US20020160171A1 - Transparent, biaxially oriented polyester film - Google Patents

Transparent, biaxially oriented polyester film Download PDF

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Publication number
US20020160171A1
US20020160171A1 US10/077,454 US7745402A US2002160171A1 US 20020160171 A1 US20020160171 A1 US 20020160171A1 US 7745402 A US7745402 A US 7745402A US 2002160171 A1 US2002160171 A1 US 2002160171A1
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Prior art keywords
film
range
polyester film
transparent
equal
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US10/077,454
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Inventor
Herbert Peiffer
Martin Mueller-Roosen
Gottfried Hilkert
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Mitsubishi Polyester Film GmbH
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Individual
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Assigned to MITSUBISHI POLYESTER FILM GMBH reassignment MITSUBISHI POLYESTER FILM GMBH ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HILKERT, GOTTFRIED, MUELLER-ROOSEN, MARTIN, PEIFFER, HERBERT
Publication of US20020160171A1 publication Critical patent/US20020160171A1/en
Priority to US10/740,008 priority Critical patent/US7112360B2/en
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
    • B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0018—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular optical properties, e.g. fluorescent or phosphorescent
    • B29K2995/0026—Transparent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/91—Product with molecular orientation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/259—Silicic material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/266—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension of base or substrate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/269—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension including synthetic resin or polymer layer or component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y10T428/31681—Next to polyester, polyamide or polyimide [e.g., alkyd, glue, or nylon, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31786—Of polyester [e.g., alkyd, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers

Definitions

  • the invention relates to a transparent, biaxially oriented polyester film composed of a layer which comprises at least 80% by weight of thermoplastic polyester.
  • the invention further relates to a process for producing the film and to the use of the film.
  • the polyester film of the invention also comprises a specific pigment system which provides improved winding of the film and gives a highly transparent film with high-gloss surfaces.
  • the film has very high suitability for use as a packaging film, in particular for metallizing or ceramic coating, and for applications in the industrial sector, e.g. as a substrate for stamping films.
  • the prior art shows how the optical properties, in particular the gloss and the haze, of biaxially oriented polyester films can be improved.
  • EP 347 646 describes a biaxially oriented polyester film which has at least one outer layer (A) which comprises a concentration of from 0.5 to 50% of a filler, the diameter of this filler being in a particular ratio to the thickness of the outer layer.
  • the outer layer also has a certain thickness and a certain degree of crystallization, which is determined with the aid of Raman spectroscopy.
  • the topography of the outer layer A makes the film particularly suitable for magnetic recording tapes.
  • the specification gives no information concerning the transparency of the film or the gloss achieved on the outer layer A.
  • a film produced as in EP-A 347 646, did not have the desired transparency, nor the desired glossy surface. The gloss of this surface and the haze of the film are outside the range claimed in this specification.
  • EP-A-0 514 129 describes a transparent multilayer film which encompasses a primary layer substrate made from polymer material which has, at least on one of its surfaces, a secondary layer made from polymer material and having glass beads and silicon dioxide particles at particular concentrations and in particular size distributions.
  • the arrangement of the secondary layer may be on one side or on both sides of the primary layersubstrate.
  • the film improves haze and processing properties, but the specification teaches nothing concerning improvement of the gloss and of the windability of the film.
  • EP-A-0 604 057 describes a transparent multilayer film which encompasses a primary layer substrate made from polymer material and substantially free from fillers, and having, on one of its surfaces, a secondary layer which is made from polymer material and which comprises a concentration of from 100 to 1000 ppm of silicone resin with a median particle diameter of from 1.5 to 12.5 ⁇ m.
  • a disadvantage of the silicone particles is that these are comparatively expensive and do not represent an acceptable solution for the packaging market.
  • films equipped with pigments of this type tend to telescope on winding. Nor does that specification give any indication at all as to how the topography of such a film is to be adjusted for simultaneous improvement of gloss and windability.
  • DE-A-16 94 404 describes a laminate with a plurality of layers of an oriented crystalizable thermoplastic film, in which at least one of the outer layers comprises an additive.
  • the additives are conventional inert inorganic or organic particles which, in the case of the inert particles such as SiO 2 , are added at a concentration of from 1 to 25% by weight to the outer layers.
  • the particle size here is from 2 to 20 ⁇ m.
  • the laminates may be metalized with aluminum for decorative purposes or used for magnetic tapes.
  • EP-A-0 502 745 describes a coextruded biaxially oriented polyester film with at least three layers, of which an outer layer A
  • a) comprises inorganic particles with a mean primary particle size D in the range from 1 to 100 nm and complying with the equation D ⁇ T ⁇ 200D, where T is the thickness of layer A,
  • b) comprises particles B with a mean primary particle size D1 in the range from 0.3 to 2 ⁇ m and with a primary particle size distribution having a relative standard deviation of not more than 0.6, and
  • the object of the present invention was to provide a biaxially oriented polyester film which has very good optical properties and in particular has very high gloss and very low haze.
  • the film should also be very easy to wind, in particular when the machine roll is processed to give wide customer rolls of high running length.
  • the film is to be very easy to produce and to process, and is to provide a very good oxygen barrier after metalization or after coating with oxidic materials.
  • the object was to provide a film with the following combination of features:
  • the gloss of the film is intended to be greater than 150, and the haze lower than 4.0%.
  • the film is intended to be very easy to wind, and this means in particular that there are to all intents and purposes no longitudinal corrugations in customer rolls produced from a machine roll. This applies in particular when these are wide customer rolls of high running length. It is intended that less than 1.0 cm 3 of oxygen per square meter and per day will diffuse through the metalized film when it is subjected to air at a pressure of 1 bar. In respect of other properties, the quality of the film is intended to be at least equal to that of the known packaging films of this type.
  • the film is also intended to be simple and cost-effective to produce, and to be very easy to process on conventional machinery. The coefficient of friction on both surfaces is intended to be less than 0.6.
  • a further intention is to ensure that cut material arising during film production can be reintroduced to the manufacturing process as regrind in amounts of up to 60% by weight, based on the total weight of the film, without any resultant significant adverse effect on the physical or optical properties of the film.
  • the object is achieved by providing a transparent, biaxially oriented polyester film with a layer which comprises at least 80% by weight of thermoplastic polyester, where the film also comprises an amount in the range from 0.05 to 0.5% by weight, based on the total weight of the film, of a pigment system which has the following features
  • the median diameter (d 50 ) is in the range from 1.5 to 5 ⁇ m and
  • FIG. 1 shows a customer roll with clearly visible corrugations.
  • FIGS. 2 and 3 show graphs for the determination of d 50 , d 10 and d 98 of particles
  • the film has one layer and preferably comprises at least 90% by weight of a thermoplastic polyester.
  • Polyesters suitable for this purpose are those 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-bishydroxymethylcyclohexane and terephthalic acid [poly-(1,4-cyclohexanedimethylene terephthalate), PCDT], or else made from ethylene glycol, naphthalene-2,6-dicarboxylic acid and biphenyl-4,4′-dicarboxylic acid (polyethylene 2,6-naphthalate bibenzoate, PENBB).
  • polyesters of which at least 90 mol%, preferably at least 95 mol%, is composed of ethylene glycol units and terephthalic acid units, or of ethylene glycol units and naphthalene-2,6-dicarboxylic acid units.
  • the film is composed of polyethylene terephthalate homopolymer. The remaining monomer units derive from other aliphatic, cycloaliphatic or aromatic diols and, respectively, dicarboxylic acids.
  • Suitable aliphatic diols are diethylene glycol, triethylene glycol, aliphatic glycols of the formula HO—(CH 2 ) n —OH, where n is an integer from 3 to 6, in particular 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol, and branched aliphatic glycols having up to 6 carbon atoms.
  • cycloaliphatic diols mention should be made of cyclohexanediols, in particular 1,4-cyclohexanediol.
  • Examples of other suitable aromatic diols have the formula HO—C 6 H 4-X—C 6 H 4 —OH, where X is —CH 2 —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —O—, —S— or —SO 2 —.
  • 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, naphthalene dicarboxylic acids (such as 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 (in particular diphenylacetylene-4,4′-dicarboxylic acid) or stilbene-x,x′-dicarboxylic acids.
  • naphthalene dicarboxylic acids such as 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 in particular diphenylacetylene-4
  • cycloaliphatic dicarboxylic acids mention should be made of cyclohexanedicarboxylic acids (in particular cyclohexane-1,4-dicarboxylic acid).
  • aliphatic dicarboxylic acids the C 3 -C 19 alkanediacids are particularly suitable, and the alkane moiety here may be straight-chain or branched.
  • polyesters One way of preparing the polyesters is the transesterification process.
  • the starting materials are dicarboxylic esters and diols, which are reacted using the customary transesterification catalysts, such as the salts of zinc, of calcium, of lithium, of magnesium or of manganese.
  • the intermediates are then polycondensed in the presence of well-known polycondensation catalysts, such as antimony trioxide or titanium salts.
  • polycondensation catalysts such as antimony trioxide or titanium salts.
  • Another equally good preparation method is the direct esterification process in the presence of polycondensation catalysts. This starts directly from the dicarboxylic acids themselves and the diols.
  • the film comprises an effective amount of from 0.05 to 0.5% by weight, based on the total weight of the film, of the pigment system of the invention.
  • the particle concentration is from 0.055 to 0.45% by weight in the preferred embodiment of the film, and is from 0.06 to 0.4% by weight in the particularly preferred embodiment, and substantially depends on the desired optical properties and the running properties of the film.
  • Typical particle systems are inorganic and/or organic particles, such as calcium carbonate, amorphous silica, talc, magnesium carbonate, barium carbonate, calcium sulfate, barium sulfate, lithium phosphate, calcium phosphate, magnesium phosphate, aluminum oxide, lithium fluoride, the calcium, barium, zinc or manganese salts of the dicarboxylic acids used, carbon black, titanium dioxide, kaolin or crosslinked polymer particles, e.g. polystyrene particles or acrylate particles.
  • inorganic and/or organic particles such as calcium carbonate, amorphous silica, talc, magnesium carbonate, barium carbonate, calcium sulfate, barium sulfate, lithium phosphate, calcium phosphate, magnesium phosphate, aluminum oxide, lithium fluoride, the calcium, barium, zinc or manganese salts of the dicarboxylic acids used, carbon black, titanium dioxide, kaolin or crosslinked polymer particles, e.g
  • the particles may be added to the polymers of each layer of the film in the respective advantageous concentrations, e.g. as a glycolic dispersion during the polycondensation, or by way of masterbatches during extrusion.
  • the concentration of the particles is greater than that prescribed, the desired optical properties (high transparency and high gloss) are no longer achieved.
  • the film becomes cloudy and the surface becomes dull (matt). If, on the other hand, the concentration of the particles is smaller than that prescribed, this adversely affects the running properties and, respectively, the processing properties of the film. The surface of the film tends to block, and it is therefore impossible to ensure good processability, in particular on high-speed machinery.
  • Preferred particles are SiO 2 in colloidal or in chain-type form. These particles are bound very effectively into the polymer matrix.
  • the particle diameter and the scattering (spread) of the diameter of the pigment system used affect the gloss, the haze, and in particular the windability of the film. It has been found that a smaller spread of the median diameter brings about a more uniform thickness of air layer between the laps of film and thus reduces any tendency toward blocking of the laps of film against one another, or, respectively, improves windability.
  • the film of the present invention comprises a pigment system in which the median diameter (the d 50 ) is in the range from 1.5 to 5.0 ⁇ m, and the spread (expressed via the SPAN 98) is less than or equal to 1.9.
  • the outer layer (A) of the film of the present invention comprises a pigment system in which the median diameter is in the range from 1.6 to 4.9 ⁇ m and the spread is less than or equal to 1.8.
  • the film of the present invention comprises a pigment system in which the median diameter is in the range from 1.7 to 4.8 ⁇ m and the spread is less than or equal to 1.7.
  • the film comprises a pigment system in which the median diameter and the spread are outside the inventive range, this has a particularly adverse effect on the windability of the film. There can also be an adverse resultant affect on the transparency of the film and its gloss.
  • the film comprises a pigment system in which the median diameter is greater than 5.0 ⁇ m and the spread is greater than 1.9, there is in particular an adverse effect on the windability of the film.
  • these films there is an exacerbated tendency toward blocking of the film laps against one another.
  • the customer rolls produced from the machine roll have an increased tendency toward formation of longitudinal corrugations, as illustrated in FIG. 1, where a number of corrugations become clearly visible around the periphery of the roll, these being more easily indented than the surroundings. These corrugations markedly restrict the processability and the use of the film.
  • the longitudinal corrugations impressed into the films, in some cases irreversibly, are namely visible in the product during/after further processing (e.g.
  • the film comprises a pigment system in which the median diameter is smaller than 1.5 ⁇ m and the spread is greater than 1.9, this likewise can become noticeable in impaired winding and impaired optical properties.
  • the large number of small pigment particles (broad distribution of pigment system and small particle diameter) form a large number of scattering centers in the film, and these reduce not only the transparency of the film but also its gloss.
  • Another result here is impairment of the windability of the roll, and indeed to the degree described above. With median diameters of less than 1.5 ⁇ m there is also a very pronounced tendency toward telescoping or off-center running of the rolls during winding.
  • the gloss-appearance film is described by the following further parameters:
  • the roughness of the film is in the range from 30 to 150 nm, preferably from 35 to 140 nm, particularly preferably from 40 to 130 nm. Roughness values smaller than 30 nm have an adverse effect on running properties when the claimed particle system is used, and values greater than 130 nm impair the optical properties of the film.
  • the value measured for surface gas flow is in the range from 4 to 200 s, preferably in the range from 5 to 180 s. At values above 200 the windability of the film is adversely affected.
  • the film may also comprise customary additives, such as stabilizers.
  • Phosphorus compounds such as phosphoric acid or phosphoric esters, are advantageously used as stabilizers.
  • the total thickness of the polyester film of the invention may vary within certain limits. It is in the range from 3 to 80 ⁇ m, in particular from 4 to 50 ⁇ m, preferably from 5 to 30 ⁇ m.
  • the invention also provides a process for producing the polyester film of the invention by an extrusion method known from the literature.
  • the procedure for this process is that melt is extruded through a flat-film die, and the resultant prefilm is drawn off on one or more rolls for solidification, and the solidified prefilm is then biaxially stretched (oriented), and the biaxially stretched film is heat-set and, where appropriate, also corona- or flame-treated on the surface intended for treatment.
  • the biaxial stretching (orientation) is generally carried out sequentially, the type of sequential biaxial stretching preferred being that which first stretches longitudinally (in the machine direction) and then stretches transversely (perpendicularly to the machine direction).
  • the polymer or the polymer mixture is first compressed and plasticized and thus homogenized in an extruder, at which juncture any additives used may already be present in the polymer or the polymer mixture.
  • the melt is then extruded through a flat-film die (slot die), and the extruded melt is drawn off on one or more take-off rolls, whereupon the melt cools and solidifies to form a prefilm.
  • the longitudinal stretching may be carried out with the aid of two rolls rotating at different speeds corresponding to the desired stretching ratio.
  • transverse stretching use is generally made of an appropriate tenter frame, clamping both edges of the film and then drawing toward the two sides at an elevated temperature, perpendicularly to the direction of running.
  • the temperature at which the stretching is carried out may vary within a relatively wide range, and depends on the properties desired from the film.
  • the longitudinal stretching is generally carried out at a temperature in the range from 80 to 130° C., and the transverse stretching in the range from 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 30 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 surfaces of the film may be in-line coated by known processes.
  • the in-line coating may serve, for example, to give improved adhesion of a metal layer or of any printing ink subsequently to be applied, or else to improve antistatic performance or processing performance.
  • planar orientation ⁇ p of the film is greater than 0.165, preferably greater than 0.166, and very preferably greater than 0.167.
  • the significant variables affecting the planar orientation ⁇ p have been found to be the process parameters for longitudinal and transverse stretching, and also the SV of the raw material used.
  • the process parameters include in particular the longitudinal and transverse stretching ratios ( ⁇ MD and ⁇ TD ), the longitudinal and transverse stretching temperatures (T MD and T TD ), the film web speed, and the 15 nature of the stretching, in particular that in the longitudinal direction of the machine.
  • LOE Low Orientation Elongation
  • REP Rapid Elongation Process
  • the film is held at a temperature of from 150 to 250° C. for a period of from about 0.1 to 10 s.
  • the film is then wound up in the usual way.
  • one or both surfaces of the film prefferably be corona- or flame treated by one of the known methods.
  • the intensity of treatment selected is expediently such as to give the film a surface tension in the range above 45 mN/m.
  • the film may also be coated to achieve other desired properties.
  • Typical coatings are layers with adhesion-promoting, antistatic, slip-enhancing, or release effect. It is, of course, possible for these additional layers to be applied to the film by in-line coating using aqueous dispersions after longitudinal strtetching and prior to transverse stretching.
  • the film of the invention has excellent optical properties, i.e. high gloss and high transparency, very good winding performance, and very good processing performance.
  • the film therefore has quite excellent suitability for use in flexible packaging, and specifically wherever its excellent processability can be utilized to full advantage, in particular on high-speed packaging machinery.
  • Other film properties Haze ⁇ 4.0 ⁇ 3.5 ⁇ 3.0 % ASTM-D 1003- 52 Planar orientation >0.165 >0.166 ⁇ 0.167 internal ⁇ p (optional)
  • Standard viscosity SV (DCA) is measured in dichloroacetic acid by a method based on DIN 53726.
  • Haze Hölz haze was measured by a method based on ASTM-D 1003-52 but, in order to utilize the most effective measurement range, measurements were made on four laps of film laid one on top of the other, and a 1° slit diaphragm was used instead of a 4° pinhole.
  • Gloss was determined to DIN 67 530. Reflectance was measured, as an optical value characteristic of a film surface. Based on the standards ASTM-D 523-78 and ISO 2813, the angle of incidence was set at 200 or 600. A beam of light hits the flat test surface at the set angle of incidence and is reflected and/or scattered thereby. A proportional electrical variable is displayed representing light rays hitting the photoelectronic detector. The value measured is dimensionless and must be stated together with the angle of incidence.
  • the principle of the test method is based on the air flow between one side of the film and a smooth silicon wafer sheet.
  • the air flows from the surroundings into an evacuated space, and the interface between film and silicon wafer sheet acts to resist flow.
  • a round specimen of film is placed on a silicon wafer sheet in the middle of which there is a hole providing the connection to the receiver.
  • the receiver is evacuated to a pressure below 0.1 mbar.
  • the time in seconds taken by the air to establish a pressure rise of 56 mbar in the receiver is determined.
  • Test conditions Test area 45.1 cm 2 Weight applied 1276 g Air temperature 23° C. Humidity 50% relative humidity Aggregated gas volume 1.2 cm 3 Pressure difference 56 mbar
  • Planar orientation is determined by measuring the refractive index with an Abbe refractometer according to internal operating prescription 24.
  • Specimen width corresponds to prism width of 10 mm
  • the specimen to be tested has to be cut out from the film with the running edge of the specimen running precisely in the direction TD.
  • the specimen to be tested has to be cut out from the film with the running edge of the specimen running precisely in the direction MD.
  • the refractive index of the mixture must be greater than 1.685.
  • the specimen cut out in the direction TD is firstly laid on top of this, in such a way that the entire surface of the prism is covered. Using a paper wipe the film is now firmly pressed flat onto the prism, so that it is firmly and smoothly positioned thereon. The excess liquid must be sucked away. A little of the test liquid is then dropped onto the film. The second prism is swung down and into place and pressed firmly into contact. The right-hand knurled screw is then used to turn the indicator scale until a transition from light to dark can be seen in the field of view in the range from 1.62 to 1.70.
  • the colors are brought together using the upper knurled screw in such a way that only one light and one dark zone are visible.
  • the sharp transition line is brought to the crossing point of the two diagonal lines (in the eyepiece) using the lower knurled screw.
  • the value now indicated on the measurement scale is read off and entered into the test record. This is the refractive index n MD in the machine direction.
  • the scale is now turned using the lower knurled screw until the range visible in the eyepiece is from 1.49 to 1.50.
  • n a or n z (in the direction of the thickness of the film) is then determined.
  • a polarization film is placed over the eyepiece. This is turned until the transition is clearly visible.
  • n MD the refractive index
  • the transition from light to dark is not sharp (colored)
  • the colors are brought together using the upper knurled screw in such a way that a sharp transition can be seen. This sharp transition line is brought into the crossing point of the two diagonal lines using the lower knurled screw, and the value indicated on the scale is read off and entered into the table.
  • the strip is turned over, and the values for the B side are measured.
  • n av (n MD +n TD +n z )/ 3
  • the median particle diameter d 50 was determined by laser on a Malvern MasterSizer by the standard method (examples of other measurement devices are the Horiba LA 500 or Sympathec Helos, which use the same principle of measurement). For the tests, the specimens were placed in a cell with water, and this was then placed into the test device. The test procedure is automatic and includes the mathematical determination of the d 50 value.
  • the d 50 value here is determined as defined from the (relative) cumulative particle size distribution curve: the point of intersection of the 50% ordinate with the cumulative curve directly gives the desired d 50 value on the abscissa axis, as shown more precisely in FIG. 2.
  • SPAN 98 The test device used to determine SPAN 98 was the same as that described above for the determination of median diameter d 50 .
  • the (relative) cumulative particle size distribution curve is again used as a basis for determining d 98 and d 10 .
  • the point of intersection of the 98% ordinate value with the cumulative curve gives the desired d 98 value directly on the abscissa axis, and the point of intersection of the 10% ordinate value with the cumulative curve gives the desired d 10 value directly on the abscissa axis, as shown more precisely in FIG. 3.
  • Chips made from polyethylene terephthalate (prepared via the transesterification process using Mn as transesterification catalyst, Mn concentration: 100 ppm) were dried at a temperature of 150° C. to residual moisture below 100 ppm and fed, with the filler of the invention, to the extruder.
  • terephthalate and 1.0% by weight of silica particles (®Sylysia 320 from Fuji, Japan) with a d 50 of 2.5 ⁇ m and a SPAN 98 of 1.4.
  • the film had the required high gloss and the required low haze. In addition, the film exhibits the desired winding performance and the desired processing performance.
  • Example 1 Using Example 1 as a basis, the concentration of particles was now increased. The result was a marginal reduction in the gloss of the film and a marginal increase in the haze. However, windability was again improved.
  • Example 1 Using Example 1 as a basis, the particle diameter was now increased while keeping the same spread. The result was a marginal reduction in the gloss of the film and a marginal increase in the haze. However, windability was again improved.
  • Example 1 Using Example 1 as a basis, another pigment system was added. Besides the abovementioned pigments, the film also comprised 500 ppm of ®Aerosil TT 6000 (from Degussa), this being a fumed silica.
  • ®Aerosil TT 6000 from Degussa
  • Example 4 Using Example 4 as a basis, the coarser pigment Sylysia 320 was used instead of Sylysia 430.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Health & Medical Sciences (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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US20040142147A1 (en) * 2001-02-26 2004-07-22 Herbert Peiffer Multilayer transparent, biaxially oriented polyester film
US20040146724A1 (en) * 2003-01-20 2004-07-29 Herbert Peiffer Multilayer, transparent, biaxially oriented polyester film, process forits production and its use
US20040157069A1 (en) * 2003-01-28 2004-08-12 Oliver Klein Biaxially oriented polyester film which is matt on one side and has characteristic shrinkage properties, process for its preparation and its uses
US20040247909A1 (en) * 2001-10-23 2004-12-09 Stefan Bartsch Matte, biaxially oriented polyester foil, method for the production thereof and its utilization
US20050042439A1 (en) * 2003-04-22 2005-02-24 Herbert Peiffer Coextruded, hot-sealable and peelable polyester film, process for its production and its use
US20050074619A1 (en) * 2003-04-22 2005-04-07 Herbert Peiffer Coextruded, hot-sealable and peelable polyester film having high peeling resistance, process for its production and its use
US20050100750A1 (en) * 2003-11-10 2005-05-12 Herbert Peiffer Peelable polyester film with self-venting, process for its production and its use
US20050100729A1 (en) * 2003-11-10 2005-05-12 Herbert Peiffer Peelable polyester film having improved oxygen barrier, process for its production and its use
US20060134383A1 (en) * 2004-12-21 2006-06-22 Matthias Konrad Biaxially oriented polyester film which comprises silicon dioxide and titanium dioxide
US7128968B2 (en) * 2003-01-28 2006-10-31 Mitsubishi Polyester Film Gmbh Biaxially oriented polyester film which is matt on one side, process for its production and its use
US7141293B2 (en) * 2003-04-22 2006-11-28 Mitsubishi Polyester Film Gmbh Coextruded, hot-sealable and peelable polyester film having high peeling resistance, process for its production and its use
US7144615B2 (en) * 2003-04-22 2006-12-05 Mitsubishi Polyester Film Gmbh Coextruded, hot-sealable and peelable polyester film, process for its production and its use
US20090220712A1 (en) * 2005-05-24 2009-09-03 Amcor Limited Polyester composition comprising silica particles and use thereof for making packaging articles

Families Citing this family (8)

* Cited by examiner, † Cited by third party
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DE10302035A1 (de) 2003-01-21 2004-07-29 Mitsubishi Polyester Film Gmbh Polyesterfolie mit verbesserter Sauerstoffbarriere, enthaltend Poly(m-xylol-adipinamid) sowie eine Deckschicht und eine Barrierebeschichtung, Verfahren zu ihrer Herstellung und ihre Verwendung
DE10302036A1 (de) 2003-01-21 2004-07-29 Mitsubishi Polyester Film Gmbh Polyesterfolie mit verbesserter Sauerstoffbarriere, enthaltend Poly(m-xylol-adipinamid) und eine Barrierebeschichtung, Verfahren zu ihrer Herstellung und ihre Verwendung
US8071695B2 (en) * 2004-11-12 2011-12-06 Eastman Chemical Company Polyeste blends with improved stress whitening for film and sheet applications
DE102004061390A1 (de) * 2004-12-21 2006-07-06 Mitsubishi Polyester Film Gmbh Matte, biaxial orientierte Polyesterfolie
DE102007028348A1 (de) 2007-06-20 2008-12-24 Mitsubishi Polyester Film Gmbh Bernsteinfarbene Polyesterfolie mit besonderer Eignung für Metallisierung und Stahllaminierung
US10563153B2 (en) 2010-05-20 2020-02-18 Ecolab Usa Inc. Rheology modified low foaming liquid antimicrobial compositions and methods of use thereof
US9221286B2 (en) * 2013-04-09 2015-12-29 Toray Plastics (America), Inc. Polyester film with smooth surface properties for winding and printing
RU2016114061A (ru) * 2013-10-30 2017-12-05 Колгейт-Палмолив Компани, Сша Упаковка и материал для её изготовления

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3154461A (en) * 1960-03-07 1964-10-27 Minnesota Mining & Mfg Matte-finish polymeric film and method of forming the same
US3515626A (en) 1965-02-22 1970-06-02 Ici Ltd Thermoplastic laminates having improved surface properties
JPS57123050A (en) * 1980-12-01 1982-07-31 Toray Industries Polyester composite film
JPS59152948A (ja) * 1983-02-18 1984-08-31 Toyobo Co Ltd 配向ポリエステルフイルム
DE3752302T2 (de) * 1986-08-27 2000-05-11 Teijin Ltd., Osaka Biaxial orientierte Polyesterfilme
US4990400A (en) * 1987-02-12 1991-02-05 Diafoil Company, Limited Polyester films, magnetic recording media and film capacitors produced therefrom
EP0679508B1 (de) 1988-06-08 1999-12-29 Toray Industries, Inc. Biaxial orientierte Verbundfolie
JPH0818456B2 (ja) * 1989-09-08 1996-02-28 帝人株式会社 スタンピングホイル
US5336079A (en) 1991-03-06 1994-08-09 Toray Industries, Inc. Biaxially oriented laminated film comprising particles in a specific ratio of particle density
GB9110590D0 (en) 1991-05-16 1991-07-03 Ici Plc Polymeric film
EP0604057A1 (de) 1992-12-23 1994-06-29 Imperial Chemical Industries Plc Polymerfilm
DE4313510A1 (de) * 1993-04-24 1994-10-27 Hoechst Ag Polyesterrohstoff und daraus hergestellte Folie
JP3789144B2 (ja) * 1994-06-14 2006-06-21 三菱化学ポリエステルフィルム株式会社 フォトレジスト用積層ポリエステルフィルム
EP0770473B1 (de) * 1995-10-25 2001-04-11 Mitsubishi Polyester Film GmbH Polyesterfolie
DE19653750A1 (de) * 1996-12-20 1998-06-25 Hoechst Diafoil Gmbh Siegelfähige biaxial orientierte Polyesterfolie, Verfahren zu ihrer Herstellung und ihre Verwendung
DE10051083A1 (de) * 2000-10-14 2002-04-25 Mitsubishi Polyester Film Gmbh Koextrudierte, zumindest einseitig matte, biaxial orientierte Polyesterfolie
DE10051084A1 (de) * 2000-10-14 2002-04-25 Mitsubishi Polyester Film Gmbh Matte, biaxial orientierte Polyesterfolie
DE10051082A1 (de) * 2000-10-14 2002-04-25 Mitsubishi Polyester Film Gmbh Matte, koextrudierte, biaxial orientierte Polyesterfolie
DE10109216A1 (de) * 2001-02-26 2002-09-05 Mitsubishi Polyester Film Gmbh Mehrschichtige transparente, biaxial orientierte Polyesterfolie

Cited By (23)

* Cited by examiner, † Cited by third party
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US20040142147A1 (en) * 2001-02-26 2004-07-22 Herbert Peiffer Multilayer transparent, biaxially oriented polyester film
US7122240B2 (en) * 2001-02-26 2006-10-17 Mitsubishi Polyester Film Gmbh Multilayer transparent, biaxially oriented polyester film
US20040247909A1 (en) * 2001-10-23 2004-12-09 Stefan Bartsch Matte, biaxially oriented polyester foil, method for the production thereof and its utilization
US20040146724A1 (en) * 2003-01-20 2004-07-29 Herbert Peiffer Multilayer, transparent, biaxially oriented polyester film, process forits production and its use
US7094465B2 (en) * 2003-01-20 2006-08-22 Mitsubishi Polyester Film Gmbh Multilayer, transparent, biaxially oriented polyester film, process for its production and its use
US6913817B2 (en) * 2003-01-28 2005-07-05 Mitsubishi Polyester Film Gmbh Biaxially oriented polyester film which is matt on one side and has characteristic shrinkage properties, process for its preparation and its uses
US20040157069A1 (en) * 2003-01-28 2004-08-12 Oliver Klein Biaxially oriented polyester film which is matt on one side and has characteristic shrinkage properties, process for its preparation and its uses
US7128968B2 (en) * 2003-01-28 2006-10-31 Mitsubishi Polyester Film Gmbh Biaxially oriented polyester film which is matt on one side, process for its production and its use
US20050074619A1 (en) * 2003-04-22 2005-04-07 Herbert Peiffer Coextruded, hot-sealable and peelable polyester film having high peeling resistance, process for its production and its use
US7186452B2 (en) * 2003-04-22 2007-03-06 Mitsubishi Polyester Film Gmbh Coextruded, hot-sealable and peelable polyester film having high peeling resistance, process for its production and its use
US7223459B2 (en) * 2003-04-22 2007-05-29 Mitsubishi Polyester Film Gmbh Coextruded, hot-sealable and peelable polyester film, process for its production and its use
US7144615B2 (en) * 2003-04-22 2006-12-05 Mitsubishi Polyester Film Gmbh Coextruded, hot-sealable and peelable polyester film, process for its production and its use
US20050042439A1 (en) * 2003-04-22 2005-02-24 Herbert Peiffer Coextruded, hot-sealable and peelable polyester film, process for its production and its use
US7141293B2 (en) * 2003-04-22 2006-11-28 Mitsubishi Polyester Film Gmbh Coextruded, hot-sealable and peelable polyester film having high peeling resistance, process for its production and its use
US20050100750A1 (en) * 2003-11-10 2005-05-12 Herbert Peiffer Peelable polyester film with self-venting, process for its production and its use
US7205040B2 (en) * 2003-11-10 2007-04-17 Mitsubishi Polyester Film Gmbh Peelable polyester film having improved oxygen barrier, process for its production and its use
US7211306B2 (en) * 2003-11-10 2007-05-01 Mitsubishi Polyester Film Gmbh Peelable polyester film with self-venting, process for its production and its use
US20050100729A1 (en) * 2003-11-10 2005-05-12 Herbert Peiffer Peelable polyester film having improved oxygen barrier, process for its production and its use
US20060134383A1 (en) * 2004-12-21 2006-06-22 Matthias Konrad Biaxially oriented polyester film which comprises silicon dioxide and titanium dioxide
US7670667B2 (en) * 2004-12-21 2010-03-02 Mitsubishi Polyester Film Gmbh Biaxially oriented polyester film which comprises silicon dioxide and titanium dioxide
US20090220712A1 (en) * 2005-05-24 2009-09-03 Amcor Limited Polyester composition comprising silica particles and use thereof for making packaging articles
EP2186853A1 (de) * 2005-05-24 2010-05-19 Amcor Limited Polyesterzusammensetzung enthaltend Kieselsäureteilchen und deren Verwendung zur Herstellung von Verpackungsartikeln
US9120915B2 (en) 2005-05-24 2015-09-01 Amcor Limited Polyester composition comprising silica particles and use thereof for making packaging articles

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JP2002275289A (ja) 2002-09-25
KR20020069481A (ko) 2002-09-04
US7112360B2 (en) 2006-09-26
DE50214083D1 (de) 2010-01-28
US20040142194A1 (en) 2004-07-22
EP1234848B1 (de) 2009-12-16
DE10109217A1 (de) 2002-09-05

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