WO2001060608A1 - Feuille polyester a orientation biaxiale, stable aux uv, scellable et blanche - Google Patents

Feuille polyester a orientation biaxiale, stable aux uv, scellable et blanche Download PDF

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Publication number
WO2001060608A1
WO2001060608A1 PCT/EP2001/001303 EP0101303W WO0160608A1 WO 2001060608 A1 WO2001060608 A1 WO 2001060608A1 EP 0101303 W EP0101303 W EP 0101303W WO 0160608 A1 WO0160608 A1 WO 0160608A1
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WO
WIPO (PCT)
Prior art keywords
polyester film
film according
film
sealable
cover layer
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PCT/EP2001/001303
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German (de)
English (en)
Inventor
Ursula Murschall
Klaus Oberländer
Günther Crass
Ulrich Kern
Herbert Peiffer
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Mitsubishi Polyester Film Gmbh
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Publication of WO2001060608A1 publication Critical patent/WO2001060608A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters

Definitions

  • the invention relates to a white, sealable, UV-stabilized, coextruded, biaxially oriented polyester film consisting of at least one base layer B and cover layers A and C applied to both sides of this base layer.
  • the film additionally contains at least one UV stabilizer as light stabilizer and a white pigment.
  • the invention further includes a method for producing the film and its use.
  • the foils and articles made from them are particularly suitable for outdoor applications such as for greenhouses and canopies.
  • the films are also very suitable for covering and thus for protecting metallic surfaces on which the films are heat-sealed.
  • films that do not contain UV-absorbing materials show yellowing and deterioration of the mechanical properties after a short time due to photooxidative degradation by sunlight.
  • the film is characterized by its characteristic white appearance, which makes it particularly attractive for the applications mentioned.
  • Sealable, biaxially oriented polyester films are known in the prior art. Sealable, biaxially oriented polyester films which are equipped with one or more UV absorbers are also known. These films, which are known from the prior art, are distinguished either by good sealing behavior, good optics or by acceptable processing behavior.
  • GB-A 1 465973 describes a coextruded, two-layer polyester film, one layer of which is composed of isophthalic and terephthalic copolyesters and the other layer of polyethylene terephthalate. There is no usable information in the script about the sealing behavior of the film. Due to the lack of pigmentation, the film cannot be produced reliably (film cannot be wound) and can only be processed with restrictions.
  • EP-A 0035835 describes a coextruded, sealable polyester film in which particles are added to improve the winding and processing behavior in the sealing layer, the average particle size of which exceeds the layer thickness of the sealing layer.
  • the particulate additives form surface protrusions that prevent unwanted blocking and sticking to rollers or guides.
  • No further details regarding the incorporation of antiblocking agents are given about the other, non-sealable layer of the film. It remains open whether this layer contains antiblocking agents. By choosing particles with a larger diameter than the sealing layer and the concentrations given in the examples, the sealing behavior of the film is deteriorated.
  • the script does not give any information on the sealing temperature range of the film.
  • the seal seam strength is measured at 140 ° C and is in a range from 63 to 120 N / m (0.97 N / 15 mm to 1.8 N / 15 mm film width).
  • EP-A 0432886 describes a coextruded multilayer polyester film which has a first surface on which a sealable layer is arranged and a second surface on which an acrylate layer is arranged.
  • the sealable cover layer can also consist of copolyesters containing isophthalic acid and terephthalic acid.
  • the film on the back has improved processing properties.
  • the script does not give any information about the sealing area of the film.
  • the seal seam strength is measured at 140 ° C. For an 11 ⁇ m thick sealing layer, a seal seam strength of 761.5 N / m (11.4 N / 15 mm) is specified.
  • a disadvantage of the rear acrylic coating is that this side no longer seals against the sealable top layer. The film can therefore only be used to a very limited extent.
  • EP-A 0515096 describes a coextruded, multilayer sealable polyester film which contains an additional additive on the sealable layer.
  • the additive can e.g. contain inorganic particles and is preferably applied to the film in an aqueous layer during its manufacture. As a result, the film should maintain the good sealing properties and be easy to process. The back contains very few particles that get into this layer mainly through the regranulate. No information is given in this document on the sealing temperature range of the film.
  • the seal seam strength is measured at 140 ° C and is more than 200 N / m (3 N / 15 mm). A seal seam strength of 275 N / m (4.125 N / 15 mm) is given for a 3 ⁇ m thick sealing layer.
  • WO 98/06575 describes a coextruded multilayer polyester film which contains a sealable cover layer and a non-sealable base layer.
  • the base layer can be constructed from one or more layers, the interior of the layers being in contact with the viable layer.
  • the other (outer) layer then forms the second non-sealable cover layer.
  • the sealable top layer can consist of copolyesters containing isophthalic acid and terephthalic acid, which, however, contain no antiblocking particles.
  • the film also contains at least one UV absorber, which is added to the base layer in a weight ratio of 0.1 to 10%.
  • Triazines for example ⁇ Tinuvin 1577 from Ciba Geigy (Basel, Switzerland) are preferably used as UV absorbers.
  • the base layer is equipped with common antiblocking agents.
  • the film is characterized by a good sealability, but does not have the desired processing behavior and exhibits also deficits in the optical properties.
  • the film can also have a matt surface, but then it has a high level of haze, which is undesirable.
  • the object of the present invention was to provide a white, sealable, UV-stabilized and biaxially oriented polyester film which does not have the disadvantages of the films mentioned according to the prior art and which is particularly notable for its very good sealability, economical production and improved processability and features improved optical properties.
  • 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 film Since the film is intended in particular for outdoor use and / or critical indoor use, it should have a high UV stability.
  • a high UV stability means that the films are not or only extremely little damaged by sunlight or other UV radiation. In particular, the films should not yellow over several years of outdoor use, should not show embrittlement or cracking of the surface, and should also not show any deterioration in the mechanical properties.
  • High UV stability means that the film absorbs the UV light and only lets light through in the visible range.
  • the object is achieved according to the invention by the provision of a white, sealable, UV-stabilized, biaxially oriented, sealable polyester film with at least one base layer B, a sealable cover layer A and a further cover layer C, the sealable cover layer A having a seal initiation temperature of ⁇ 110 ° C. and has a seal seam strength of> 1.3 N / 15 mm.
  • the top layer preferably also has the following properties: an average roughness R a of less than 30 nm, a measured value range for the gas flow of 500-4000 s and a gloss of greater than 120 (measuring angle 20 °).
  • the polyester film preferably has a whiteness of greater than 70 and a planar orientation of less than 0.165 and the weathering test / UV stability according to ISO 4892 is less than 20%.
  • thermoplastics initiates degradation processes in thermoplastics, as a result, not only does the visual appearance change as a result of color change or yellowing, but also the mechanical-physical properties are adversely affected.
  • Polyethylene terephthalates for example, begin to absorb UV light below 360 nm, their absorption increases considerably below 320 nm and is very pronounced below 300 nm. The maximum absorption is between 280 and 300 nm.
  • UV stabilizers or UV absorbers as light stabilizers are chemical compounds that can intervene in the physical and chemical processes of light-induced degradation. Soot and other pigments can partially protect against light. However, these substances are unsuitable for transparent films because they are used for discoloration or Lead color change. For transparent, matt films, only organic and organometallic compounds are suitable which give the thermoplastic to be stabilized no or only an extremely slight color or color change, ie which are soluble in the thermoplastic.
  • UV stabilizers suitable as light stabilizers for the purposes of the present invention are UV stabilizers which absorb 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 350 nm. These are particularly suitable if they are thermally stable in the temperature range from 260 to 300 ° C. H. do not decompose and do not lead to outgassing.
  • Suitable UV stabilizers as light stabilizers are, for example, 2-hydroxybenzophenones, 2-hydroxybenzotriazoles, nickel organic compounds, salicylic acid esters, cinnamic acid ester derivatives, resorcinol monobenzoates, oxalic acid anilides, hydroxybenzoic acid esters, hindered amines and triazines, the 2-hydroxybenzotriazoles being preferred.
  • the film according to the invention contains 0.01% by weight to 5.0% by weight of 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- ( hexyl) oxy-phenol of the formula or 0.01% to 5.0% by weight of 2,2-methylene-bis (6- (2H-benzotriazol-2-yl) -4- (1, 1, 2,2-tetramethylpropyl) - phenol of the formula
  • mixtures of these two UV stabilizers or mixtures of at least one of these two UV stabilizers with other UV stabilizers can also be used, the total concentration of light stabilizer preferably being between 0.01% by weight and 5.0% by weight. -%, based on the weight of crystallizable polyethylene terephthalate.
  • the UV stabilizer or stabilizers are preferably contained in the cover layer (s). If necessary, the core layer can also be equipped with a UV stabilizer.
  • UV stabilizers absorb the UV light and thus offer protection
  • the person skilled in the art would have used commercially available stabilizers. He would have noticed that the UV stabilizer has a poor thermal stability and decomposes and outgasses at temperatures between 200 ° C and 240 ° C; he must incorporate large amounts (approx. 10 to 15% by weight) of UV stabilizer so that the UV light is absorbed and so that the film is not damaged.
  • UV-stabilized film is characterized by excellent stretchability so that it is reliable and stable on high speed film lines up to
  • the film has at least three layers and then comprises as layers the base layer B, the sealable cover layer A and the cover layer C.
  • the base layer B of the film preferably consists of at least 90% by weight of a thermoplastic polyester.
  • 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, as can also occur in layer A (or layer C).
  • Suitable other aliphatic diols are, for example, diethylene glycol, ethylene 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.
  • cyclohexanediols in particular cyclohexane-1,4-diol
  • 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.
  • bisphenols of the formula HO-C 6 H 4 -C 6 H 4 -OH are also very suitable.
  • 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.
  • cycloaliphatic dicarboxylic acids cyclohexanedicarboxylic acids (in particular cyclohexane-1,4-dicarboxylic acid) should be mentioned.
  • the (C 3 -C 19 ) alkanedioic acids are particularly suitable for the aliphatic dicarboxylic acids, it being possible for the alkane portion to be straight-chain or branched.
  • the production of the polyesters can e.g. according to the transesterification process.
  • the starting point is dicarboxylic acid esters and diols, which are reacted with the usual transesterification catalysts, such as zinc, calcium, lithium, magnesium and manganese salts.
  • the intermediates are then polycondensed in the presence of generally customary polycondensation catalysts, such as antimony trioxide or titanium salts.
  • the preparation can also be carried out by the direct esterification process in the presence of polycondensation catalysts. Here one starts directly from the dicarboxylic acids and the diols.
  • the sealable cover layer A applied to the base layer B by coextrusion is based on polyester copolymers and consists essentially of copolyesters which are composed predominantly of isophthalic and terephthalic acid units and of ethylene glycol units. The remaining monomer units come from other aliphatic, cycloaliphatic or aromatic diols or dicarboxylic acids, as can also occur in the base layer.
  • the preferred copolyesters that provide the desired sealing properties are those constructed from ethylene terephthalate and ethylene isophthalate units and from ethylene glycol units. The proportion of ethylene terephthalate is 40 to 95 mol% and the corresponding proportion of ethylene isophthalate is 60 to 5 mol%.
  • copolyesters in which the proportion of ethylene terephthalate is 50 to 90 mol% and the corresponding proportion of ethylene isophthalate is 50 to 10 mol% and very preferred are copolyesters in which the proportion of ethylene terephthalate is 60 to 85 mol% and the corresponding The proportion of ethylene isophthalate is 40 to 15 mol%.
  • the same polymers as described above for the base layer B can be used for the other, non-sealable top layer C or for any intermediate layers that are present.
  • the desired sealing and processing properties of the film according to the invention are obtained from the combination of the properties of the copolyester used for the sealable cover layer and the topographies of the sealable cover layer A and the non-sealable cover layer C.
  • the seal initiation temperature of ⁇ 110 ° C and the seal seam strength of> 1.3 N / 15 mm is achieved if the copolymers described in more detail above are used for the sealable cover layer A.
  • the best sealing properties of the film are obtained if no further additives, in particular no inorganic or organic fillers, are added to the copolymer. In this case, the lowest seal starting temperature and the highest seal seam strengths are obtained for a given copolyester.
  • the handling of the film is poor in this case, since the surface of the sealable cover layer A tends to block. The film can hardly be wrapped and is not suitable for further processing on high-speed packaging machines. In order to improve the handling of the film and the processability, it is necessary to modify the sealable cover layer A.
  • the topography of the sealable cover layer A is preferably characterized by the following set of parameters:
  • the roughness of the sealable top layer, characterized by the R a value, should be less than 30 nm.
  • the sealing properties are negatively influenced in the sense of the present invention.
  • the measured value of the gas flow should be in the range of 500 ⁇ 1000 s. At values below 500 s, the sealing properties are negatively influenced in the sense of the present invention, and at values above 4000 s, the handling of the film becomes poor.
  • the topography of the non-sealable cover layer C should preferably be characterized by the following set of parameters:
  • the coefficient of friction (COF) of this side against itself should be less than 0.5. Otherwise the winding behavior and further processing of the film are unsatisfactory.
  • COF coefficient of friction
  • Value should be> 40 nm and ⁇ 100 nm. Values smaller than 40 nm have negative effects on the winding and processing behavior of the film and values larger than 100 nm impair the optical properties (gloss) of the film.
  • the measured value of the gas flow should be in the range below 120 s. At values from 120 s, the winding and processing behavior of the film is negatively affected.
  • the number of elevations N per mm 2 of film surface is correlated with the respective height h using the following equation: 0.29 - 3.30 * log h / ⁇ m ⁇ log N / mm 2 ⁇ 1.84 - 2.70 * log h / ⁇ m 0.01 ⁇ m ⁇ h ⁇ 10 ⁇ m
  • the UV stabilizer is preferably contained in the non-sealable top layer C.
  • the base layer B or the sealable cover layer A can also be equipped with UV stabilizers as required.
  • the concentration of the stabilizer or stabilizers relates to the weight of the thermoplastics in the layer equipped with UV stabilizer (s).
  • the films according to the invention generally have no yellowing, no embrittlement, no loss of gloss on the surface, no cracking on the surface and no deterioration in the mechanical properties.
  • the light stabilizer can be metered in at the thermoplastic raw material manufacturer or metered into the extruder during film production.
  • the addition of the light stabilizer via masterbatch technology is particularly preferred.
  • the light stabilizer is fully dispersed in a solid carrier material.
  • the carrier materials are the polyethylene terephthalate itself or other polymers which are sufficiently compatible with the thermoplastic. It is important with masterbatch technology that the grain size and bulk density of the masterbatch is similar to the grain size and bulk density of the thermoplastic, so that homogeneous distribution and thus homogeneous UV stabilization can take place.
  • the base layer B can additionally contain conventional additives, such as stabilizers and / or antibiotic agents.
  • the two other layers A and C also contain conventional additives such as stabilizers and / or antibiotic agents. They are expediently added to the polymer or the polymer mixture before the melting. For example, phosphorus compounds such as phosphoric acid or phosphoric acid esters are used as stabilizers.
  • Typical antibiotic agents are inorganic and / or organic particles, for example calcium carbonate, amorphous silica, talc, magnesium carbonate, barium carbonate, calcium sulfate, barium sulfate, lithium phosphate, calcium phosphate, magnesium phosphate, aluminum oxide, LiF, calcium barium, Zinc or manganese salts of the dicarboxylic acids used, carbon black, titanium dioxide, kaolin or cross-linked polystyrene or acrylate particles.
  • inorganic and / or organic particles for example calcium carbonate, amorphous silica, talc, magnesium carbonate, barium carbonate, calcium sulfate, barium sulfate, lithium phosphate, calcium phosphate, magnesium phosphate, aluminum oxide, LiF, calcium barium, Zinc or manganese salts of the dicarboxylic acids used, carbon black, titanium dioxide, kaolin or cross-linked polystyrene or acrylate particles.
  • the particles can the individual layers in the respective advantageous concentrations, e.g. as a glycolic dispersion during polycondensation or via masterbatches during extrusion.
  • Preferred particles are SiO 2 in colloidal and in chain-like form. These particles are very well integrated into the polymer matrix and only produce slightly Vacuoles.
  • the particle diameters of the particles used are not restricted. To solve the problem, however, it has proven to be expedient to use particles with an average primary particle diameter of less than 100 nm, preferably less than 60 nm and particularly preferably less than 50 nm and / or particles with an average primary particle diameter of greater than 1 ⁇ m, preferably greater than 1.5 ⁇ m and particularly preferably greater than 2 ⁇ m. However, these particles described last should not have an average particle diameter that is greater than 5 ⁇ m.
  • the base layer contains the pigmentation necessary for achieving the aforementioned properties, in particular the desired degree of whiteness of the film.
  • Suitable white pigments are preferably titanium dioxide, barium sulfate, calcium carbonate, kaolin, silicon dioxide, with titanium dioxide and barium sulfate being preferred. It has proven particularly advantageous to select barium sulfate in a grain size of 0.3-0.8 ⁇ m, preferably 0.4-0.7 ⁇ m. This gives the film a brilliant white appearance without being yellowish.
  • the white pigment is also preferably metered in using masterbatch technology, but can also be incorporated directly at the raw material manufacturer.
  • the concentration of the white pigment is between 12% by weight and 40% by weight, preferably between 14% by weight and 35% by weight, particularly preferably between 16% by weight and 25% by weight, based on the weight the layer of the polyester used.
  • the film consists of three layers, the
  • Base layer B and cover layers A and C applied to both sides of this base layer, cover layer A being sealable against itself and against cover layer C.
  • the top layer C has more pigments (ie higher pigment concentration) than the top layer A.
  • the Pigment concentration in this second top layer C is between 0.1 and 1.0%, advantageously between 0.12 and 0.8% and in particular between 0.15 and 0.6%.
  • the other sealable cover layer A, which is opposite the cover layer C, is less filled with inert pigments.
  • the concentration of the inert particles in layer A is between 0.01 and 0.2% by weight, preferably between 0.015 and 0.15% by weight and in particular between 0.02 and 0.1% by weight.
  • an intermediate layer between the base layer and the cover layers.
  • This can in turn consist of the polymers described for the base layers. In a particularly preferred embodiment, it consists of the polyester used for the base layer. It can also contain the usual additives described.
  • the thickness of the intermediate layer is generally greater than 0.3 ⁇ m and is preferably in the range from 0.5 to 15 ⁇ m, in particular in the range from 1.0 to 10 ⁇ m and very particularly preferably in the range from 1.0 to 5 ⁇ m.
  • the thickness of the cover layers A and C is generally greater than 0.1 ⁇ m and is generally in the range from 0.2 to 4.0 ⁇ m, advantageously in the range from 0.2 to 3, 5 ⁇ m, in particular in the range from 0.3 to 3 ⁇ m and very particularly preferably in the range from 0.3 to 2.5 ⁇ m, it being possible for the outer layers A and C to be of the same or different thickness.
  • the total thickness of the polyester film according to the invention can vary. It is 5 to 350 ⁇ m, in particular 5 to 300 ⁇ m, preferably 5 to 250 ⁇ m, layer B having a share of preferably 5 to 90% of the total thickness.
  • the invention further relates to a process for producing the polyester film according to the invention by the coextrusion process known per se.
  • the polymers for the base layer B and the two outer layers A and C are fed to three extruders. Any foreign bodies or impurities that may be present can be filtered off from the polymer melt before extrusion.
  • the melts are then formed into flat melt films in a multi-layer nozzle and layered on top of one another.
  • the multilayer film is then pulled off and solidified with the aid of a cooling roller and, if appropriate, further rollers.
  • the film is then stretched biaxially (oriented), heat-set and optionally corona or flame treated on the surface layer intended for the treatment.
  • the stretching in the longitudinal direction can be carried out with the aid of two rolls running at different speeds in accordance with the desired stretching ratio.
  • a corresponding tenter frame is generally used for transverse stretching.
  • the temperature at which the stretching is carried out can vary within a relatively wide range and depends on the desired properties of the film.
  • the longitudinal stretching is carried out at 80 to 130 ° C and the transverse stretching at 90 to 150 ° C.
  • the longitudinal stretching ratio is generally in the range from 2.5: 1 to 6: 1, preferably from 3: 1 to 5.5: 1.
  • the transverse stretching ratio is generally in the range from 3.0: 1 to 5.0: 1, preferably from 3.5: 1 to 4.5: 1.
  • one or both surface (s) of the film can be coated in-line by the known methods. In the- Line coating can serve, for example, to improve the adhesion of the metal layer or a possibly applied printing ink, but also to improve the antistatic behavior or the processing behavior.
  • the strength of the film is in The direction of the thickness is so great that when measuring the seal seam strength, the seal seam is definitely separated and the film does not tear and tear.
  • the process parameters include in particular the stretching ratios in the longitudinal and transverse directions ( ⁇ MD and ⁇ TD ), the stretching temperatures in the longitudinal and transverse directions (T MD and T TD ), the film web speed and the type of stretching, in particular that in the longitudinal direction of the Machine.
  • LOE Low Orientation Elongation
  • REP Rapid Elongation Process
  • the film In the subsequent heat setting, the film is held at a temperature of 150 to 250 ° C. for about 0.1 to 10 s. The film is then wound up in the usual way.
  • one or both surface (s) of the film are / are preferably corona or flame treated by one of the known methods.
  • the treatment intensity is generally in the range of over 45 mN / m.
  • the film can also be coated.
  • Typical coatings are adhesion-promoting, antistatic, slip-improving or adhesive layers. It is advisable to apply these additional layers to the film via inline coating using aqueous dispersions before the stretching step in the transverse direction.
  • the film according to the invention is notable for excellent sealability, very good stability to UV light, very good handling and very good processing behavior.
  • the sealable cover layer A seals not only against itself (fin sealing) but also against the non-sealable cover layer C (lap sealing). With lap sealing, the sealing start temperature is only shifted upwards by approx. 10 K and the sealing seam strength is not deteriorated by more than 0.3 N / 15 mm.
  • the film impresses with an excellent whiteness of> 70 (according to Berger), which also gives the film a very attractive, effective advertising appearance.
  • the film Due to its excellent sealing properties, its very good handling and its very good processing properties, the film is particularly suitable for processing on high-speed machines.
  • the film is suitable for a variety of different applications, for example for interior cladding, for trade fair construction and trade fair items, as displays, for signs, for protective glazing of machines and vehicles, in the lighting sector, in shop and shelf construction, as promotional items and as a lamination medium.
  • the white film according to the invention is also suitable for outdoor applications, such as for greenhouses, roofing, external cladding, covering of materials such as Steel sheets, applications in the construction sector and illuminated advertising profiles, shadow mats, electrical applications.
  • Table 1 summarizes the most important film properties according to the invention. Table 1
  • the films were weathered on both sides with the Atlas Ci 65 Weather Ometer from Atlas on both sides and then with regard to the mechanical properties, the discoloration, the
  • the standard viscosity SV (DCE) is measured based on DIN 53726 in dichloroacetic acid.
  • Heat-sealed samples (sealing seam 20 mm x 100 mm) are produced with the sealing device HSG / ET from Brugger, whereby the film is sealed at different temperatures with the help of two heated sealing jaws at a sealing pressure of 2 bar and a sealing time of 0.5 s. Test strips of 15 mm width were cut from the sealed samples. The T-seal 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 achieved.
  • seal seam strength was determined by the T-Peel method.
  • the friction was determined according to DIN 53 375.
  • the sliding friction number was measured 14 days after production. surface tension
  • the surface tension was determined using the so-called ink method (DIN 53364).
  • 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 set at 20 °. A light beam hits the flat test surface at the set angle of incidence and is reflected or scattered by it. The light rays striking the photoelectronic receiver are displayed as a proportional electrical quantity. The measured value is dimensionless and must be specified with the angle of incidence.
  • the size distribution of elevations on film surfaces is determined using a scanning electron microscope and an image analysis system.
  • the scanning electron microscope XL30 CP from Philips with an integrated image analysis program AnalySIS from Soft-Imaging System is used.
  • foil samples are placed flat on a sample holder. Then they are vaporized at an angle a with a thin metal layer (e.g. made of silver). Where a is the angle between the sample surface and the direction of propagation of the metal vapor. This oblique vaporization creates a shadow behind the elevation. Since the shadows are not yet electrically conductive, the sample is then sputtered or sputtered with a second metal (e.g. gold), whereby the second coating strikes the sample surface perpendicularly and therefore no shadows are created during the second coating.
  • a thin metal layer e.g. made of silver
  • the sample surfaces prepared in this way are imaged in a scanning electron microscope (SEM).
  • SEM scanning electron microscope
  • the shadows of the bumps are due to the material contrast of the metals visible.
  • the sample is oriented in the SEM so that the shadows run parallel to an image edge.
  • the following conditions are set on the SEM for image acquisition: secondary electron detector, working distance 10 mm, acceleration voltage 10 kV and spot 4.5.
  • the brightness and contrast are set so that all image information is displayed as gray values and the intensity of the background noise is so small that it is not detected as a shadow.
  • the length of the shadows is measured with the image analysis.
  • the threshold value for shadow detection is placed at the point where the 2nd derivative of the gray value distribution of the image crosses the zero point.
  • the image is smoothed with an NxN filter (size 3, 1 iteration).
  • NxN filter size 3, 1 iteration.
  • the magnification, the frame size and the number of evaluated images are chosen so that a total of 0.36 mm 2 film surface are evaluated.
  • the surveys determined in this way are divided into classes in order to arrive at a frequency distribution. The division is made into 0.05 mm wide classes between 0 and 1 mm, whereby the smallest class (0 to 0.05 mm) is not used for further evaluations.
  • the diameters (spread perpendicular to the direction of the shadow) of the elevations are similarly classified into 0.2 mm wide classes from 0 to 10 mm, whereby the smallest class is also used for further evaluation.
  • the principle of the measuring method is based on the air flow between a film side and a smooth silicon wafer plate.
  • the air flows from the surroundings into an evacuated room, the interface between the film and the silicon wafer plate serving as flow resistance.
  • a round film sample is placed on a silicon wafer plate, in the middle of which a hole ensures the connection to the recipient.
  • the recipient is evacuated to a pressure less than 0.1 mbar.
  • the time in seconds that the air needs to cause a pressure increase of 56 mbar in the recipient is determined. Measurement conditions: measuring area 45.1 cm 2
  • the refractive index of the mixture must be greater than 1.685.
  • the sample cut out in the TD direction is first placed thereon so that the entire prism surface is covered. With help of a Paper handkerchief, the film is now firmly ironed onto the prism, so that the film lies firmly and smoothly. The excess liquid must be sucked off. Then a little of the measuring liquid is dripped onto the film. The second prism is folded down and pressed firmly.
  • the refractive index is determined in n ⁇ or n z (in the thickness direction of the film).
  • the strip is turned over and the values for the B side are measured.
  • the values for the A-side and the B-side are combined to mean refractive values.
  • Orientation values are then derived from the refractive indices according to the following
  • the surface defects are determined visually.
  • the modulus of elasticity, the tensile strength and the elongation at break are measured in the longitudinal and transverse directions according to ISO 527-1-2.
  • UV stability is tested according to the test specification ISO 4892 as follows:
  • Xenon lamp inner and outer filter made of borosilicate irradiation cycles 102 minutes of UV light, then 18 minutes of UV light with
  • the color change of the samples after artificial weathering is measured with a spectrophotometer according to DIN 5033.
  • Yellowness index is the deviation from the colorlessness in the "yellow” direction and is measured in accordance with DIN 6167. Yellowness index (YID) of ⁇ 5 are not visible.
  • Polyethylene terephthalate chips (produced by the transesterification process using Mn as the transesterification catalyst, Mn concentration: 100 ppm) were dried at 150 ° C. to a residual moisture content of below 100 ppm and fed to the extruder for the base layer B. Chips of polyethylene terephthalate and a filler were also fed to the extruder for the non-sealable top layer C.
  • chips were made from a linear polyester consisting of an amorphous copolyester with 78 mol% ethylene terephthalate and 22 mol% ethylene isophthalate (produced by the transesterification process with Mn as the transesterification catalyst, Mn concentration: 100 ppm).
  • the copolyester was dried at a temperature of 100 ° C. to a residual moisture content of below 200 ppm and fed to the extruder for the sealable outer layer A.
  • the UV stabilizer 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- (hexyl) -oxyphenol ( ® Tinuvin 1577) is metered in in the form of masterbatches.
  • the masterbatches expose themselves 5% by weight of ® Tinuvin 1577 as active ingredient and 95% by weight of polyethylene terephthalate (for the top layer C), or 95% by weight of polyethylene isophthalate (for the top layer A) together.
  • the 5% by weight ® Tinuvin 1577 will only be added to the two thick cover layers 20% by weight of the respective masterbatches using the masterbatch technology.
  • Bahumsuifat was used as the white pigment.
  • a white three-layer film with ABC structure and a total thickness of 20 ⁇ m was produced by coextrusion and subsequent stepwise orientation in the longitudinal and transverse directions.
  • the thickness of the respective cover layers is shown in Table 2.
  • Cover layer A mixture of: 20.0% by weight UV masterbatch based on polyethylene isophthalate
  • Top layer C mixture of:
  • the film had the required good sealing properties, the desired degree of whiteness and shows the desired handling and processing behavior.
  • the film structure and the properties achieved in films produced in this way are shown in Tables 2 to 4 (film structure and results).
  • the film in this and in all the following examples was weathered on both sides for 1000 hours per side using the Atlas Ci 65 Weather Ometer from Atlas according to the test specification ISO 4892 and then tested for mechanical properties, discoloration, surface defects and gloss.
  • the cover layer thickness of the sealable layer A was increased from 1.5 to 2.0 ⁇ m. This has improved the sealing properties, in particular the seal seam strength has increased significantly (see Tables 2 to 4).
  • Example 3 the copolymer for the sealable outer layer A was changed. Instead of the amorphous copolyester with 78 mol% polyethylene terephthalate and 22 mol% ethylene terephthalate, an amorphous copolyester with 70 mol% polyethylene terephthalate and 30 mol% ethylene terephthalate was used.
  • the raw material was processed on a twin-screw extruder with degassing without it having to be pre-dried.
  • the cover layer thickness of the sealable layer A was again 2.5 ⁇ m and that of the non-sealable layer B was 2.0 ⁇ m.
  • the sealing properties have improved as a result, in particular the seal seam strength has become significantly greater.
  • the pigment concentration in the two outer layers was slightly increased (see Tables 2 to 4).
  • Comparative Example 1 In comparison to Example 1, the sealable outer layer A was now not pigmented. Although the sealing properties have improved somewhat as a result, the handling of the film and the processing behavior have become unacceptably worse (see Tables 2 and 3). Comparative Example 2
  • Example 1 Compared to Example 1, the sealable top layer A has now been pigmented as highly as the non-sealable top layer C. The handling and the processing properties of the film have improved as a result of this measure, but the sealing properties have become significantly poorer (see Tables 2 and 3). Comparative Example 3
  • Example 2 In comparison to Example 1, the non-sealable top layer A was pigmented significantly less. The handling of the film and the processing behavior of the film has become significantly worse (see tables 2 and 3).
  • Example 1 from EP-A 0 035 835 was reworked.
  • the sealing behavior of the film, the handling of the film and the processing behavior of the film are worse than in the examples according to the invention (see Tables 2 and 3).
  • Packaging machines low manufacturing costs -: tendency to stick to rollers or other mechanical parts, block problems during winding and processing

Landscapes

  • Laminated Bodies (AREA)

Abstract

L'invention concerne une feuille polyester à orientation biaxiale, coextrudée, stable aux UV, scellable et blanche. Cette feuille polyester est composée d'au moins une couche de base B et de couches de recouvrement A et C appliquées des deux côtés de cette couche de base. La feuille contient également au moins un stabilisateur UV comme agent de protection contre la lumière et un pigment blanc. L'invention concerne également un procédé de production de la feuille et son utilisation.
PCT/EP2001/001303 2000-02-19 2001-02-07 Feuille polyester a orientation biaxiale, stable aux uv, scellable et blanche WO2001060608A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10007727.7 2000-02-19
DE2000107727 DE10007727A1 (de) 2000-02-19 2000-02-19 Weiße, siegelfähige, UV stabilisierte, biaxial orientierte Polyesterfolie, Verfahren zu ihrer Herstellung und ihre Verwendung

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WO2001060608A1 true WO2001060608A1 (fr) 2001-08-23

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1176005A2 (fr) * 2000-07-26 2002-01-30 Mitsubishi Polyester Film GmbH Film composite multicouches de polyester transparent et orienté biaxialement
EP1176163A2 (fr) * 2000-07-26 2002-01-30 Mitsubishi Polyester Film GmbH Film de polyester transparent et orienté biaxialement
EP1219413A1 (fr) * 2000-12-20 2002-07-03 Mitsubishi Polyester Film GmbH Feuille de polyester scellable, mate sur une face, à orientation biaxiale

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05230238A (ja) * 1992-02-18 1993-09-07 Toyobo Co Ltd 白色ポリエステルフィルム
WO1997037849A1 (fr) * 1996-04-10 1997-10-16 Imperial Chemical Industries Plc Carte multicouche
JPH11268214A (ja) * 1998-03-24 1999-10-05 Toray Ind Inc 積層ポリエステルフィルム
EP0947982A2 (fr) * 1998-04-01 1999-10-06 Mitsubishi Polyester Film GmbH Film de polyester multicouche à orientation biaxiale, son procédé de fabrication et son utilisation comme supports d'enregistrements magnétiques
EP0952176A1 (fr) * 1998-04-22 1999-10-27 Mitsubishi Polyester Film GmbH Film de polyester stratifié orienté biaxialement, son procédé de fabrication et son utilisation

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05230238A (ja) * 1992-02-18 1993-09-07 Toyobo Co Ltd 白色ポリエステルフィルム
WO1997037849A1 (fr) * 1996-04-10 1997-10-16 Imperial Chemical Industries Plc Carte multicouche
JPH11268214A (ja) * 1998-03-24 1999-10-05 Toray Ind Inc 積層ポリエステルフィルム
EP0947982A2 (fr) * 1998-04-01 1999-10-06 Mitsubishi Polyester Film GmbH Film de polyester multicouche à orientation biaxiale, son procédé de fabrication et son utilisation comme supports d'enregistrements magnétiques
EP0952176A1 (fr) * 1998-04-22 1999-10-27 Mitsubishi Polyester Film GmbH Film de polyester stratifié orienté biaxialement, son procédé de fabrication et son utilisation

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 017, no. 689 (C - 1143) 16 December 1993 (1993-12-16) *
PATENT ABSTRACTS OF JAPAN vol. 2000, no. 01 31 January 2000 (2000-01-31) *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1176005A2 (fr) * 2000-07-26 2002-01-30 Mitsubishi Polyester Film GmbH Film composite multicouches de polyester transparent et orienté biaxialement
EP1176163A2 (fr) * 2000-07-26 2002-01-30 Mitsubishi Polyester Film GmbH Film de polyester transparent et orienté biaxialement
EP1176163A3 (fr) * 2000-07-26 2002-03-20 Mitsubishi Polyester Film GmbH Film de polyester transparent et orienté biaxialement
EP1176005A3 (fr) * 2000-07-26 2002-03-20 Mitsubishi Polyester Film GmbH Film composite multicouches de polyester transparent et orienté biaxialement
US6420019B1 (en) 2000-07-26 2002-07-16 Mitsubishi Polyester Film Gmbh Multilayer, transparent, biaxially oriented polyester film
EP1219413A1 (fr) * 2000-12-20 2002-07-03 Mitsubishi Polyester Film GmbH Feuille de polyester scellable, mate sur une face, à orientation biaxiale
US6852387B2 (en) 2000-12-20 2005-02-08 Mitsubishi Polyester Film Gmbh One-sided mat, sealable, biaxially oriented polyester film

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