EP1863637A1 - Film d'etiquettes destine a un procede par moule de soufflage - Google Patents

Film d'etiquettes destine a un procede par moule de soufflage

Info

Publication number
EP1863637A1
EP1863637A1 EP06707585A EP06707585A EP1863637A1 EP 1863637 A1 EP1863637 A1 EP 1863637A1 EP 06707585 A EP06707585 A EP 06707585A EP 06707585 A EP06707585 A EP 06707585A EP 1863637 A1 EP1863637 A1 EP 1863637A1
Authority
EP
European Patent Office
Prior art keywords
film
layer
microporous layer
film according
nucleating agent
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Withdrawn
Application number
EP06707585A
Other languages
German (de)
English (en)
Inventor
Karl-Heinz Kochem
Bertram Schmitz
Mathias Roth
Wilfrid Tews
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Treofan Germany GmbH and Co KG
Original Assignee
Treofan Germany GmbH and Co KG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Treofan Germany GmbH and Co KG filed Critical Treofan Germany GmbH and Co KG
Publication of EP1863637A1 publication Critical patent/EP1863637A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0083—Nucleating agents promoting the crystallisation of the polymer matrix
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/704—Crystalline
    • 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
    • B32B2519/00—Labels, badges
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/24—Crystallisation aids
    • C08L2205/242—Beta spherulite nucleating agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • 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
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/1376—Foam or porous material containing
    • 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
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249986—Void-containing component contains also a solid fiber or solid particle
    • 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
    • Y10T428/31938—Polymer of monoethylenically unsaturated hydrocarbon

Definitions

  • the present invention relates to a microporous layer biaxially oriented film containing propylene polymers and at least one ⁇ -nucleating agent, the microporosity of which is produced by converting ⁇ -crystalline polypropylene when the film is stretched and its use as an in-mold label in blow molding.
  • Label films cover an extensive and technically complex field. A distinction is made between different labeling techniques, which are fundamentally different with regard to the process conditions and inevitably place different technical requirements on the label materials. All labeling processes have in common that, as the end result, visually appealing labeled containers must result, in which good adhesion to the labeled container must be ensured.
  • the labeling various techniques are very used for applying the label ⁇ . A distinction is made between self-adhesive labels, wrap-around labels, shrink-on labels, in-mold labels, patch labeling, etc. The use of a thermoplastic film as a label is possible in all these different labeling methods.
  • In-mold labeling also differentiates between different techniques that use different process conditions. All in-mold labeling is common that the label participates in the actual molding process of the container and is applied during its. However, very different shaping methods are used, such as injection molding, blow molding, deep drawing.
  • a label is inserted into the injection mold and back-injected by a molten plastic. Due to the high temperatures and pressures, the label connects to the injection molding and becomes an integral, non-removable component of the molding.
  • cups and lids of ice cream or margarine cups are made.
  • individual labels are removed from a stack or cut from a roll and inserted into the injection mold.
  • the mold is designed so that the melt stream is injected behind the label and the front of the film rests against the wall of the injection mold.
  • the hot melt combines with the label.
  • the tool opens, the molded part with label is ejected and cools down. As a result, the label must adhere wrinkle-free and visually flawless on the container.
  • the injection pressure When spraying the injection pressure is in a range of 300 to 600 bar.
  • the plastics used have a melt flow index of around 40 g / 10 min.
  • the injection temperatures depend on the plastic used.
  • the mold is additionally cooled to avoid sticking of the mold to the mold.
  • unoriented thick plastic plates usually cast PP or PS, heated to a thickness of about 200 .mu.m and pulled or pressed by vacuum or punch tools in a corresponding mold. Again, the single label is inserted into the mold and connects to the actual container during the molding process. Significantly lower temperatures are used so that label adhesion to the container can be a critical factor. The good adhesion must be ensured even at these low processing temperatures. The processing speeds of this method are lower than in injection molding.
  • the pressure during inflation of the molten tube is about 4-15 bar and the temperatures are much lower than in injection molding.
  • the plastic materials have a lower MFI than in injection molding to form a dimensionally stable molten tube and therefore behave differently during the cooling process than the low viscosity materials for injection molding.
  • the film on the side facing the container must have a roughness in the micron range, which allows displacement of the air during labeling.
  • Such roughness for example, by a special recipe of
  • US Pat. No. 5,254,302 describes a BOPP film whose reverse side has been modified by embossing a defined surface structure. After embossing, the film is coated on this side with a hot-melt adhesive system such that the surface structure is retained. The adhesive system ensures the adhesion of the label film to the molding and the structured surface prevents the formation of bubbles.
  • US Pat. No. 4,986,866 describes a multi-layered paper-like label film having a sealable cover layer which is mechanically coined by means of rollers before the drawing process. Again, this surface structure is to ensure the venting and allow bubble-free adhesion of the label.
  • DE 199 49 898 describes the use of a polypropylene film with an average roughness of at least 3.5 ⁇ m for the labeling in the blow molding process. This roughness is produced by a polypropylene blend in the topcoat, which blend consists of polypropylene and incompatible or partially compatible thermoplastic polymers.
  • orange peel occurs as a further independent unwanted effect in blow-molding labeling.
  • This effect has nothing to do with the big bubbles caused by lack of ventilation.
  • Orange peel does not appear in the form of isolated more or less large bubbles, but rather the entire label surface is uneven with some regularity, so that the appearance of the surface texture of an orange is very similar, therefore often referred to as orange peel.
  • this disorder is also referred to as dermis or "leathery effect”.
  • Various solutions have been proposed to reduce the orange peel effect.
  • One direction of development is based on the assumption that the orange peel results from shrinkage of the blow molded container on cooling.
  • the moldings of the in-mold shrink during cooling Injection molding very strong, yet this method is much less prone to disturbing orange peel effects.
  • EP 0 559 484 describes a film for in-mold labeling, wherein no distinction is made between injection molding in-mold and blow-molding in-mold.
  • the film has a top layer of polyethylene and fillers applied to a vacuole-containing base layer.
  • the polyethylene layer is the
  • Container facing and on the opposite outside can more
  • Layers are applied. According to this teaching, the occurrence of a dermis effect can be masked by further pigmented outer layers.
  • EP 0 546 741 describes a film having a vakuolen inconveniencen cover layer, which is applied to a non-vacuole-containing base layer.
  • the vakuolen inconvenience cover layer faces the container in the in-mold process.
  • the orange peel is formed by shrinkage of the vacuum-containing label film during injection molding and can be avoided by avoiding too much vacuole formation and reducing the filler content of the film.
  • the in-mold label film should have a shrinkage of at least 4% in both directions at 130 0 C and 10min.
  • EP 0 865 909 describes the use of "microvoided" films for labels.
  • the film contains a ⁇ -nucleating agent, by which an increased proportion of ⁇ -crystalline polypropylene is produced in the prefilm during cooling of the melt film. When stretching the pre-foil "microvoids" are generated. It is described that the film has good printability.
  • EP 1 501 886 describes the use of a biaxially oriented polypropylene microporous film containing ⁇ -nucleating agents.
  • the microporosity is generated by converting ⁇ -crystalline polypropylene on stretching the film. Due to the high porosity, the film can advantageously be used for labeling containers during blow molding.
  • the methods of making the film are very slow in practice to ensure the required high porosities.
  • high porosities mechanically weaken the film in such a way that it frequently breaks down in the stretching frame. This makes the film more expensive and makes economic use difficult despite technical advantages.
  • the object of the present invention was to provide a label film which should have a good adhesion and no orange peel in the in-mold labeling in the blow-molding process and which can be produced with sufficient production speed and production reliability.
  • the object on which the invention is based is achieved by a biaxially oriented film with a porous layer containing polypropylene and ⁇ -nucleating agent. contains medium and whose microporosity is produced by conversion of ß-crystalline polypropylene during stretching of the film and whose Gurley value is> 10,000 s.
  • the microporous layer is an outer layer of the film.
  • the object is further achieved by the use of this film for labeling containers during blow molding.
  • a film having a microporous layer whose Gurley value is greater than 10,000s can be used excellently in blow-molding labeling and no orange peel occurs under a wide variety of process conditions when this microporosity is indirectly produced by ⁇ -nucleating agents.
  • a high porosity of the film is required in order to ensure a good venting via the high gas permeability of the porous layer, which is in contact with the container.
  • the high porosities although favorable, are not required.
  • the net-like structure of the porous layer contributes to deaeration even with comparatively low gas permeabilities (high Gurley values) and prevents blistering during labeling surprisingly effectively when this layer faces the container during labeling.
  • high Gurley values gas permeabilities
  • the film is mechanically much more stable overall, which reduces the number of tears in the production. The invention thus has considerable economic advantages and the film according to the invention can be used without blistering during blow-mold labeling.
  • FIGS. 2a and 2b show the typical structure of a vacuole-containing layer in cross-section (2a) and in a plan view (2b).
  • vacuole The vacuoles are distributed over the entire layer and reduce the density of the films or of the layer, but these films still have a good barrier, for example to water vapor, since the vacuoles are closed and the structure as a whole is not permeable Opaque films with a vacuole-containing layer result in the blow-molding process, the unwanted orange peel.
  • the porous layer is gas-permeable and has an open-pore network structure. This structure is not caused by incompatible fillers or particles, but by a technically very different process.
  • the microporous layer contains polypropylene and ⁇ -nucleating agents. This mixture of polypropylene with ß-nucleating agent is first melted as usual in the film production in an extruder and extruded through a slot die as a melt film on a cooling roll. The ⁇ -nucleating agent promotes the crystallization of ⁇ -crystalline polypropylene during cooling of the melt film, resulting in an unstretched prefilm with a high content of ⁇ -crystalline polypropylene.
  • the temperature and stretching conditions can be chosen so that the ß crystallites convert into the thermally stable alpha phase of the polypropylene. Since the density of the ⁇ -crystallites is lower, this conversion is accompanied by volume shrinkage, thereby resulting in the characteristic porous structure, similar to a ruptured network.
  • the composition of the microporous layer hereinafter also referred to as layer, will now be described in detail in detail.
  • the microporous layer contains propylene homopolymer and / or a propylene block copolymer, optionally additionally other polyolefins, and at least one .beta.-nucleating agent, and optionally additionally conventional additives, for example stabilizers, neutralizing agents, lubricants, antistatic agents, pigments in respective effective amounts.
  • Vakuolenintierende fillers such as calcium carbonate or polyester, such as PET or PBT, omitted, so that the layer contains less than 5 wt .-%, preferably 0 to at most 1 wt .-% of Vakuoleninit Schlden fillers. Such small amounts can get into the layer, for example via the incorporation of film regenerate.
  • the layer contains at least 70% by weight, preferably from 80 to 99.95% by weight, in particular from 90 to 97% by weight, of a propylene homopolymer and / or propylene block copolymer and from 0.001 to 5% by weight, preferably 0, 1 to 3 wt .-% of at least one ß-nucleating agent, each based on the weight of the layer.
  • Suitable propylene homopolymers contain 80 to 100 wt .-%, preferably 90 to 100 wt .-% of propylene units and have a melting point of 140 0 C or higher, preferably 150 to 17O 0 C, and generally a
  • Suitable propylene block copolymers contain predominantly, ie more than 50% by weight, preferably 70 to 99% by weight, in particular 90 to 99% by weight, of propylene units.
  • Suitable comonomers in appropriate amount are ethylene, butylene or higher alkene homologues, of which ethylene is preferred.
  • the melt flow index of the block copolymers is within a range of 1 to 15 g / 10 min, preferably 2 to 10 g / 10min (230 0 C; 2.16 kg).
  • the melting point is above 140 0 C, preferably in a range of 150 to 165 0 C.
  • the stated percentages by weight relate to the respective polymer.
  • Blends of propylene homopolymer and propylene block copolymer contain these two components in any mixing ratios.
  • the ratio of propylene homopolymer to propylene block copolymer ranges from 10 to 90 wt% to 90 to 10 wt%, preferably, 20 to 70 wt% to 70 to 20 wt%.
  • Such mixtures of homopolymer and block copolymer are particularly preferred and improve the appearance of the microporous layer, as well as the stretchability.
  • the porous layer may contain other polyolefins in addition to the propylene homopolymer and / or propylene block copolymer.
  • the proportion of these other polyolefins is generally below 30 wt .-%, preferably in a range of 1 to 20 wt .-%.
  • polystyrene resins include, for example, random copolymers of ethylene and propylene having an ethylene content of 20% by weight or less, random copolymers of propylene with C 4 -C 8 olefins having an olefin content of 20% by weight or less, terpolymers of propylene, Ethylene and butylene having an ethylene content of 10% by weight or less and having a butylene content of 15% by weight or less, or polyethylenes such as HDPE, LDPE, VLDPE, MDPE and LLDPE.
  • ⁇ -nucleating agents for the microporous layer basically all known additives are suitable which promote the formation of ⁇ -crystals upon cooling of a polypropylene melt.
  • Such ß-nucleating agents, as well as their Operation in a polypropylene matrix are well known in the art and will be described in detail below.
  • highly active ⁇ -nucleating agents are preferably used in the porous layer which can produce a ⁇ -content of 10-80%, preferably 20-60%, upon cooling of the melt film.
  • a two-component nucleation system of calcium carbonate and organic dicarboxylic acids is suitable, which is described in DE 3610644, which is hereby incorporated by reference.
  • Particularly advantageous are calcium salts of dicarboxylic acids, such as calcium pimelate or calcium suberate as described in DE 4420989, to which also expressly incorporated by reference.
  • the dicarboxamides in particular N, N-dicyclohexyl-2,6-naphthalenedicarboxamides described in EP-0557721 are also suitable ⁇ -nucleating agents.
  • the cooling of the melt film is preferably carried out at a temperature of 60 to 130 0 C, in particular 80 to 120 0 C.
  • the very slow cooling which promotes the growth of ß-KristaHite, compared to EP 1 501 886 done faster.
  • the withdrawal speed ie the The speed at which the melt film passes over the first chill roll should be chosen so that the residence times at the given temperatures allow the growth of the ⁇ crystals.
  • the production rate can be increased to such an extent that the concentration of ⁇ -crystallites in the prefilm is in the range of 20 to 60%, so that the film thus produced has a Gurley value of 10,000 to 300,000 s after the biaxial stretching.
  • the take-off speed can vary greatly depending on the dimension of the take-off roll and its temperature and is preferably less than 35 m / min, in particular 1 to 20 m / min.
  • Particularly preferred embodiments contain from 0.001 to 5 wt .-%, preferably 0.05 to 3.0 wt .-%, in particular 0.1 to 1, 0 wt .-% calcium pimelate or calcium suberate in the microporous layer of propylene - homopolymer.
  • the microporous label film is single-layered and consists only of the microporous layer. It goes without saying, however, that this monolayer film can optionally be provided with a printing or a coating or an additional cover layer before it is used as a label film in blow molding.
  • the thickness of the porous layer is generally in a range of 20 to 150 ⁇ m, preferably 30 to 100 ⁇ m.
  • the outer surface of the porous layer is not covered with further layers, i. neither printing nor coating, lamination or any other processing which would result in the pores of the porous layer being covered on this side of the film.
  • the surface of the porous layer forms a surface of the film.
  • the microporous layer on the outside may be provided with a corona, flame or plasma treatment to improve the adhesive properties and wettability.
  • the density of the microporous layer is generally in a range of 0.3 to 0.85 g / cm 3 , preferably 0.4 to 0.7 g / cm 3 'which corresponds to the density of the film in single-layered embodiments.
  • a particularly low density does not lead to an enhancement of the orange peel effect, as with vacuole-containing, opaque films.
  • opaque films teach pamphlets that a too low density by excessive voiding leads to an enhanced orange peel effect. Surprisingly, this is not the case with porous films.
  • the density can be reduced to extremely low levels and the film can still be applied properly during blow molding, without a disturbing orange peel occurs.
  • the microporous layer can be provided with a further covering layer, the microporous layer, in the case of the use according to the invention of this multilayered embodiment, facing the container and joining with the molded body during blow molding.
  • the additional cover layer forms the outside of the label in the use according to the invention.
  • the additional covering layer can be applied for example by lamination or lamination of the porous layer with another film. Preferably, it is a coextruded topcoat. Optionally, a coating is possible.
  • Coatings can be applied by conventional methods. Coatings are for example of acrylic acids, acrylates, PVOH or other polymers which are suitable as sealable or printable surface layers. Such coatings are described in detail, for example, in US Pat. No. 6,013,353 (column 6), to which disclosure reference is expressly made.
  • the optionally coextruded cover layer generally contains at least 70% by weight, preferably 75 to ⁇ 100% by weight, in particular 90 to 98% by weight, of a polyolefin, preferably of a propylene polymer and optionally further conventional additives such as neutralizing agent, stabilizer, antistatic agents, lubricants, for example fatty acid amides or siloxanes or antiblocking agents in respective effective amounts.
  • a polyolefin preferably of a propylene polymer
  • optionally further conventional additives such as neutralizing agent, stabilizer, antistatic agents, lubricants, for example fatty acid amides or siloxanes or antiblocking agents in respective effective amounts.
  • the propylene polymer of the cover layer is, for example, a propylene homopolymer as already described above or for the porous layer
  • Copolymer of propylene and ethylene or propylene and butylene or propylene and another olefin of 5 to 10 carbon atoms are also suitable for the topcoat.
  • terpolymers of ethylene and propylene and butylene or ethylene and propylene and another olefin of 5 to 10 carbon atoms are also suitable for the topcoat.
  • mixtures or blends of two or more of said copolymers and terpolymers can be used.
  • ethylene-propylene random copolymers and ethylene-propylene-butylene terpolymers are preferred, in particular ethylene-propylene random copolymers having an ethylene content of 2 to 10% by weight, preferably 5 to 8% by weight, or random Ethylene-propylene-butylene-1 terpolymers having an ethylene content of 1 to 10 wt .-%, preferably 2 to 6 wt .-%, and a Butylen- 1 content of 3 to 20 wt .-%, preferably 8 to 10 Wt .-%, each based on the weight of the co- or terpolymer.
  • the above-described random copolymers and terpolymers generally have a melt flow index of 1.5 to 30 g / 10 min, preferably from 3 to 15 g / 10 min.
  • the melting point is in the range of 105 0 C to 14O 0 C.
  • the above-described blend of copolymers and terpolymers has a melt flow index of 5 to 9 g / 10 min and a melting point of 120 to 150 0 C. All Schmelzflußindices given above are at 230 0 C and a force of 2.16 kg (DIN 53735) measured.
  • this cover layer is generally in a range of 0.1 to 10 .mu.m, preferably 0.5 to 5 .mu.m.
  • the surface of this cover layer is generally in a range of 0.1 to 10 .mu.m, preferably 0.5 to 5 .mu.m.
  • the surface of this cover layer is generally in a range of 0.1 to 10 .mu.m, preferably 0.5 to 5 .mu.m.
  • Topcoat to improve the printability with a corona, flame or
  • the density of the film is not through the porous covering layer, which also contains no vacuoles, increases only insignificantly compared to single-layered embodiments and therefore generally ranges from 0.35 to 0.85 g / cm 3, preferably from 0.4 to 0.65 g / cm 3, for these embodiments ,
  • the topcoat may additionally contain customary additives such as stabilizers, neutralizing agents, antiblocking agents, lubricants, antistatic agents, etc., in customary amounts.
  • customary additives such as stabilizers, neutralizing agents, antiblocking agents, lubricants, antistatic agents, etc., in customary amounts.
  • the porous film according to the invention is preferably produced by the extrusion process known per se or by the coextrusion process (flat film process).
  • the procedure is that the polypropylene, which is mixed with ß-nucleating agent, melted in an extruder and extruded through a flat die onto a take-off roll, on which the melt solidifies to form the ß-crystallites.
  • the corresponding coextrusion takes place together with the cover layer.
  • the cooling temperatures and cooling times are chosen so that a sufficient proportion of ⁇ -crystalline polypropylene is formed in the prefilm.
  • This prefilm with ß-crystalline polypropylene is then stretched biaxially so that it comes to the transformation to a transformation of ß-crystallites in alpha polypropylene.
  • the biaxially stretched film is finally heat-set and optionally corona-, plasma- or flame-treated on one or both surfaces.
  • the biaxial stretching (orientation) will generally be performed sequentially, preferably stretching first longitudinally (in the machine direction) and then transversely (perpendicular to the machine direction).
  • the take-off roller or the draw-off rollers in order to promote the formation of a high proportion of beta-crystalline polypropylene at a temperature of 60 to 130 0 C, preferably maintained from 80 to 12O 0 C.
  • the temperature is less than 14O 0 C, preferably 90 to 125 0 C.
  • the draw ratio is in the range 3: 1 to 5: 1
  • the stretching in the transverse direction is carried out at a temperature of greater than 140 0 C, preferably at 145 to 16O 0 C.
  • the transverse stretch ratio is stretched in a range of 3: 1 to 7: 1.
  • the longitudinal stretching will be carried out expediently with the help of two different speeds corresponding to the desired stretching ratio and the transverse stretching with the aid of a corresponding clip frame.
  • the biaxial stretching of the film is generally followed by its heat-setting (heat treatment), the film being kept at a temperature of 110 to 150 ° C. for about 0.5 to 10 seconds. Subsequently, the film is wound in the usual manner with a winding device.
  • one or both surfaces of the film are corona, plasma or flame treated by one of the known methods.
  • Such a surface treatment is particularly preferred on the opposite surface of the porous layer (outside of the label), if in the context of further processing, a printing and / or metallization is provided.
  • the film is passed between two conductor elements serving as electrodes, with such high voltage, usually alternating voltage (about 10,000 V and 10,000 Hz), applied between the electrodes so that spraying or corona discharges can take place.
  • high voltage usually alternating voltage (about 10,000 V and 10,000 Hz)
  • Spray or corona discharge the air is ionized above the film surface and reacts with the molecules of the film surface, so that polar deposits are formed in the substantially non-polar polymer matrix.
  • Treatment intensities are within the usual range, with 38 to 45 mN / m being preferred.
  • a porous film having an opaque appearance is obtained.
  • the porous layer has a net-like structure with interconnected pores (see Figures 3a and 3b), which is permeable to gases.
  • these films in a single-layer embodiment have a Gurley value in the range from 10,000 to 300,000 sec.
  • the porous layer has a corresponding structure so that comparable Gurley values for the layer are present.
  • the porous film is used in the blow molding process. Details of the blow molding process have already been described above in connection with the prior art.
  • the porous film is used for labeling polyethylene containers during blow molding.
  • the film is inserted so that the porous layer faces the container. Suitable blow molding processes are also described, for example, in ISDN 3-446-15071-4, to which reference is hereby expressly made.
  • the melt flow index of the propylene polymers was measured according to DIN 53 735 at 2.16 kg load and 230 ° C. and at 190 ° C. and 2.16 kg for polyethylenes.
  • Density The density is determined according to DIN 53 479, method A.
  • the DSC method is used to determine the .beta.-crystalline portion (for example in the prefilm) in polypropylene.
  • Gurley value The permeability of the films was measured with the Gurley Tester 4110, according to ASTM D 726-58. It determines the time (in seconds) that 100 cm 3 of air will take to permeate through the 1 inch 2 (6,452 cm 2 ) label area. The pressure difference across the film corresponds to the pressure of a water column of 12.4 cm in height. The time required then corresponds to the Gurley value.
  • the film had the following composition: about 50 wt .-% propylene homopolymer (PP) with an n-heptane-soluble content of 4.5 wt .-% (based on 100% PP) and a melting point of 165 0 C; and a melt flow index of 3.2 g / 10 min at 230 0 C and 2.16 kg load (DIN 53 735) and about 49.9 wt .-% propylene-ethylene block copolymer having an ethylene content of about 5 wt. -% based on the block copolymer and a MFI (23O 0 C and 2.16 kg) of 6 g / 10 min
  • the film additionally contained stabilizer and neutralizing agent in conventional amounts.
  • the molten polymer mixture was withdrawn after extrusion via a first take-off roll and another rolling center and solidified, then stretched longitudinally, transversely stretched and fixed, the following conditions were selected in detail:
  • the porous film thus prepared was about 95 ⁇ m thick and had a density of 0.50 g / cm 3 and showed a uniform white-opaque appearance.
  • the Gurley value was 95,000 sec.
  • Comparative Example 1 A film was produced as described in Example 1. In contrast to Example 1, the residence time on the take-off roll was increased to 55 sec. Thus, the production rate in Example 1 was more than three times as high as in this Comparative Example 1.
  • the Gurley value of the film according to Comparative Example 1 was about 1040 sec and the density 0.35 g / cm 3 at a film thickness of about 80 .mu.m.
  • Comparative Example 2 An opaque three-layer film with a layer structure ABC with a total thickness of 80 ⁇ m was produced by coextrusion and by subsequent stepwise orientation in the longitudinal and in the transverse direction.
  • the cover layers had a thickness of 0.6 ⁇ m each.
  • the films according to the examples and comparative examples were cut to label shape, as usual provided on the blow molding machine and inserted into the mold before the blow molding process, wherein the films were inserted according to Example 1 and Comparative Example 1 so that the microporous layer facing the container ,
  • a blow molding machine was equipped with a tool for a bulbous bottle. The blow molding machine was charged with HD-PE blown stock with an MFI of 0.4 g / 10 min. The HDPE was extruded at a mass temperature of about 200 0 C through a ring nozzle hose-shaped. The mold was closed, sealing the bottom of the molten tube. In the upper end of the tube, a lance was retracted and inflated the tube with a pressure of 10 bar in the mold. The mold was then moved apart and the container removed.
  • the porous label sheets of Example 1 and Comparative Example 1 were integral with the container and all exhibited a perfectly smooth appearance without any signs of orange peel.
  • the opaque vacuolate-containing film according to the comparative example was also bonded to the container and showed the characteristic appearance of the orange peel.
  • the inventive films according to Examples 1 showed no impairment in adhesion or appearance despite significantly increased Gurley values, ie lower gas permeabilities. Thus, the films could be advantageously produced at more than twice the production speed as Comparative Example 1 without causing problems in the use according to the invention.

Abstract

L'invention concerne un film à orientation biaxiale doté d'une couche microporeuse qui contient un polymère de propylène et au moins un agent de ß-nucéation et dont la microporosité est réalisée par transformation du polypropylène ß-cristallin lors de l'étirage du film. L'invention concerne enfin l'utilisation pour l'étiquetage de contenants dans le cas de moules de soufflage. La valeur Gurley des films s'élève à une valeur comprise entre 10.000 et 300.000 Gurley.
EP06707585A 2005-03-19 2006-03-16 Film d'etiquettes destine a un procede par moule de soufflage Withdrawn EP1863637A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005012871 2005-03-19
PCT/EP2006/002417 WO2006099990A1 (fr) 2005-03-19 2006-03-16 Film d'etiquettes destine a un procede par moule de soufflage

Publications (1)

Publication Number Publication Date
EP1863637A1 true EP1863637A1 (fr) 2007-12-12

Family

ID=36691606

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06707585A Withdrawn EP1863637A1 (fr) 2005-03-19 2006-03-16 Film d'etiquettes destine a un procede par moule de soufflage

Country Status (8)

Country Link
US (2) US20090041965A1 (fr)
EP (1) EP1863637A1 (fr)
CN (1) CN101142082B (fr)
AU (1) AU2006226596B2 (fr)
CA (1) CA2601989C (fr)
HK (1) HK1118256A1 (fr)
MX (1) MX2007011517A (fr)
WO (1) WO2006099990A1 (fr)

Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2103426B1 (fr) * 2008-03-20 2011-09-28 Borealis Technology OY Film soufflé
ES2457219T3 (es) * 2008-05-02 2014-04-25 Treofan Germany Gmbh & Co. Kg Lámina de membrana monocapa para baterías con función de desconexión
ES2589605T3 (es) * 2008-05-02 2016-11-15 Treofan Germany Gmbh & Co. Kg Lámina de membrana para baterías con función de desconexión
ES2423583T3 (es) * 2008-05-02 2013-09-23 Treofan Germany Gmbh & Co. Kg Lámina de membrana multicapa microporosa a base de polipropileno para baterías con función de desconexión
EP2325244B1 (fr) 2009-11-19 2012-03-14 Borealis AG Carbonate de calcium à surface enrobée pour polyoléfines
TWI564151B (zh) * 2011-03-30 2017-01-01 住友電木股份有限公司 薄膜及包裝體
US9067705B2 (en) 2011-06-17 2015-06-30 Berry Plastics Corporation Process for forming an insulated container having artwork
MX2013014905A (es) 2011-06-17 2014-11-14 Berry Plastics Corp Manguito aislante para taza.
JP6235466B2 (ja) 2011-06-17 2017-11-22 ベリー プラスチックス コーポレイション 断熱容器
CA2845225C (fr) 2011-08-31 2022-11-15 Berry Plastics Corporation Materiau polymere pour contenant isole
US20130344268A1 (en) * 2012-06-26 2013-12-26 Alfred CHOI Moulded article and label therefor
MX2015005207A (es) 2012-10-26 2016-03-21 Berry Plastics Corp Material polimerico para un recipiente aislado.
KR102597627B1 (ko) 2012-11-06 2023-11-02 셀가드 엘엘씨 공중합체 멤브레인, 섬유, 제품 및 방법
US9957365B2 (en) 2013-03-13 2018-05-01 Berry Plastics Corporation Cellular polymeric material
RU2015143424A (ru) 2013-03-14 2017-04-19 Берри Пластикс Корпорейшн Сосуд
EP3033208A4 (fr) 2013-08-16 2017-07-05 Berry Plastics Corp. Matériau polymère pour contenant isolé
WO2016118838A1 (fr) 2015-01-23 2016-07-28 Berry Plastics Corporation Matériau polymère pour contenant isotherme
US20190283488A1 (en) * 2016-05-18 2019-09-19 Adhetec Adhesive marking device
CA3013585A1 (fr) 2017-08-08 2019-02-08 Berry Global, Inc. Contenant isole

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2262063B (en) 1991-12-07 1996-01-10 Courtaulds Films & Packaging Polymeric films
CN1004076B (zh) 1985-04-01 1989-05-03 中国科学院上海有机化学研究所 β-晶型聚丙烯生产方法
US4883697A (en) * 1986-07-23 1989-11-28 The Procter & Gamble Company Thermoplastic in-mold labeling label structure for deformable thermoplastic packages
US5079057A (en) * 1986-12-29 1992-01-07 Owens-Illinois Plastic Products Inc. Plastic container with multilayer label applied by in-mold labeling
US4986866A (en) * 1989-12-15 1991-01-22 Oji Yuka Goseishi Co., Ltd. Process for producing synthetic label paper
US5176953A (en) * 1990-12-21 1993-01-05 Amoco Corporation Oriented polymeric microporous films
JP3140075B2 (ja) * 1991-03-04 2001-03-05 株式会社ユポ・コーポレーション インモールド用ラベル
US6235823B1 (en) 1992-01-24 2001-05-22 New Japan Chemical Co., Ltd. Crystalline polypropylene resin composition and amide compounds
GB2266491B (en) 1992-03-06 1996-06-12 Courtaulds Films & Packaging Polymeric films
DE4420991A1 (de) * 1994-06-16 1995-12-21 Danubia Petrochem Deutschland Thermoformen von ß-nukleierten Polypropylenen
DE4420989B4 (de) 1994-06-16 2005-04-14 Borealis Polymere Holding Ag Verfahren zur Erhöhung des Anteils der ß-Modifikation in Polypropylen
US6013353A (en) * 1996-05-07 2000-01-11 Mobil Oil Corporation Metallized multilayer packaging film
GB2323323A (en) * 1997-03-18 1998-09-23 Hoechst Trespaphan Gmbh Polymeric label
US6228316B1 (en) * 1998-04-24 2001-05-08 Moseley, Iii Ben P. P. Polypropylene film suitable for use in in-mold labeling process
GB9818560D0 (en) 1998-08-27 1998-10-21 Hoechst Trespaphan Gmbh Polymeric films
DE19949898C2 (de) * 1999-10-15 2003-01-30 Trespaphan Gmbh Verwendung einer Polyolefinfolie als In-Mould-Etikett
KR100739978B1 (ko) * 2001-02-21 2007-07-16 신닛폰 리카 가부시키가이샤 다공성 폴리프로필렌 축차 이축 연신 필름 및 그의 제조방법
AU2003221529A1 (en) * 2002-04-24 2003-11-10 Treofan Germany Gmbh & Co. Kg. Use of polypropylene films for in-mold labeling
CN101035676B (zh) 2004-10-07 2011-04-13 特里奥凡德国有限公司及两合公司 用于深拉法的标签膜

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2006099990A1 *

Also Published As

Publication number Publication date
WO2006099990A1 (fr) 2006-09-28
US20090041965A1 (en) 2009-02-12
HK1118256A1 (en) 2009-02-06
AU2006226596A1 (en) 2006-09-28
CN101142082B (zh) 2010-10-06
CA2601989A1 (fr) 2006-09-28
US20130037983A1 (en) 2013-02-14
MX2007011517A (es) 2007-10-11
AU2006226596B2 (en) 2010-11-18
CA2601989C (fr) 2014-06-17
CN101142082A (zh) 2008-03-12
US8968632B2 (en) 2015-03-03

Similar Documents

Publication Publication Date Title
EP1796903B1 (fr) Film d'etiquettes destine a un procede d'emboutissage
WO2006099990A1 (fr) Film d'etiquettes destine a un procede par moule de soufflage
EP1885558B2 (fr) Feuille-barriere multicouche coextrudee comportant au moins une couche de feuille a base de copolymere ethylene-alcool vinylique (evoh), son procede de production, et son utilisation
EP2170605B1 (fr) Feuille à étiquettes pour procédé d'emboutissage
EP1501886B1 (fr) Utilisation de films polypropylene pour l'etiquetage au moulage
EP1224069B1 (fr) Etiquette a base de film en polyolefine
DE10235557B4 (de) Etikettenfolie für In-Mould-Verfahren
WO2004050353A2 (fr) Feuille a orientation biaxiale presentant une couche de copolymere ethylene/alcool vinylique (evoh)
EP2205435B1 (fr) Feuille pour étiquettes enveloppantes
EP2421698B1 (fr) Feuille d'étiquettes
WO2005100019A2 (fr) Feuille de polypropylene a orientation biaxiale destinee a des etiquettes
EP2387493B1 (fr) Utilisation d'une feuille d'étiquettes pour procédé par emboutissage profond
EP2684675B1 (fr) Polymer film for in-mould labelling
EP1115552B1 (fr) Etiquette constituee d'un film de polyolefine
WO2020058323A1 (fr) Étiquette surmoulée
DE19931722A1 (de) Etikett aus Polyolefinfolie

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20071019

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20091023

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20151001