EP1282509A1 - Weisse, zumindest einseitig matte, biaxial orientierte polyesterfolie mit cycloolefincopolymer (coc), verfahren zu ihrer herstellung und ihre verwendung - Google Patents
Weisse, zumindest einseitig matte, biaxial orientierte polyesterfolie mit cycloolefincopolymer (coc), verfahren zu ihrer herstellung und ihre verwendungInfo
- Publication number
- EP1282509A1 EP1282509A1 EP01943315A EP01943315A EP1282509A1 EP 1282509 A1 EP1282509 A1 EP 1282509A1 EP 01943315 A EP01943315 A EP 01943315A EP 01943315 A EP01943315 A EP 01943315A EP 1282509 A1 EP1282509 A1 EP 1282509A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- film
- white
- range
- weight
- coc
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
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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
-
- 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
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
- B29K2023/38—Polymers of cycloalkenes, e.g. norbornene or cyclopentene
-
- 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
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/0012—Mechanical treatment, e.g. roughening, deforming, stretching
- B32B2038/0028—Stretching, elongating
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/514—Oriented
- B32B2307/518—Oriented bi-axially
-
- 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
- B32B2310/00—Treatment by energy or chemical effects
- B32B2310/14—Corona, ionisation, electrical discharge, plasma treatment
-
- 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
- B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate
-
- 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
- B32B2553/00—Packaging equipment or accessories not otherwise provided for
-
- 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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
- B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
- B32B37/153—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state at least one layer is extruded and immediately laminated while in semi-molten state
-
- 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
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/0008—Electrical discharge treatment, e.g. corona, plasma treatment; wave energy or particle radiation
-
- 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
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
- Y10T428/2495—Thickness [relative or absolute]
-
- 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.]
- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
- Y10T428/2495—Thickness [relative or absolute]
- Y10T428/24967—Absolute thicknesses specified
-
- 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]
- Y10T428/31786—Of polyester [e.g., alkyd, etc.]
- Y10T428/31797—Next to addition polymer from unsaturated monomers
Definitions
- the present invention relates to a white, at least one-sided matt, biaxially oriented and coextruded polyester film which comprises at least one base layer and at least one matt cover layer, at least the base layer containing a polyester raw material and a cycloolefin copolymer (COC).
- the invention further relates to a method for producing the polyester film and its use.
- DE-A 23 53 347 describes a process for producing a single-layer or multilayer, milky polyester film, which is characterized in that a mixture of particles of a linear polyester with 3 to 27% by weight of a homopolymer or copolymer of Produces ethylene or propylene, the mixture is extruded as a film, the film is quenched and biaxially oriented by stretching in directions perpendicular to one another and the film is heat-set.
- a disadvantage of the process is that the regrind obtained in the production of the film (essentially a mixture of polyester raw material and ethylene or propylene copolymer) can no longer be used, since otherwise the film turns yellow. The process is therefore uneconomical and the yellowish film produced with regenerated material was not able to establish itself on the market.
- EP-A-0300060 describes a single-layer polyester film which, apart from
- Polyethylene terephthalate also contains 3 to 40% by weight of a crystalline propylene polymer and 0.001 to 3% by weight of a surface-active substance.
- the surface-active substance causes the number of vacuoles in the film to increase and, at the same time, their size to decrease to the desired extent. This will achieved a higher opacity and a lower density of the film.
- a further disadvantage of the film is that the regrind obtained in the production of the film (essentially a mixture of polyester raw material and propylene homopolymer) can no longer be used, since otherwise the film turns yellow. The process is therefore uneconomical and the yellow-tinged film produced with regenerated material was not able to establish itself on the market.
- EP-A-0 360 201 describes an at least two-layer polyester film which contains a base layer with fine vacuoles, the density of which is between 0.4 and 1.3 kg / dm 3 and has at least one cover layer, the density of which is greater than 1 , 3 kg / dm 3 .
- the vacuoles are achieved by adding 4 to 30% by weight of a crystalline propylene polymer and then biaxially stretching the film.
- the additional cover layer improves the manufacturability of the film (no streaking on the surface of the film), the surface tension is increased and the roughness of the laminated surface can be reduced.
- a further disadvantage is that the regrind obtained in the production of the film (essentially a mixture of polyester raw material and propylene homopolymer) can no longer be used, since otherwise the film turns yellow. The process is therefore uneconomical and the film with yellow tint produced with regenerated material was not able to establish itself on the market.
- EP-A-0 795 399 describes an at least two-layer polyester film which contains a base layer with fine vacuoles, the density of which is between 0.4 and 1.3 kg / dm 3 and has at least one cover layer, the density of which is greater than 1 , 3 kg / dm 3 .
- the vacuoles are added by adding 5 to
- thermoplastic polymer 45 wt .-% of a thermoplastic polymer to the polyester raw material in the base and subsequent biaxial stretching of the film.
- Polypropylene, polyethylene, polymethylpentene, polystyrene or polycarbonate are mentioned as thermoplastic polymers, polypropylene being the preferred thermoplastic polymer.
- the additional cover layer improves the manufacturability of the film (no streaking on the surface of the film), the surface tension is increased and the roughness of the laminated surface can vary Be adapted to requirements.
- a further modification of the film in the base layer and / or in the outer layers with white pigments (usually TiO 2 ) and / or with optical brighteners enables the film properties to be adapted to the respective application requirements.
- a further disadvantage is that the regrind obtained in the production of the film (in
- DE-A 195 40 277 describes a single-layer or multilayer polyester film which contains a base layer with fine vacuoles, the density of which lies between 0.6 and 1.3 kg / dm 3 and has a birefringence in the plane of -0.02 to 0.04 is sufficient.
- the vacuoles are removed by adding 3 to 40
- thermoplastic resins used include Polypropylene, polyethylene, polymethyl-pentene, cyclic olefin polymers, polyacrylic resins, polystyrene or polycarbonate are mentioned, polypropylene and polystyrene being preferred raw materials.
- the claimed film is distinguished in particular by a superior tear strength and isotropic properties.
- the regrind obtained in the production of the film can no longer be used, since otherwise the color of the film is changed undefined, which is very undesirable. The process is therefore uneconomical and the film with color tone produced with regenerated material could not prevail on the market.
- the object of the present invention was to provide a white, at least one-sided matt, biaxially oriented polyester film which is characterized by improved producibility, ie low manufacturing costs.
- Waste material as regrind in an amount of 10 to 70% by weight, based on the total weight of the film, can be used again for the manufacturing process without the physical and optical properties of the film produced with regrind being negatively influenced.
- the addition of regenerated material should not cause any noteworthy yellowing of the
- the object is achieved according to the invention by a white, at least one-sided matt, biaxially oriented polyester film with at least one base layer B and at least one matt cover layer A, both made of polyester raw material, the characteristic features of which can be seen in the fact that at least the base layer B additionally contains cycloolefin copolymer (COC) in an amount in the range of 2 to 60 wt .-%, based on the weight of the base layer B, wherein the glass transition temperature T g of the cycloolefin copolymer (COCs) is in the range of 70 to 270 ° C.
- COC cycloolefin copolymer
- a white, biaxially oriented polyester film in the sense of the present invention refers to a film which has a degree of whiteness of more than 70%, preferably more than 75% and particularly preferably more than 80%. Furthermore, the opacity of the film according to the invention is more than
- the amount of cycloolefin copolymer (COC) in the base layer B should be greater than 2% by weight, otherwise the degree of whiteness is less than 70%.
- the amount of COC is greater than 60% by weight, the film can no longer be produced economically, since it can no longer be stretched in a process-safe manner.
- the glass transition temperature T g of the COC used is greater than 70 ° C. Otherwise, if the glass transition temperature T g of the COC used is less than 70 ° C, the raw material mixture is difficult to process because it is difficult to extrude. The one you want Whiteness is no longer achieved and the regrind used results in a film that tends to yellow. On the other hand, if the glass transition temperature T g of the selected COC is greater than 270 ° C, the raw material mixture in the extruder will no longer be sufficiently homogenized. This then results in a film with undesirably inhomogeneous properties.
- the glass transition temperature T g of the COCs used is in a range from 90 to 250 ° C. and in the particularly preferred embodiment in a range from 110 to 220 ° C.
- the degree of whiteness and the opacity of the film can be set precisely and adapted to the respective requirements. This measure makes it possible to largely dispense with other common whitening and opaque additives.
- the film according to the invention is characterized by a high / or. through a particularly high degree of whiteness and a high / or. through a particularly high opacity, the color change of the film remains extremely low due to the addition of regenerated material.
- the film according to the invention is multilayered. Multi-layer embodiments are at least two-layered and always comprise the COC-containing base layer B and at least one matt cover layer A.
- the COC-containing layer forms the base layer B of the film with at least one or with double-sided cover layer (s), optionally one-sided there may be one or both sides of the intermediate layer.
- the COC-containing layer also forms an intermediate layer of the multilayer film.
- COC-containing intermediate layers have a five-layer structure and, in addition to the COC-containing base layer B, have COC-containing intermediate layers on both sides.
- the COC-containing layer can, in addition to the base layer, form cover layers on one or both sides on the base or intermediate layer.
- the base layer is that layer which makes up more than 30 to 99.5%, preferably 70 to 95%, of the total film thickness.
- the top layer is the layer that the outer layer of the
- the respective embodiment of the invention is a non-transparent, opaque
- non-transparent films are understood to mean those films whose light transmission according to ASTM-D 1003-77 under
- the COC-containing layer (the base layer B) of the film according to the invention contains a polyester raw material, preferably a polyester homopolymer, a COC and optionally further additives in effective amounts.
- this layer contains at least 20% by weight, preferably 40 to
- polyester raw material 96% by weight, in particular 70 to 96% by weight, polyester raw material, based on the weight of the layer.
- the base layer B of the film contains a thermoplastic polyester.
- Terephthalic acid units or consist of ethylene glycol and naphthalene-2,6-dicarboxylic acid units.
- the remaining monomer units come from other aliphatic, cycloaliphatic or aromatic diols or dicarboxylic acids.
- Suitable other aliphatic diols are, for example, diethylene glycol, triethylene glycol, aliphatic glycols of the general formula HO- (CH 2 ) n -OH, where n represents an integer from 3 to 6 (in particular propane-1,3-diol, butane-1) , 4-diol, pentane-1, 5-diol and hexane-1, 6-diol) or branched aliphatic glycols with up to 6 carbon atoms.
- cyclohexanediols in particular cyclohexane-1,4-diol
- 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.
- Suitable other aromatic dicarboxylic acids are preferably benzenedicarboxylic acids, naphthalene dicarboxylic acids (for example naphthalene-1, 4- or 1,6-dicarboxylic acid), biphenyl-x.x'-dicarboxylic acids (especially biphenyl-4,4'-dicarboxylic acid) , Diphenylacetylene-x, x'-dicarboxylic acids (especially diphenylacetylene-4,4'-dicarboxylic acid) or Stiiben-x.x'-dicarboxylic acids.
- cyclohexanedicarboxylic acids (in particular cyclohexane-1,4-dicarboxylic acid) should be mentioned.
- aliphatic dicarboxylic acids the (C 3 -C 19 ) alkanedioic acids are particularly suitable, 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 mixed with the usual transesterification catalysts such as zinc, calcium, lithium, magnesium and man- O 01/85449 _ g _ PCT / EPO 1/04969
- the intermediates are then polycondensed in the presence of generally customary polycondensation catalysts, such as antimony trioxide or titanium salts.
- polycondensation catalysts such as antimony trioxide or titanium salts.
- Production can also be carried out using the direct esterification process in the presence of polycondensation catalysts. Here one starts directly from the dicarboxylic acids and the diols.
- the COC-containing layer contains a cycloolefin copolymer (COC) in an amount of at least 2.0% by weight, preferably 4 to 50% by weight and particularly preferably 6 to 40% by weight, based on the weight of the layer or based on the weight of the film in single-layer embodiments. It is essential for the present invention that the COC is incompatible with the polyethylene terephthalate and does not form a homogeneous mixture in the melt with the latter.
- COC cycloolefin copolymer
- Cycloolefin polymers are homopolymers or copolymers which contain polymerized cycloolefin units and optionally acyclic olefins as comonomers. Cycloolefin polymers which contain 0.1 to 100% by weight, preferably 10 to 99% by weight, particularly preferably 50 to 95% by weight, based in each case on the total mass of the cycloolefin polymer, of polymerized cycloolefin units are suitable for the present invention. Particularly preferred are polymers which are composed of the monomers of the cyclic olefins of the formulas I, II, III, IV, V or VI:
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are identical or different and represent a hydrogen atom or a C 1 -C 30 hydrocarbon radical; or two or more of the radicals R 1 to R 8 are cyclically linked, the same radicals in the different formulas having the same or different meaning.
- C ⁇ C ⁇ hydrocarbon residues are, for example, linear or branched O 01/85449 _ IQ - PCT / EP01 / 04969
- the COCs can contain 0 to 45% by weight, based on the total mass of the cycloolefin polymer, of polymerized units of at least one monocyclic olefin of the formula VII:
- n is a number from 2 to 10.
- the COCs can optionally contain 0 to 99% by weight, based on the total mass of COC, of polymerized units of an acyclic olefin of the formula VIII:
- R 9 , R 10 , R ⁇ and R 12 are the same or different and represent a hydrogen atom or C ⁇ C ⁇ hydrocarbon radicals, for example a C Cs alkyl radical or C 6 -C 14 aryl radical.
- cycloolefin polymers which are obtained by ring-opening polymerization of at least one of the monomers of the formulas I to VI and subsequent hydrogenation.
- Cycloolefin homopolymers are composed of a monomer of the formulas I-VI.
- cycloolefin copolymers are suitable which contain at least one cycloolefin of the formulas I to VI and acyclic olefins of the formula VIII as comonomer.
- acyclic olefins are those which have 2 to 20 carbon atoms, in particular unbranched acyclic olefins with 2 to 10 carbon atoms, such as for example ethylene, propylene and / or butylene.
- the proportion of polymerized units of acyclic olefins of the formula VIII is up to 99% by weight, preferably 5 to 80% by weight, particularly preferably 10 to 60% by weight, based on the total weight of the respective COC.
- COCs described above those are particularly preferred which contain polymerized units of polycyclic olefins having a norbornene structure, particularly preferably norbornene or tetracyclododecene.
- COCs which contain polymerized units of acyclic olefins, in particular ethylene, are also particularly preferred. Again, are particularly preferred
- Norbomene / ethylene and tetracyclododecene / ethylene copolymers which contain 5 to 80% by weight, preferably 10 to 60% by weight, of ethylene (based on the weight of the copolymer).
- the cycloolefin polymers generically described above generally have glass transition temperatures T g between -20 ° C. and 400 ° C.
- COCs can be used for the invention which have a glass transition temperature T g of greater than 70 ° C., preferably greater than 90 ° C. and in particular greater than 110 ° C.
- the viscosity number (decalin, 135 ° C, DIN 53 728) is advantageously between 0.1 and 200 ml / g, preferably between 50 and 150 ml / g.
- the COCs are produced by heterogeneous or homogeneous catalysis with organometallic compounds and are described in a large number of documents.
- the extrusion temperature is above the glass transition temperature T g of the COC, generally at least 5 K, preferably 10 to 180 K, in particular 15 to 150 K, above the glass transition temperature T g of the COC.
- the matt cover layer A contains added additives in the form of inert inorganic antiblocking agents and optionally a blend or a mixture of two components (I) and (II).
- Typical antiblocking 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, lithium fluoride, calcium, barium , Zinc or manganese salts of the dicarboxylic acids used, carbon black, titanium dioxide, kaolin or crosslinked polymer particles, for example
- Polymers of the individual layers of the film are added in the respective advantageous concentrations, for example as a glycolic dispersion during the polycondensation or via masterbatches during the extrusion. Pigment concentrations of 0 to 25% by weight have proven to be particularly suitable (based on the weight of the respective layer).
- a detailed description of the antiblocking agents can be found, for example, in EP-A-0 602 964.
- Component (I) of the mixture or blend is an ethylene terephthalate homopolymer or ethylene terephthalate copolymer or a mixture of ethylene terephthalate homo- or copolymers.
- Component (II) of the mixture or blend is an ethylene terephthalate
- Copolymer which consists of the condensation product of the following monomers or their derivatives capable of forming polyesters:
- component (II) where the percentages are based in each case on the total amount of the monomers forming component (II).
- component (II) For a detailed description of component (II), reference is made to the content of EP-A 0 144 878, to which reference is expressly made here.
- Mixtures for the purposes of the present invention are understood to mean mechanical mixtures which are produced from the individual components.
- the individual constituents are generally poured together as pressed small-sized shaped bodies, for example lenticular or spherical granules, and mechanically mixed with one another using a suitable vibrating device.
- Another possibility for the preparation of the mixture is that the respective components (I) and (II) in granulate form are fed separately to the extruder for the top layer according to the invention and the mixture is carried out in the extruder or in the subsequent melt-carrying systems becomes.
- a blend in the sense of the present invention is an alloy-like composite of the individual components (I) and (II) which can no longer be broken down into its original components.
- a blend has properties like a homogeneous substance and can be characterized accordingly by suitable parameters.
- the ratio (weight ratio) of the two components (I) and (II) of the mixture for the top layer or the blend can vary within wide limits and depends on the intended use of the multilayer film.
- the matt cover layer A is characterized by the following set of parameters:
- the roughness of the matt cover layer A is in the range from 200 to 1000 nm, preferably from 220 to 950 nm and particularly preferably from 250 to 900 nm. Values smaller than 200 nm have negative effects on the degree of mattness of the Surface while larger
- the measured value of the gas flow should be in the range from 0 to 50 s, preferably from 1 to 45 s. At values above 50 s, the degree of mattness of the film is negatively influenced.
- the base layer B and the other layers can additionally contain conventional additives such as stabilizers, antiblocking agents and other fillers.
- the additives are expediently added to the polymer or the polymer mixture before the melting.
- phosphorus compounds such as phosphoric acid or phosphoric acid esters are used as stabilizers.
- the base layer or the other additional layers can contain further pigmentation. It has proven to be particularly advantageous here as additional additives barium sulfate with a grain size of 0.3 to 0.8 ⁇ m, preferably from 0.4 to 0.7 ⁇ m or titanium dioxide with a grain size of 0.05 to 0.3 ⁇ m to select, measured according to the
- the amount of barium sulfate or titanium dioxide is in the range from 1 to 25% by weight, preferably from 1 to 20% by weight, and very preferably from 1 to 15% by weight.
- the total thickness of the film can vary within wide limits and depends on the intended use.
- the preferred embodiments of the film according to the invention have total thicknesses of 4 to 400 ⁇ m, 8 to 300 ⁇ m, in particular 10 to 300 ⁇ m, being preferred.
- the thickness of the intermediate layer (s) which may be present is generally in each case 0.5 to 15 ⁇ m, independently of one another, with intermediate layer thicknesses of 1 to 10 ⁇ m, in particular 1 to 8 ⁇ m, being preferred.
- the values given relate to an intermediate layer.
- the thickness of the cover layer (s) is selected independently of the other layers and is preferably in the range from 0.1 to 10 ⁇ m, in particular from 0.2 to 5 ⁇ m, preferably from 0.3 to 4 ⁇ m, with cover layers applied on both sides with respect to the thickness and composition can be the same or different.
- the thickness of the base layer B results accordingly from the difference between the total thickness of the film and the thickness of the applied top and intermediate layer (s) and can therefore vary within wide limits analogously to the total thickness.
- the invention further relates to a method for producing the polyester film according to the invention by the extrusion or coextrusion method known per se.
- Layers of the film-like melts are co-extruded through a flat die, the film thus obtained for solidification on one or more rollers is pulled off, the film is then biaxially stretched (oriented), the biaxially stretched film is heat-set and optionally corona or flame-treated on the surface layer intended for the treatment.
- the stretching in the longitudinal direction is preferably carried out with the aid of two rollers rotating at different peripheral 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 properties desired
- 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.
- the stretching can also take place in a simultaneous stretching frame (simultaneous stretching), the number of stretching steps and the sequence (lengthways / crosswise) not being of decisive importance for the property profile of the film.
- stretching temperatures of ⁇ 125 ° C and particularly favorable of ⁇ 115 ° C are favorable here.
- the stretching ratios correspond to those in the conventional sequential 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 cooled and then wound up in the usual way. To set other desired properties, however, the film can still before winding be chemically treated or corona or flame treated. The treatment intensity is adjusted so that the surface tension of the film is generally above 45 mN / m.
- the film can also be coated to set further properties. Typical coatings are adhesion-promoting, antistatic, slip-improving or adhesive layers. It is advisable to apply these additional layers to the film via in-line coating using aqueous dispersions after the longitudinal and before the transverse stretching.
- the particular advantage of the film according to the invention is its high degree of whiteness and its high opacity.
- the degree of whiteness of the film is more than 70%, preferably more than 75% and particularly preferably more than 80%.
- the opacity of the film according to the invention is more than 55%, preferably more than 60% and particularly preferably more than 65%.
- the gloss of the top layer A is less than 80, preferably less than 70 and particularly preferably less than 60.
- Another particularly surprising advantage of the invention lies in the fact that in the production of the film inherent waste material as regenerate in an amount of 10 to 70% by weight, based on the total weight of the film, can be used again for the production process without the physical properties of the film made with the regenerated material are negatively influenced.
- the regenerated material essentially consisting of polyester raw material and COC
- an advantage of the invention is that the production costs of the film according to the invention are comparable to conventional opaque films according to the prior art.
- the other processing and use-relevant properties of the film according to the invention remain essentially unchanged or are even improved.
- the film is ideal for packaging light and / or air sensitive food and beverages.
- it is also ideally suited for use in the industrial sector, for example in the manufacture of stamping foils or as a label foil.
- the film is of course particularly suitable for
- the processing and winding behavior of the film is extremely good.
- a measure of the processing behavior is the coefficient of friction of the film, which is less than 0.6.
- the winding behavior is decisively influenced by the roughness of the film. It has been found that the winding of the film according to the invention is particularly good when the mean roughness is in a range from 50 to 1000 nm while retaining the other properties.
- the roughness can be by varying the COC concentration, the mattness of the top layer A and the process parameters in the manufacturing process in the specified range.
- Table 1 summarizes the most important film properties according to the invention in a particularly illustrative manner:
- the unit measurement method area is particularly preferred
- the standard viscosity SV (DCE) is measured in dichloroacetic acid based on DIN 53726.
- the intrinsic viscosity (IV) is calculated from the standard viscosity as follows
- the friction was determined according to DIN 53 375.
- the sliding friction number was measured 14 days after production.
- the surface tension was determined using the so-called ink method (DIN 53 364).
- the roughness R a of the film was determined according to DIN 4768 with a cut-off of 0.25 mm.
- the degree of whiteness and the opacity are determined with the aid of the electric reflectance photometer "ELREPHO" from Zeiss, Oberkochem (DE),
- Standard illuminant C 2 ° normal observer.
- the opacity is determined in accordance with DIN 53 146.
- WG whiteness
- RY, RZ, RX corresponding reflection factors when using the Y, Z and X color measurement filter.
- the light transmittance is measured based on ASTM-D 1033-77.
- 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 60 °. 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 glass transition temperature T g was determined on the basis of film samples using the
- 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.
- a white, one-sided matt, opaque three-layer film with ABC structure and a total thickness of 23 ⁇ 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.
- Matte top layer A mixture of:
- masterbatch made from 95% by weight of polyethylene terephthalate (SV value of 800) and 5.0% by weight of ®Sylobloc 44 H (synthetic SiO 2 from Fa.
- Base layer B mixture of:
- Top layer C mixture of:
- the film had the required good properties and showed the desired handling and processing behavior.
- the properties achieved in films produced in this way are shown in Table 2.
- Example 2 shows that hardly any yellow discoloration of the film has become visible.
- Example 2 In comparison to Example 1, a film with a thickness of 96 ⁇ m was now produced.
- the amount of COC in the base layer was 8% by weight.
- Base layer B mixture of:
- Example 2 shows that hardly any yellow discoloration of the film has become visible.
- Base layer B mixture of:
- Example 1 from EP-A 0 300 060 was reworked.
- an additional 50% by weight of regrind was processed.
- Table 2 shows that a clear yellowing of the film has become visible
- Base layer B mixture of:
- Example 1 from EP-A 0 360 201 was reworked. In a modification of the example, an additional 50% by weight of regrind was processed. Table 2 shows that a clear yellowing of the film has become visible
- Base layer B mixture of:
- Example 1 from DE-A 19540 277 was reworked. In a modification of the example, an additional 50% by weight of regrind was processed. Table 2 shows that a clear yellowing of the film has become visible
- Base layer B mixture of:
Landscapes
- Laminated Bodies (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Wrappers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10022942A DE10022942A1 (de) | 2000-05-11 | 2000-05-11 | Weisse, zumindest einseitig matte, biaxial orientierte Polyesterfolie mit Cycloolefincopolymer, Verfahren zu ihrer Herstellung und ihre Verwendung |
DE10022942 | 2000-05-11 | ||
PCT/EP2001/004969 WO2001085449A1 (de) | 2000-05-11 | 2001-05-03 | Weisse, zumindest einseitig matte, biaxial orientierte polyesterfolie mit cycloolefincopolymer (coc), verfahren zu ihrer herstellung und ihre verwendung |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1282509A1 true EP1282509A1 (de) | 2003-02-12 |
Family
ID=7641559
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP01943315A Withdrawn EP1282509A1 (de) | 2000-05-11 | 2001-05-03 | Weisse, zumindest einseitig matte, biaxial orientierte polyesterfolie mit cycloolefincopolymer (coc), verfahren zu ihrer herstellung und ihre verwendung |
Country Status (6)
Country | Link |
---|---|
US (1) | US6893706B2 (de) |
EP (1) | EP1282509A1 (de) |
JP (1) | JP2003532562A (de) |
KR (1) | KR20020089581A (de) |
DE (1) | DE10022942A1 (de) |
WO (1) | WO2001085449A1 (de) |
Families Citing this family (19)
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DE10002178A1 (de) * | 2000-01-20 | 2001-07-26 | Mitsubishi Polyester Film Gmbh | Matte, UV-stabile, koextrudierte Polyesterfolie, Verfahren zu ihrer Herstellung und ihre Verwendung |
DE10002169A1 (de) * | 2000-01-20 | 2001-07-26 | Mitsubishi Polyester Film Gmbh | Matte, UV-stabile, thermoformbare, koextrudierte Polyesterfolie, Verfahren zu ihrer Herstellung und ihre Verwendung |
DE10009286A1 (de) * | 2000-02-28 | 2001-08-30 | Mitsubishi Polyester Film Gmbh | Weisse, biaxial orientierte, schwer entflammbare und UV-stabilisierte Polyesterfolie mit Cycloolefincopolymer, Verfahren zu ihrer Herstellung und ihre Verwendung |
DE10011652A1 (de) * | 2000-03-10 | 2001-09-13 | Mitsubishi Polyester Film Gmbh | Biaxial orientierte Polyesterfolie mit hohem Weißgrad, Verfahren zu ihrer Herstellung und ihre Verwendung |
DE10026177A1 (de) * | 2000-05-26 | 2001-11-29 | Mitsubishi Polyester Film Gmbh | Weiße, hochglänzende Polyesterfolie enthaltend Cycloolefincopolymer (COC), Verfahren zu ihrer Herstellung und ihre Verwendung |
DE10030235A1 (de) * | 2000-06-20 | 2002-01-03 | Mitsubishi Polyester Film Gmbh | Weiße, siegelfähige, thermoformbare, biaxial orientierte und koextrudierte Polyesterfolie mit Cycloolefincopolymer, Verfahren zu ihrer Herstellung und ihre Verwendung |
DE10035328A1 (de) * | 2000-07-20 | 2002-01-31 | Mitsubishi Polyester Film Gmbh | Opake Polyesterfolie enthaltend Cycloolefincopolymer (COC) mit guter Oberflächenhaftung, Verfahren zu ihrer Herstellung und ihre Verwendung |
WO2004093775A1 (ja) * | 2003-04-23 | 2004-11-04 | Otsuka Pharmaceutical Factory, Inc. | 薬液充填プラスチックアンプルおよびその製造方法 |
US7273894B2 (en) * | 2003-12-02 | 2007-09-25 | Eastman Chemical Company | Compositions for the preparation of void-containing articles |
US20070004813A1 (en) * | 2004-09-16 | 2007-01-04 | Eastman Chemical Company | Compositions for the preparation of void-containing articles |
US20060121219A1 (en) * | 2004-12-07 | 2006-06-08 | Eastman Chemical Co. | Void-containing polyester shrink film with improved density retention |
US20070134470A1 (en) * | 2005-12-09 | 2007-06-14 | Martin Jesberger | Multilayer, white, biaxially oriented polyester film |
CN101529281B (zh) * | 2006-10-27 | 2011-09-07 | 东丽株式会社 | 光反射板用白色聚酯膜 |
KR20090009107A (ko) * | 2007-07-19 | 2009-01-22 | 도레이 카부시키가이샤 | 백색 폴리에스테르필름 |
DE102008056870A1 (de) * | 2008-11-12 | 2010-05-20 | Mitsubishi Polyester Film Gmbh | Mehrschichtige, weiße, biaxial orientierte Polyesterfolie mit metallisch glänzender Deckschicht |
KR101976118B1 (ko) * | 2012-06-29 | 2019-09-10 | 코오롱인더스트리 주식회사 | 폴리에스테르 필름의 제조방법 |
US10329393B2 (en) | 2012-12-12 | 2019-06-25 | Eastman Chemical Company | Copolysters plasticized with polymeric plasticizer for shrink film applications |
US11028299B2 (en) | 2013-11-19 | 2021-06-08 | Mitsubishi Polyester Film, Inc | Anti-powdering and anti-static polymer film for digital printing |
GB201504760D0 (en) * | 2015-03-20 | 2015-05-06 | Dupont Teijin Films Us Ltd Partnership | PV cells |
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DE10009286A1 (de) * | 2000-02-28 | 2001-08-30 | Mitsubishi Polyester Film Gmbh | Weisse, biaxial orientierte, schwer entflammbare und UV-stabilisierte Polyesterfolie mit Cycloolefincopolymer, Verfahren zu ihrer Herstellung und ihre Verwendung |
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DE10026177A1 (de) * | 2000-05-26 | 2001-11-29 | Mitsubishi Polyester Film Gmbh | Weiße, hochglänzende Polyesterfolie enthaltend Cycloolefincopolymer (COC), Verfahren zu ihrer Herstellung und ihre Verwendung |
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DE10035328A1 (de) * | 2000-07-20 | 2002-01-31 | Mitsubishi Polyester Film Gmbh | Opake Polyesterfolie enthaltend Cycloolefincopolymer (COC) mit guter Oberflächenhaftung, Verfahren zu ihrer Herstellung und ihre Verwendung |
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-
2000
- 2000-05-11 DE DE10022942A patent/DE10022942A1/de not_active Withdrawn
-
2001
- 2001-05-03 US US10/275,827 patent/US6893706B2/en not_active Expired - Fee Related
- 2001-05-03 WO PCT/EP2001/004969 patent/WO2001085449A1/de not_active Application Discontinuation
- 2001-05-03 KR KR1020027014893A patent/KR20020089581A/ko not_active Application Discontinuation
- 2001-05-03 EP EP01943315A patent/EP1282509A1/de not_active Withdrawn
- 2001-05-03 JP JP2001582083A patent/JP2003532562A/ja not_active Withdrawn
Non-Patent Citations (2)
Title |
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None * |
See also references of WO0185449A1 * |
Also Published As
Publication number | Publication date |
---|---|
US20030180560A1 (en) | 2003-09-25 |
JP2003532562A (ja) | 2003-11-05 |
KR20020089581A (ko) | 2002-11-29 |
WO2001085449A1 (de) | 2001-11-15 |
DE10022942A1 (de) | 2001-11-15 |
US6893706B2 (en) | 2005-05-17 |
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