiblocking agents and / or pH stabilizers, in amounts of 0.05 to 5% by weight, preferably 0.1 to 3% by weight ,

The substances or compositions mentioned are as diluted - before preferably aqueous - solution, emulsion or dispersion on one or both Sides of the film applied. The solvent is then removed. If the coatings are applied in-line before transverse stretching, it is sufficient usually undergo heat treatment prior to transverse stretching to Volatilize solvent and 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.

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

In one development, the film according to the invention is also UV-stable equipped. Light, especially the ultraviolet portion of solar radiation, i.e. H. the wavelength range from 280 to 400 nm, induced in thermoplastics Degradation processes, as a result of which not only the visual appearance by changing color or yellowing changes, but by that too the mechanical-physical properties of the films made of thermoplastics be influenced extremely negatively. The prevention of this photooxidative Mining operations is of considerable technical and economic importance, otherwise the application possibilities of numerous thermoplastics  are drastically restricted. For example, polyethylene terephthalates begin absorbing UV light below 360 nm, their absorption decreases below 320 nm considerably and is very low below 300 nm embossed. The maximum absorption is between 280 and 300 nm. In The presence of oxygen is mainly observed in chain cleavages, however no networking. Carbon monoxide, carbon dioxide and carboxylic acids represent the quantitatively predominant photo-oxidation products the direct photolysis of the ester groups still have to undergo oxidation reactions The formation of peroxide radicals should also be considered Cause carbon dioxide. Photooxidation of polyethylene terephthalates can also via the elimination of hydrogen in the α-position of the ester groups Hydroperoxides and their decomposition products and related to them Chain cleavages lead (H. Day, D. M. Wiles: J. Appl. Polym. Sci 16, 1972, page 203).

UV stabilizers, d. H. UV absorbers as light stabilizers are chemical Compounds involved in the physical and chemical processes of light intervention induced degradation. Soot and other pigments can partially Effect sun protection. However, these substances are for brightly colored or even Covered colored films are unsuitable because they are used for discoloration or color change to lead. Suitable UV stabilizers as light stabilizers are UV stabilizers, the at least 70%, preferably 80%, particularly preferably 90%, of the UV Light in the wavelength range from 180 nm to 380 nm, preferably 280 to Absorb 350 nm. These are particularly suitable if they are in the Temperature range of 260 to 300 ° C are thermally stable, d. H. not in Decompose fission products and do not outgas. Suitable UV stabilizers as Light stabilizers are, for example, 2-hydroxybenzophenones, 2-hydroxybenzo triazoles, nickel-organic compounds, salicylic acid esters, cinnamic acid esters Derivatives, resorcinol monobenzoates, oxalic acid anilides, hydroxybenzoic acid esters,  Benzoxazinone, sterically hindered amines and triazines, the 2-hydroxy benzotriazoles, the benzoxazinones and the triazines are preferred.

It was completely surprising for the experts that the use of UV Stabilizers in combination with an antimicrobial finish too usable films with excellent properties. The specialist would have probably first tried some UV stability over one Reaching the oxidation stabilizer would have to be done immediately after weathering found that the film quickly turns yellow.

UV stabilizers which absorb UV radiation are known from the literature and thus offer protection. The specialist would then probably have one of these known and commercial UV stabilizers used, but found that the UV stabilizer has poor thermal stability and Temperatures between 200 and 240 ° C decomposed or outgassed in fission products. In order not to damage the film, it would have large amounts (approx. 10 to 15% by weight) need to work on the UV stabilizer so that it really has the UV light effectively absorbed. At these high concentrations, however, the film yellows after the production. The mechanical properties too negatively influenced. Unusual problems arise when stretching, such as Demolition due to lack of strength, d. H. E-module, nozzle deposits, what leads to profile fluctuations, deposition of UV stabilizer on the rollers, what affects the optical properties (severe turbidity, Adhesive defect, inhomogeneous surface), and deposits in the stretch and Fixation frames that drip onto the film.

It was therefore surprising that even with low concentrations of UV Stabilizer an excellent UV protection is achieved. Particularly surprising was that the yellowness index of the film did not change compared to one stabilized film does not change within the measurement accuracy. It also occur  no outgassing, nozzle deposits or frame evaporation, which gives the film an excellent appearance, an excellent profile and a has excellent flatness. The UV-stabilized film can be stretch perfectly, so that they are reliable and stable so-called "high speed film lines" up to speeds of 420 m / min can be produced reliably. The film is also economical producible profitably. Furthermore, it is very surprising that that too Regenerate can be used again without negatively affecting the yellowness index of the film influence.

In a very particularly preferred embodiment, the film according to the invention contains 0.1 to 5.0% by weight of 2- (4,6-diphenyl- [1,3,5] triazin-2-yl) -5 as UV stabilizer -hexyloxy-phenol of the formula

or 0.1 to 5.0% by weight of 2,2'-methylene-bis- [6-benzotriazol-2-yl-4- (1,1,2,2-tetra methyl-propyl) phenol] formula

or 0.1 to 5.0% by weight of 2,2 '- (1,4-phenylene) -bis - ([3.1] benzoxazin-4-one) of the formula

In a further embodiment, mixtures of these UV Stabilizers or mixtures of at least one of these UV stabilizers can be used with other UV stabilizers, the total concentration tration of light stabilizers, preferably between 0.1 and 5.0% by weight, particularly preferably in the range from 0.5 to 3.0% by weight, based on the Weight of the finished layer.

In a further embodiment, the film according to the invention is flame inhibiting equipped. Flame retardant means that the film in one so - called fire protection test the conditions according to DIN 4102 part 2 and in particular the requirements of DIN 4102 Part 1 are met and in the Building material class B 2 and especially B1 of the flame retardant materials can be classified. Furthermore, the should be flame retardant if necessary equipped film the UL test 94 "Horizontal Burning Test for Flammability of Plastic Material "exist, so that they are classified in the class 94 VTM-0 can. The film accordingly contains a flame retardant, which also has the  Masterbatch technology is metered directly during film production, whereby the proportion of the flame retardant in the range from 0.5 to 30.0% by weight, preferably from 1.0 to 20.0% by weight, based on the weight of the layer of the crystallizable thermoplastic. In the masterbatch, the share of the Flame retardant in general 5 to 60 wt .-%, preferably 10 to 50 wt .-%, each based on the total weight of the masterbatch. suitable Flame retardants are, for example, bromine compounds, chlorinated paraffins and other chlorine compounds, antimony trioxide and aluminum hydroxide. The However, halogen compounds have the disadvantage that they contain halogen By-products can arise. In the event of fire arise in particular Hydrogen halides. Another disadvantage is the low lightfastness of one equipped with foil. Other suitable flame retardants are for example organic phosphorus compounds such as carboxyphosphinic acids, their anhydrides and dimethyl methanephosphonate. It is essential 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 useful his. Phenolic stabilizers are generally used as hydrolysis stabilizers, Alkali or alkaline earth stearates and / or alkali or alkaline earth carbonates in quantities from 0.01 to 1.0% by weight. Phenolic stabilizers are used in one Amount of 0.05 to 0.6 wt .-%, in particular 0.15 to 0.3 wt .-% and with a Molar mass of more than 500 g / mol preferred. Pentaerythritol tetrakis-3- (3,5-di-tert-butyl butyl-4-hydroxy-phenyl) propionate or 1,3,5-trimethyl-2,4,6-tris- (3,5-di-tert.- butyl-4-hydroxy-benzyl) benzene are particularly advantageous.

In this preferred embodiment, the invention contains heavy flammable film as the main component a crystallizable PET, 1 wt .-% to 20% 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. Methanephosphonic acid dimethyl ester is a flame retardant prefers. Have these proportions of flame retardant and hydrolysis stabilizer proved to be favorable even if the main component of the film is not Is PET, but is another thermoplastic.

Surprisingly, fire protection tests according to DIN 4102 and the UL Test showed that it was quite sufficient in the case of a three-layer film is to equip the 0.5 to 2 µm 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.

Surprisingly, films according to the invention meet in the thickness range 10 to 350 µm the requirements of building material classes B2 and B1 according to DIN 4102 and UL test 94.

Where a very good sealability is required and where this property is not Can be achieved via an online coating is the one according to the invention Foil at least three layers and then includes a special one Embodiment the base layer B, a sealable cover layer C and the previously described matt top layer A.

The sealable deck applied to base layer B by coextrusion Layer C is based on polyester copolymers and consists of essentially from copolyesters, mainly from isophthalic acid, bibenzene carboxylic acid and terephthalic acid units and from ethylene glycol units are composed. The remaining monomer units come from others aliphatic, cycloaliphatic or aromatic diols or dicarboxylic acids, as they can also occur in the base layer. The preferred copolyesters,  that provide the desired sealing properties are those that from ethylene terephthalate and ethylene isophthalate units and from ethylene glycol Units are built. The proportion of ethylene terephthalate is 40 to 95 mol% and the corresponding proportion of ethylene isophthalate 60 to 5 mol%. Preferred copolyesters are those in which the proportion of ethylene terephthalate is 50 to 90 mol% and the corresponding proportion of ethylene isophthalate 50 to 10 mol% is and very preferred are copolyesters in which the proportion of ethylene terephthalate 60 to 85 mol% and the corresponding proportion of ethylene isophthalate is 40 to 15 mol%. In contrast to the matt cover layer A is the cover layer C sealable.

The desired sealing and processing properties of the fiction moderate film are made from the combination of the properties of the used Copolyesters for the sealable top layer and the topographies of the seals capable top layer C and the matt top layer A obtained.

The seal starting temperature of 110 ° C and the seal seam strength of at least 1.3 N / 15 mm is achieved if C the copolymers described in more detail above can be used. The best Sealing properties of the film are obtained if the copolymer does not other additives, especially no inorganic or organic fillers be added. In this case you get with a given copolyester the lowest seal starting temperature and the highest seal seam strengths. In this case, however, the handling of the film is poor because of the surface the sealable top layer C tends to block. The film can be hardly wrap and is for further processing on high-speed Packaging machines not suitable. To improve the handling of the Foil and processability, it is necessary to seal the cover layer C to modify. This is best done with the help of suitable ones Antiblocking agents of a selected size, in a certain  Concentration of the sealing layer are added in such a way that on the one hand minimizes blocking and on the other hand only the sealing properties to be insignificantly deteriorated.

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 base layer and / or the cover layers can in addition to the above Masterbatch technology metered antimicrobial agent and the previously described additives additionally other conventional additives, such as stabilizers and antiblocking agents. You will expediently the polymer or Polymer mixture added before melting.

Mixtures of two or more different ones can also be used as additives Antiblocking agents or mixtures of antiblocking agents of the same combination settlement, but different particle size can be selected. The particles can the individual layers in the usual concentrations, eg. B. as glycolic dispersion, during polycondensation or via masterbatches be added during extrusion. Have proven to be particularly suitable Pigment concentrations of 0.0001 to 10 wt .-% based on the weight of the Cover layers proved. By adding these particles to the top layer A you have another advantageous way to vary the degree of matting of the film. As the pigment concentration increases, there is usually an increase the degree of mattness of the film. A detailed description of the Antiblocking agents can be found, for example, in EP-A 602 964.

The present invention also relates to a method for the production this slide. It comprises the production of a film from base and cover layers  through coextrusion, the biaxial stretching of the film and the heat setting the stretched film.

It is important that the masterbatch containing the antimicrobial and optionally containing the flame retardant, pre-crystallized or pre-dried is. 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. up to 150 ° C, especially 30 ° C to 130 ° C, filled. During the approx 6-hour, preferably 5-hour, in particular 4-hour, dwell time the raw material mixture is at 10 to 70 rpm, preferably 15 to 65 rpm, in particular 20 to 60 rpm, stirred. The pre-crystallized or pre-dried raw material mixture is also in a downstream evacuated container at 90 ° C 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.

Granules from the Mixture component a) and granules from mixture component b) in desired mixing ratio and optionally the pre-dried Triclosan masterbatch fed directly to the extruder. It has come in handy proven for the extrusion of the matt top layer according to the invention To use twin-screw extruder, such as z. B. in EP-A 0 826 478 is described. The materials melt at about 300 ° C and a residence time  from about 5 min and can be extruded. Under these conditions transesterification reactions can take place in the extruder, in which further Can form copolymers from the homopolymers and the copolymers.

The polymers for the base layer and the pre-dried triclosan Masterbatch and any other masterbatches are expediently via fed to another extruder. Any foreign objects or Impurities can be removed from the polymer melt before extrusion Filter off. The melts then become flat in a multi-layer nozzle Melt films formed and layered on top of each other. Then will the multilayer film with the help of a cooling roller and, if necessary, further Rolled off and solidified.

The biaxial stretching is generally sequential or simultaneous carried out. In the sequential stretching, it is preferably only in Longitudinal direction (i.e. in the machine direction) and then in the transverse direction (i.e. stretched perpendicular to the machine direction). This leads to an orientation of the Molecular chains. The stretching in the longitudinal direction can be done with the help of two according to the desired stretching ratio running at different speeds Carry out rolling. One generally uses one for transverse stretching Tenter frame. With simultaneous stretching, the film is simultaneously and stretched transversely in a tenter frame.

The temperature at which the drawing is carried out can be in a relative large range vary and depends on the desired properties the slide. In general, the longitudinal stretching at 80 to 130 ° C and the Lateral stretching is carried out at 90 to 150 ° C. The longitudinal stretch ratio is generally in the range from 2.5: 1 to 6: 1, preferably from 3: 1 to 5.5: 1 Cross-stretch ratio is generally in the range from 3.0: 1 to 5.0: 1, preferably from  3.5: 1 to 4.5: 1. If desired, the transverse stretching can be used again connect a longitudinal stretching and even a further transverse stretching.

In the subsequent heat-setting, the film is left for about 0.1 to 10 s kept at a temperature of 150 to 250 ° C. Then the slide in wound up in the usual way.

The polyester film according to the invention preferably also contains a second one Cover layer C, which on the opposite side of the cover layer A Base layer B is arranged. Structure, thickness and composition of the second Top layer can be independent of the existing top layer can be selected, with the second cover layer also the ones already mentioned Polymers, antimicrobial agents or polymer mixtures for the basic or may contain the first top layer, but not with those of the first cover layer must be identical. The second top layer can also contain other common top layer polymers, which also with antimicrobial Active ingredient can be equipped.

If necessary, there may be between the base layer and the cover layers still have an intermediate layer. It can be used for the base layer described polymers exist. In a particularly preferred Embodiment consists of that used for the base layer Polyester. You can also the described antimicrobial agent and contain the usual additives described. The thickness of the intermediate layer is in generally larger than 0.3 μm and is preferably in the range from 0.5 to 15 μm, in particular 1.0 to 10 µm.

The thickness of the cover layers is generally greater than 0.1 μm and lies preferably in the range from 0.2 to 5 μm, in particular 0.2 to 4 μm, the Cover layers can be of the same or different thickness.  

The total thickness of the polyester film according to the invention can vary further Limits vary and depend on the intended use. It is generally 1 to 500 μm, preferably 3 to 350 μm, in particular 6 to 300 μm, the base layer preferably accounting for approximately 40 to 90% of the total thickness.

The film according to the invention can be easily recycled without polluting the environment. Their manufacturing costs are only marginally higher than those of a film Standard polyester raw materials. The other processing and use relevant properties remain essentially unchanged or even are improved. In addition, it is ensured in the manufacture of the film that Regenerate in a proportion of up to 50% by weight, preferably 10 to 50% by weight, based on the total weight of the film, can be reused can without significant physical properties of the film be adversely affected.

So it was more than surprising that using masterbatch technology, a suitable predrying and / or pre-crystallization an antimicrobial equipped film with the required property profile economically and without Gluing can be made in the dryer and that the film also after Temperature load does not become brittle and does not break when bent.

It was also very surprising that with this excellent result and the yellowness index of the film compared to the required antimicrobial effect a film not equipped with Triclosan within the measurement accuracy is not adversely affected. There are also no outgassings, nozzle placement stanchions or frame evaporation, so that the film has an excellent appearance has an excellent profile and flatness. The The film according to the invention is also distinguished by an excellent Stretchability, so that they are reliable and stable on so-called  High speed film lines up to speeds of 420 m / min can be manufactured. This means that production is also economically profitable.

Furthermore, the film according to the invention is characterized by a low gloss, especially on the film surface A, and by a comparative low haze. It also has good winding and processing processing behavior. It is also worth mentioning that the top layer according to the invention can be easily written on with a ballpoint pen, felt-tip pen or fountain pen.

The gloss of the film surface A is less than 70. In a preferred one In one embodiment, the gloss of this side is less than 60 and in one particularly preferred embodiment less than 50 (each with a Angle of incidence of 60 °). This film surface conveys one particularly high advertising character and is therefore particularly suitable as outer surface of a packaging.

The haze of the film is less than 40%. In a preferred embodiment the haze of the film is less than 35% and especially in one preferred embodiment less than 30%. By comparative slight haze of the film (compared to a matt mono film, see Comparative example), the film z. B. can be printed in reverse printing or it Viewing windows can be installed through which z. B. the contents very well is recognizable.

Due to the surprising combination of excellent properties the film according to the invention in its various configurations excellent in a wide range of applications, e.g. B. as Packaging material in the food, pharmaceutical and medical sectors, but also in the disposal area, in advertising, especially for trade fair construction and Trade fair articles, in the construction sector, in the lighting sector, to name just a few areas  call. It is used as a decoration, furniture and packaging film in Shopfitting and shelf construction, as promotional items, illuminated advertising profiles, for signs, as Interior or exterior cladding, as a display, laminating medium, for plants houses, canopies, covers, as a shadow mat etc. It is also for the production of labels, as a release film for the production of GRP Semi-finished products, suitable as stamping foils or in-mold labels.

The following were used to characterize the raw materials and the films Methods used:

measurement methods

DIN = German Institute for Standardization
ISO = International Organization for Standardization
ASTM = American Society for Testing and Materials

Disc diffusion test

The film according to the invention and a reference film, which is not antimicrobial. The one to be checked Place the film on the nutrient agar in a petri dish and then very thinly covered with agar in which the test organisms are are located. Unless there is a substance effective against the organism the test organism becomes the film sample and thus the entire surface of the Overgrown petri dish. A substance that inhibits growth develops noticeable in that at least the film to be examined is not is overgrown or the vegetation around the film is inhibited (Hemmhof). Escherichia coli NCTC 8196 was used as the test culture used.  

SV (DCE) and IV (DVE)

The standard viscosity SV (DCE), based on DIN 53726, is measured in dichloroacetic acid. The intrinsic viscosity (IV) is calculated from the standard viscosity as follows

IV (DCE) = 6.67 x 10 ^-4 SV (DCE) + 0.118

friction

The friction was determined according to DIN 53 375. The sliding friction number became 14 Measured days after production.

surface tension

The surface tension was measured using the so-called ink method (DIN 53 364).

cloudiness

The haze of the film was measured according to ASTM-D 1003-52. The cloudiness Hölz measurement was determined based on ASTM-D 1003-52, where however, in order to utilize the optimal measuring range on four above one another lying film layers measured and instead of a 4 ° perforated aperture a 1 ° gap aperture was used.

shine

The gloss was determined in accordance with DIN 67 530. The reflector value was measured as an optical parameter for the surface of a film. Based on the standards ASTM-D 523-78 and ISO 2813 the angle of incidence was 20 ° or 60 ° set. A light beam hits the at the set angle of incidence flat test surface and is reflected or scattered by it. The on the Light beams striking photoelectronic receivers are called proportional  electrical size is displayed. The measured value is dimensionless and must be included the angle of incidence.

roughness

The roughness R _{a of} the film was determined in accordance with DIN 4768 with a cut-off of 0.25 mm.

Weathering (both sides), UV stability

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

fire behavior

The fire behavior was according to DIN 4102 part 2, building material class B2 and after 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 onset temperature is the temperature at which a seal seam strength of at least 0.5 N / 15 mm is achieved.

Seal strength

Two 15 mm wide films were used to determine the seal seam strength strips laid on top of each other and at 130 ° C, a sealing time of 0.5 s and one Sealing 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.

The examples and comparative examples below are each multilayer, matt films of different thicknesses, which are on an extrusion sionsstraße were produced.

All foils were 1000 on both sides according to the test specification ISO 4892 Hours per side weathered with the Atlas Ci 65 Weather Ometer from Atlas and then regarding the mechanical properties, the discoloration, the surface defects, the turbidity and the gloss checked.

The following examples illustrate the invention without restricting it.

example 1 A) Production of component b) of the cover layer

A copolyester with 90 mol% of isophthalic acid units and 10 mol% on units from the sodium salt of 5-sulfoisophthalic acid as acid component and 100 mol% ethylene glycol as the diol component was after manufactured the following processes:  

A 2 liter reaction vessel made of stainless steel, which was equipped with an anchor stirrer, a thermocouple for measuring the temperature of the vessel contents, an 18 inch Claisen / Vigreux distillation column with cooler and receiver, an inlet opening and a heating jacket, was at 190 ° C preheated, flushed with nitrogen and filled with 1065.6 g of dimethyl isophthalate, 180.6 g of dimethyl 5-sulfoisophthalate sodium salt and 756.9 g of ethylene glycol. In addition, 0.439 g of sodium carbonate decahydrate as a buffer and 0.563 g of manganese (II) acetate tetrahydrate as a transesterification catalyst were added to a vessel. The mixture was heated with stirring while methanol was distilled off. During the distillation, the vessel temperature was gradually raised to 250 ° C. When the weight of the distillate corresponded to the theoretical yield of methanol, an ethylene glycol solution containing 0.188 g of phosphorous acid was added. The distillation column was replaced with a curved steam outlet with template. 20 g of pure ethylene carbonate were added to the reaction mixture, and violent gas evolution (CO ₂ ) started immediately. The CO ₂ evolution subsided after about 10 minutes. A vacuum of 240 mm Hg was then set and the polycondensation catalyst (0.563 g Sb ₂ O ₃ , slurried in ethylene glycol) was added. The reaction mixture was stirred for 10 minutes while maintaining the negative pressure of 240 mm Hg. The pressure was then further reduced in steps of 10 mm Hg / min from 240 mm Hg to 20 mm Hg. As soon as the vacuum in the system was reduced to 20 mm Hg, the vessel temperature was raised from 250 ° C to 290 ° C at a rate of 2 ° C / min. At a temperature of 290 ° C in the vessel, the stirrer speed was reduced and the pressure was reduced to a maximum of 0.1 mm Hg. At this point an ampere meter reading of the stirrer motor was carried out. The viscosity of the polymer was controlled by letting the polycondensation proceed according to fixed values for the change in the amperage of the stirrer motor of (in each case) 2.3 A. When the desired molecular weight was reached, the vessel was pressurized with nitrogen to force the liquid polymer from the bottom plug of the vessel into a quench bath of ice water.

B) Preparation of the mixture for the outer layer A

85% by weight of component a) (polyethylene terephthalate with a SV value of 680) with 15% by weight of component b) Twin screw extruder fed and both components together at about Extruded 300 ° C and fed to the top layer channel A of a multi-layer nozzle.

Through coextrusion and subsequent gradual orientation in longitudinal and The cross direction then became a matt three-layer film with A-B-C structure and a total thickness of 12 microns. The cover layers were thick of 1.5 µm each.

Base layer B

93% by weight of polyethylene terephthalate (RT 49 from KoSa, Germany) with an SV value of 800
5% by weight of masterbatch of 99% by weight of polyethylene terephthalate (RT 49) and 1.0% by weight of silica particles (®Sylobloc 44H from Grace) with an average particle size of 4.5 μm
2% by weight masterbatch of 10% by weight triclosan and 90% by weight polyethylene terephthalate (T 94 VV from KoSa, Germany)

Top layer A

85% by weight of component a) and 15% by weight of component b)

Top layer C

88% by weight of polyethylene terephthalate (RT 49) with an SV value of 800,
10% by weight of masterbatch of 99% by weight of polyethylene terephthalate (RT 49) and 1.0% by weight of silica particles (®Sylobloc 44 H) with an average particle size of 4.5 μm,
2% by weight of masterbatch made from 10% by weight of triclosan and 90% by weight of polyethylene terephthalate (T 94 VV)

The individual process steps were carried out as follows:

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, 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 2

Analogously to Example 1, a 50 μm thick A-B-C film was produced. In the sub In contrast to Example 1, the film contained to improve the UV stability additionally 0.6% by weight of the UV stabilizer 2- (4,6-diphenyl- [1,3,5] triazin-2-yl) -5- hexyloxy-phenol (®Tinuvin 1577 from Ciba-Geigy) in the base layer B and the top layer C. The UV stabilizer was in the form of a masterbatch (20% by weight Tinuvin, 80% by weight PET) added.  

Tinuvin 1577 has a melting point of 149 ° C and is thermal up to approx. 330 ° C stable.

Example 3

A 19 μm thick coextruded A-B-C film was produced.

The main component of the 16 μm thick base layer B was PET, 0.2% by weight Triclosan, 0.2% by weight of hydrolysis stabilizer and 4% by weight of flame retardant. The layer also contained 30% by weight of the material inherent in the film production accruing self-regeneration.

The outer layers A and C were identical to the outer layers from example 1.

The PET from which the transparent film was made had one Standard viscosity SV (DCE) of 810, indicating an intrinsic viscosity IV (DCE) of 0.658 dl / g.

Triclosan was added in the form of a masterbatch which, in addition to PET Contained 10 wt .-% triclosan.

The hydrolysis stabilizer and the flame retardant were in the form of a Masterbatches added. The masterbatch consisted of 20% by weight Flame retardant, 1% by weight hydrolysis stabilizer and 79% by weight PETBB together.

The hydrolysis stabilizer was pentaerythritol tetrakis [3- (3,5- di-tert-butyl-4-hydroxy-phenyl) propionate], in which the flame retardant Methanephosphonate.  

Example 4

Analogously to Example 3, a 19 μm thick ABC film was produced. In contrast to Example 3, the film was coated on one side on the top layer C after the longitudinal stretching by means of a "reverse gravure-roll coating" method with an aqueous dispersion. In addition to water, the dispersion contained 4.2% by weight of a hydrophilic polyester (PET / IPA polyester containing 5-Na-sulfoisophthalic acid, SP41, Ticona, USA), 0.15% by weight of colloidal silicon dioxide (®Nalco 1060) as an antiblocking agent and 0.15% by weight ammonium carbonate 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 main component of the 10 μm thick base layer B was PET, 0.3% by weight Triclosan and 30 wt .-% of the inherent in the film production Eigenregenerates.

For the 1 µm thick sealable top layer C 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 Transesterification catalyst, Mn concentration: 100 ppm).

The top layer C furthermore contained 3.0% by weight of a masterbatch of 97.75% by weight of copolyester and 1.0% by weight of silica particles (®Sylobloc 44 H) and 1.25% by weight of pyrogenic SiO ₂ ( ®Aerosil TT 600 from Degussa).

Cover layer A was identical to cover layer A from example 1.  

The PET from which the transparent film was made had one Standard viscosity SV (DCE) of 810, indicating an intrinsic viscosity IV (DCE) of 0.658 dl / g.

Example 6

Analogously to Example 5, a 12 μm thick, matte, coextruded, sealable ABC film was produced. 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 a “reverse gravure roll coating” method. In addition to water, the dispersion contained 4.2% by weight of hydrophilic polyester (PET / IPA polyester containing 5-sodium sulfoisophthalic acid, SP41, Ticona, USA), 0.15% by weight of colloidal silicon dioxide (®Nalco 1060) as an antiblocking agent and 0.15% by weight ammonium carbonate as 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, matt, coextruded, sealable A-B C-film made. In contrast to Example 6, the film was uncoated.

The film was corona treated on top layer C. The intensity became like this chosen that the surface tension after the corona treatment at more than 45 mN / m.

Example 8

Analogously to Example 2, a 50 μm thick A-B-C film was produced.

Analogously to Example 2, the film contained, in addition to triclosan, to improve the UV Stability an additional 0.6% by weight of the UV stabilizer 2- (4,6-diphenyl- [1,3,5] triazin-2-yl) -5-hexyloxy-phenol (®Tinuvin 1577 from Ciba-Geigy) in  layers B and C. The UV stabilizer was in the form of a 20% by weight Masterbatches added.

The base layer of the film also contained 0.2% by weight of hydrolysis stabilizer and 4 wt% flame retardant. The hydrolysis stabilizer and the flame Protective agents were added in the form of a master batch. The master batch consisted of 20 wt .-% flame retardant, 1 wt .-% hydrolysis stabilizer and 79 wt% PET together. The hydrolysis stabilizer was pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxy-phenyl) propionate] the flame retardant around methyl methanephosphonate.

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 a hydrophilic polyester (5-Na-sulfoisophthalic acid-containing PET / IPA polyester, SP41, Ticona, USA), 0.15% by weight of colloidal silicon dioxide (®Nalco 1060) as an antiblocking agent and 0.15% by weight ammonium carbonate 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 9

Analogously to Example 8, a 50 μm thick A-B-C film was produced and contained it So triclosan, UV stabilizer, flame retardant and hydrolysis stabilizer. in the The difference to example 8 was only the 46 µm thick base layer with triclosan, UV stabilizer, flame retardant and hydrolysis stabilizer equipped.

The 2 µm thick matt cover layer A was identical to that in Example 1. The 2 µm thick sealable cover layer C was identical to that in Example 5. The film remained uncoated.  

Comparative Example (VB) 1

Analogously to Example 1, a 12 μm thick, matt A-B-C film was produced. in the In contrast to Example 1, the film did not contain triclosan, so it was not antimicrobial.

The properties of the films produced can be found in Table 1.

After 1000 hours of weathering per side with Atlas Ci 65 Weather Ometer showed the PET films from Examples 2, 8 and 9 hardly changed Characteristics.

After 1000 hours of weathering per side with an Atlas CI 65 Weather Ometer instructed the films from the other examples and comparative example 1 cracks and embrittlement on the surfaces. A precise one Property profile - especially the mechanical properties - could therefore can no longer be measured. The film also showed one visually visible yellowing.  

Claims (18)

1. Multi-layer, biaxially oriented and heat-set film according to DE 101. , , (int. No. 01 / 002MFE) with a base layer made of a crystallizable thermoplastic and at least one cover layer with a matt surface, the cover layer comprising a mixture of

• a) a polyethylene terephthalate homopolymer or copolymer and
• b) a polyethylene terephthalate copolymer, the dicarboxylic acid units to
  65 to 95 mol% of isophthalic acid units, too
  0 to 20 mol% of units of aliphatic dicarboxylic acids of the formula HO ₂ C- [CH ₂ ] _n -CO ₂ H, where n is an integer from 1 to 11, and to
  5 to 15 mol% of units of aromatic dicarboxylic acids which, bound to the aromatic part, have at least one sulfonate group, and
  whose diol units are units of aliphatic or cyclo aliphatic diols with 2 to 11 carbon atoms,

and at least one layer of the film has an antimicrobial content of 2,4,4'-trichloro-2'-hydroxy-diphenyl ether (triclosan), characterized in that the film has at least one additional functionality. 2. Film according to claim 1, characterized in that the additional Functionality is that it stabilizes against UV radiation,  flame retardant, on one side or on both sides coated, sealable and / or corona or flame treated. 3. Film according to claim 1 or 2, characterized in that contains at least one layer therein a UV stabilizer. 4. Film according to claim 3, characterized in that the UV Stabilizer 2- (4,6-diphenyl- [1,3,5] triazin-2-yl) -5-hexyloxyphenol, 2,2'- Methylenebis [6-benzotriazol-2-yl-4- (1,1,2,2-tetramethyl-propyl) -phenol] or 2,2 '- (1,4-phenylene) bis- [3,1] benzoxazin-4-one]. 5. A film according to claim 3 or 4, characterized in that the proportion the UV stabilizer 0.1 to 5.0% by weight, preferably 0.5 to 3.0% by weight, is, based in each case on the total weight of the at least one Layer. 6. Film according to one or more of claims 1 to 5, characterized characterized in that at least one layer in it is a flame contains protective agents. 7. Film according to claim 6, characterized in that the flame preservative a bromine compound, a chlorinated paraffin or another Chlorine compound, antimony trioxide, aluminum hydroxide or an organic Is phosphorus compound. 8. A film according to claim 6 or 7, characterized in that the proportion the flame retardant 0.5 to 30.0% by weight, preferably 1.0 to 20.0% by weight, each based on the weight of the layer of crystallizable thermoplastics.   9. Film according to one or more of claims 1 to 8, characterized characterized in that they additionally have at least one other antimicrobial contains active compound, preferably 10,10'-oxy-bisphenox-arsine, N- Trihalomethylthio-phthalimide, diphenylantimon-2-ethylhexanoate, Copper-8-hydroxy-quinoline, tributyltin oxide and its derivatives or a Derivative of halogenated diphenyl ether compounds, derivatives of 2,4,4'-trichloro-2-hydroxy-diphenyl ether are particularly preferred. 10. Film according to one or more of claims 1 to 9, characterized characterized in that it additionally comprises a sealable top layer. 11. Film according to one or more of claims 1 to 10, characterized characterized in that they have an additional on at least one side Has coating, preferably with a thickness of 5 to 100 nm, particularly preferably with a thickness of 20 to 70 nm. 12. Film according to one or more of claims 1 to 11, characterized characterized in that it is corona or flame treated. 13. Film according to one or more of claims 1 to 12, characterized characterized in that the gloss of the top layer with the matt Surface area less than 70, preferably less than 60, especially preferably less than 50, determined in each case at an angle of incidence of 60 °. 14. A method for producing the film according to one or more of the Claims 1 to 13, characterized in that the base layer and the Cover layers are coextruded, the film is then stretched and biaxially is then heat set.   15. The method according to claim 14, characterized in that the Triclosan in the form of a pre-crystallized or pre-dried master batches are added before coextrusion. 16. The method according to claim 14 or 15, characterized in that additional antimicrobial compounds, UV stabilizers and / or flame retardants in the form of at least one master batch be added to the extrusion. 17. The method according to one or more of claims 14 to 16, characterized characterized in that the additional coating by "Reverse gravure-roll coating "is applied. 18. Use of the film according to one or more of claims 1 to 13 as decorative film, as packaging or for medical Applications.