Classifications

• • 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
  • B32B27/08—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 of synthetic resin
• • 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
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)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
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
  • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)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
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
• • 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
  • B32B2307/724—Permeability to gases, adsorption
  • B32B2307/7242—Non-permeable
• • 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
  • B32B2307/724—Permeability to gases, adsorption
  • B32B2307/7242—Non-permeable
  • B32B2307/7246—Water vapor barrier
• • 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
  • B32B2307/74—Oxygen absorber
• • 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
  • B32B2323/00—Polyalkenes
  • B32B2323/04—Polyethylene
• • 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
  • B32B2329/00—Polyvinylalcohols, polyvinylethers, polyvinylaldehydes, polyvinylketones or polyvinylketals
  • B32B2329/04—Polyvinylalcohol
• • 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
  • B32B2439/00—Containers; Receptacles
• • 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
  • B32B2439/00—Containers; Receptacles
  • B32B2439/80—Medical packaging
• • 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]
  • Y10T428/1355—Elemental metal containing [e.g., substrate, foil, film, coating, 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]
  • Y10T428/24959—Thickness [relative or absolute] of adhesive layers
• • 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
  • Y10T428/24975—No layer or component greater than 5 mils thick
• • 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
  • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
  • Y10T428/2835—Web or sheet containing structurally defined element or component and having an adhesive outermost layer including moisture or waterproof 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
  • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
  • Y10T428/2852—Adhesive compositions

Definitions

• the invention relates to layered materials, in particular multilayer packaging materials for oxygen-sensitive products.
• the materials according to the invention are particularly suitable for the production of blister packs for pharmaceutical and other products. Further aspects of the invention relate to a method for producing such layered materials and their preferred uses.
• barrier properties, in particular for oxygen, of the known packaging materials for sensitive pharmaceutical products are usually not sufficient.
• the known packaging materials are often complex to manufacture and unsatisfactory in terms of processing properties, such as deep-drawability, adequate adhesion between the individual layers, transparency of the multilayer or activation of the oxygen absorber.
• Multilayer films can be produced by coextrusion and / or lamination.
• multi-layer packaging films and packaging materials for sensitive goods consist of a thin gas barrier core layer, which can be connected to cover layers via an adhesion promoter layer or a laminating adhesive layer.
• US Pat. No. 6,589,384 B2 and US Pat. No. 6,462,163 B2 relate to certain solvent-free polyurethane adhesive layers, layer thicknesses well below 5 ⁇ m being obtained from the coating weights indicated.
• the object of the present invention was therefore to provide a layered material which avoids the disadvantages of the prior art, offers very good barrier properties and at the same time can be produced easily and quickly and, in particular, can be processed advantageously into blister packs.
• Another task was to provide one layered material with good oxygen absorption properties.
• the layered material contains at least the following layers in succession adjacent to one another: a) a gas barrier layer based on EVOH; b) an adhesive layer based on at least one anhydride-modified polymer; c) an oxygen absorber layer based on at least one polymeric, non-particulate oxygen absorber.
• This layer sequence improves the gas barrier unexpectedly, especially for oxygen, but also for other gases such as CO 2 or moisture. It is important that an adhesive layer based on an anhydride-modified polymer is arranged between the gas barrier layer containing or based on EVOH and the oxygen absorber layer based on at least one polymeric, non-particulate oxygen absorber. It is assumed, without restricting the invention to the correctness of this assumption, that in the above layer sequence on the contact surfaces of the layers or in the layers themselves material properties are obtained which differ from those of the individual layers as such and to surprisingly increased barrier properties interact. This was all the more surprising which, as for example in WO 02/44034 A2, expressly teaches the direct connection of an EVOH oxygen barrier layer and an oxygen absorber layer to an ethylenically unsaturated polymeric oxygen absorber.
• a layer based on an adhesion promoter in the form of an anhydride-modified polymer is thus used as the adhesive layer between the gas barrier layer and the oxygen absorber layer.
• the coupling agent is selected from anhydride-modified polyolefins, in particular anhydride-modified polyethylene or polypropylene.
• anhydride-modified polymers or polyolefins are familiar to those skilled in the art as such.
• suitable adhesion promoters are given in a non-limiting manner in the examples. When such adhesion promoters are used in the layered materials according to the invention, particularly good processability and bond strength have also been found.
• the term "based on” is used in the present specification to include both “consisting of", “consisting essentially of” or “containing”.
• the corresponding layer preferably has more than 50%, particularly preferably at least 75%, in particular at least 90% of the components specified in each case.
• the adhesive layer consists predominantly, ie to more than 50% by weight, of at least one adhesive agent. A proportion of more than 75% by weight, in particular more than 90% by weight, is further preferred. It was observed that the barrier properties increase with the proportion of the adhesion promoter (the anhydride-modified polymer) in the adhesive layer.
• the adhesive layer consists of more than 95% by weight, in particular more than 99% by weight, of the above-mentioned adhesive agent.
• the adhesion promoter layer thus consists essentially or exclusively of at least one adhesion promoter in the form of one or more anhydride-modified polymers.
• the gas barrier layer adjoining the adhesive layer on one side contains or is based on EVOH (ethylene / vinyl alcohol copolymer).
• a gas barrier layer is preferably understood here to mean a layer which offers a considerable barrier function for gaseous substances such as in particular oxygen and carbon dioxide. This layer should have a permeability of ⁇ 10 cm 3 / m 2 dbar for 100 ⁇ m thick films according to barrier systems familiar to the person skilled in the art. It was also found here that the barrier properties increase with the proportion of EVOH, in particular in connection with the adjacent adhesion promoter layer and the oxygen absorber layer.
• the gas barrier layer consists predominantly, ie more than 50% by weight, of EVOH.
• polyamide can also be present in the gas barrier layer in addition to EVOH.
• a layer of EVOH can be provided on one or both sides with a separate layer of polyamide. It was found that in this way, compared to gas barrier layers made from pure EVOH, films / layers which are more economical but in many cases practically equivalent can be produced.
• an EVOH layer is therefore provided as an gas barrier layer on the side opposite the adhesive layer with an adjacent layer of polyamide.
• the oxygen absorber layer adjacent to the adhesive layer on the other side is based on at least one polymeric, non-particulate oxygen absorber. It was found that no equivalent results can be achieved with non-polymeric oxygen absorbers.
• Polymer is to be understood here in particular to mean homopolymeric, copolymeric and terpolymeric compounds and polymeric compounds of a higher order. The term “polymer” should also be understood as a differentiation from “monomer” or "not present as a polymer”. Without the invention being restricted to the correctness of this assumption, it is assumed that polymeric oxygen absorbers enable a particularly advantageous interaction with the adjacent adhesive layer based on at least one anhydride-modified polymer.
• the oxygen absorber layer therefore preferably contains no particulate components. It was also found here that the barrier properties increase with the proportion of the oxygen absorber, in particular in connection with the adjacent adhesion promoter layer and the gas barrier layer. According to a preferred embodiment of the invention, the oxygen absorber layer consists predominantly, ie more than 50% by weight, of the above-mentioned oxygen absorber. A proportion of more than 75% by weight, in particular more than 90% by weight, is further preferred. Particularly advantageous results are obtained when the oxygen absorber layer consists of more than 95% by weight, in particular more than 99% by weight, of the above-mentioned oxygen absorber.
• the oxygen absorber layer thus consists essentially or exclusively of the above-mentioned oxygen absorber.
• a catalyst for the reduction of the oxygen absorber in particular a transition metal catalyst as known to the person skilled in the art, for example from WO02 / 44034, as well as a photoinitiator and optionally an antioxidant can be included.
• ethylenically unsaturated polymeric oxygen absorbers are, for example, the low molecular weight ethylenically unsaturated compounds such as polybutadiene oligomer or polybutadiene diols as described in WO 99/15433 A, catalyst-free absorbers such as quinones, photoreducible dyes and carbonyl compounds, in particular anthraquinones, as described in WO96 / 34070 and WO94 / 12590 are described, aliphatic hydrocarbons with at least one unsaturated group and / or at least one unsaturated fatty acid compound, and systems composed of polydienes or polyethylene-butylene copolymers as described in EP 0 835 685 and EP 0 965 381, and oxidizable polydienes or polyethers as described in WO01 / 83318.
• the related revelations are expressly included in the description by reference.
• q lf q 2 , q 3 , q 4 and r are independently selected from hydrogen, methyl or ethyl; m is - (CH 2 ) n - wherein n represents an integer from 0 to 4 (inclusive) and, if r represents hydrogen, at least one of q l7 q 2 , q 3 and q 4 also represents hydrogen.
• the oxygen absorber is preferably an ethylene / vinylcyclohexene copolymer (EVCH).
• the oxygen absorber polymer preferably also has a connecting group which connects the ethylenic backbone to the cyclic olefin group. The connection group is selected from
• the cyclic olefin group is preferably a cycloalkenyl group with structure I. Is more preferred in the structure I, n is 1, and qi, q 2 , q3; q 4 and r are each hydrogen. Even more preferably, the oxygen absorber polymer is a cyclohexenyl methyl acrylate homopolymer (CHAA), a cyclohexenyl methyl acrylate copolymer, a cyclohexenyl methyl methacrylate homopolymer (CHMA), a cyclohexenyl methyl methacrylate copolymer or a mixture of more than one of the above components.
• CHMA cyclohexenyl methyl methacrylate homopolymer
• the oxygen absorber polymer is an ethylene / methyl acrylate / cyclohexenyl methyl acrylate copolymer (EMCM).
• the oxygen absorber layer can contain at least one photoinitiator and optionally at least one antioxidant, as is familiar to the person skilled in the art and described, for example, in WO 02/44034 A2. The relevant disclosure of WO 02/44034 is also expressly incorporated into the present description by reference.
• the total thickness of the adhesion promoter layers is preferably at least about 10 ⁇ m. According to a preferred embodiment of the invention, the total thickness of the adhesion promoter layer (s) is at least about 15 ⁇ m, in particular at least about 20 ⁇ m. In many cases, a total thickness of the adhesion promoter layer (s) of between approximately 20 and 40 ⁇ m, in particular of approximately 20 ⁇ m, is preferred, especially if the layer material according to the invention is to be used as a thermoformable multilayer film.
• adhesion promoter layer with a thickness of at least approximately 5 ⁇ m, preferably at least approximately 6 ⁇ m, particularly preferably at least approximately 8 ⁇ m. In some cases, at least one adhesion promoter layer with a thickness of at least about 10 ⁇ m, in some cases even at least about 15 ⁇ m, is particularly advantageous.
• the entire layered material preferably contains, depending on the other layers contained, between one and three adhesion promoter layers.
• the adhesion promoter layer (b) located between the gas barrier layer (a) and the oxygen absorber layer (c) has a thickness of at least 5 ⁇ m, in particular at least 10 ⁇ m, more preferably at least 15 ⁇ m, more preferably at least 20 ⁇ m.
• the adhesion promoter layers consist predominantly, that is to say more than 50% by weight, of at least one adhesion promoter. Frequently, a proportion of more than 75% by weight, particularly preferably more than 90% by weight, will provide particularly advantageous results.
• the adhesion promoter layer (s) can therefore preferably consist essentially or exclusively of at least one adhesion promoter.
• At least one adhesion promoter layer in particular an adhesive layer not arranged between the gas barrier layer and the oxygen absorber layer (if present) comprises a mixture of an adhesion promoter with at least one further component
• the proportion of the adhesion promoter in the mixture can also be less than about 50% by weight.
• the proportion of the adhesion promoter in the mixture will be at least about 10% by weight.
• the further component (s) in the adhesion promoter layer can, for example, be selected such that they fulfill further useful functions in the layered material, for example as a gas or moisture barrier or oxygen absorber (see below).
• the coupling agent is selected from anhydride-modified polyolefins, in particular anhydride-modified polyethylene or polypropylene.
• anhydride-modified polyolefins are known to the person skilled in the art.
• suitable adhesion promoters are given in a non-limiting manner in the examples. When such adhesion promoters are used in the layered materials according to the invention, particularly good processability and bond strength have also been found.
• Adhesion promoters which can be melted with different polymers in extruders, are used in coextrusion.
• the adhesion promoters used according to the invention are preferably thermoplastically processable polymers such as, for example, ionomeric copolymers, vinyl chloride copolymers, polystyrene copolymers or anhydride-grafted polymers. Examples are, for example, polymers modified with maleic anhydride or with rubber, such as the Plexar series from Quantum Chemical Corp.
• laminating resins or laminating adhesives When laminating, two or more layers are connected by means of laminating resins or laminating adhesives.
• Laminating or laminating resins are usually liquid and only polymerize in a "drying process".
• the laminating adhesives used according to the invention are preferably polymerizable polyesters, phenolic resins, for example from DuPont, or polyurethane systems, which are preferably solvent-free and are preferably suitable for food packaging.
• At least one further gas barrier layer can optionally be contained in the layered material according to the invention.
• the composition of the gas barrier layer can be chosen arbitrarily from materials familiar to the person skilled in the art.
• the gas barrier layer is preferably based on polyacrylonitrile (PAN), polyamide (PA), polyethylene halides such as PVC, PVDC, PVF, PVDF, halogen-containing copolymers, cycloolefinic polymers (COC), polyethylene terephthalate (PET), polycarbonate (PC), EVOH, Polyethylene naphthalein (PEN), liquid crystalline polymers or copolymers (LCP) or inorganic-organic hybrid polymers or their mixtures or copolymers.
• PAN polyacrylonitrile
• PA polyamide
• PVC polyethylene halides
• PVDC polyethylene halides
• PVF polyethylene halogen-containing copolymers
• COC cycloolefinic polymers
• PET polyethylene terephthalate
• the gas barrier layer (s) present in the layered material has a layer thickness of in each case or in total less than 100 ⁇ m, preferably less than 80 ⁇ m, in particular less than 50 ⁇ m.
• adhesive layers are provided on both sides adjacent to the gas barrier layer.
• the layered material has at least one cover layer, which preferably serves as a water vapor barrier.
• Materials with a water permeability of less than 10 g / m 2 d (ISO 15106-3) are generally referred to as water vapor barriers.
• Such a cover layer is preferably based on filled or unfilled polymers, in particular selected from polyesters such as polyethylene terephthalate), polyurethanes, polyolefins such as polyethylene or polypropylene, polyethylene halides such as PVC, PVDC, PVF, PVDF, halogen-containing copolymers, polyolefin copolymers such as ethylene vinyl acetate (EVA ), liquid crystalline polymers (LCP's), PAN, PEN, COC or their mixtures or copolymers.
• polyesters such as polyethylene terephthalate
• polyurethanes such as polyethylene or polypropylene
• polyethylene halides such as PVC, PVDC, PVF, PVDF, halogen-containing copolymers
• polyolefin copolymers such as ethylene vinyl acetate (EVA ), liquid crystalline polymers (LCP's), PAN, PEN, COC or their mixtures or copolymers.
• At least one further oxygen absorber layer can optionally be contained in the layered material according to the invention.
• any oxygen absorber can be used for this. Suitable materials are familiar to the person skilled in the art. A general definition can be found, for example, in "Active Food Packaging", ML Rooney, Blackie Academic & Professional, 1995, Chapter 4.
• oxygen absorbers are generally used, which consist of metal powder, in particular iron, and a hygroscopic salt, as described in WO 99/47596.
• WO 97/22469 describes the use of linseed oil, squalene or ascorbic acid derivatives.
• Recent developments are based on low molecular weight, ethylenically unsaturated substances, as are described, for example, in EP 888 719. Both metal powder and, for example, ascorbic acid derivatives are activated in the presence of moisture. Recent developments such as low molecular weight, ethylenically unsaturated substances are usually self-activating and can be used for dry packaging materials.
• Oxygen absorbers are mixed into suitable plastics or described as a layer in a multi-layer structure (US 5,529,833 and WO 97/22469).
• Application examples are crown caps for beverage bottles or PET bottles with an oxygen-absorbing barrier layer.
• 0 2 absorbers are used in the oxygen absorber layer (s) contained in the layered material according to the invention, which are self-activating or by radiation such as UV, VIS, X-ray or ⁇ radiation, by water or Humidity or can be activated thermally. Particular preference is given in particular to activated (activated) 0 2 absorbers which emit oxygen even at low relative humidity (RH ⁇ 20%); these are particularly suitable for moisture-sensitive pharmaceuticals.
• the structure and the composition of the layered material provide an excellent barrier function against moisture and oxygen, which exceeds that of conventional materials.
• the packaging materials according to the invention have a high barrier compared to 0 2 compared to conventional film variants, the barrier of which is referred to as "high"( ⁇ 1.0 cm 3 0 2 / (m 2 d bar), measured in accordance with DIN 53380, part 3, see example 1).
• the oxygen permeability of the layered material, as described in Example 1 is less than 0.1 cm 3 / (m 2 d bar).
• the CO 2 permeability can also be unexpectedly greatly reduced.
• the CO 2 permeability determined as described in Example 1 (DIN 53380 T2 at 23 ° C.), is ⁇ 50 cm 3 / (m 2 d bar), in particular ⁇ 25 cm 3 / (m 2 d bar), more preferably ⁇ 10 cm 3 / (m 2 d bar), more preferably ⁇ 5 cm 3 / (m 2 d bar), particularly preferably ⁇ 2 cm 3 / (m 2 d bar).
• the individual components of the multilayer packaging material according to the invention are selected in such a way that highly transparent and easily deep-drawn films can be produced, as are particularly desired for the production of blister packs for pharmaceutical products.
• the layered materials comprise in sequence: a) A top layer (to the outside later), which preferably serves as a water vapor barrier (see above) and consists of filled or unfilled polymers, in particular selected from polyester such as polyethylene terephthalate), polyurethanes, polyolefins such as polyethylene or polypropylene, polyethylene halides such as PVC, PVDC, PVF, PVDF, halogen-containing copolymers, polyolefin copolymers such as ethylene vinyl acetate (EVA), liquid-crystalline polymers (LCP's), PAN, PEN, COC or mixtures thereof, preferably polyolefins, in particular polyethylenes;
• a top layer to the outside later
• a top layer which preferably serves as a water vapor barrier (see above) and consists of filled or unfilled polymers, in particular selected from polyester such as polyethylene terephthalate), polyurethanes, polyolefins such as polyethylene or polypropylene, polyethylene halides
• Adhesion promoter layer an adhesive layer (adhesion promoter layer) as defined above, the adhesion promoter preferably being selected from: ionomeric copolymers, vinyl chloride copolymers, modified ethylene vinyl acetates, polymerizable polyesters, phenolic resins, polystyrene copolymers or anhydride-modified polymers, 2-components -Adhesives, 1-component or 2-component laminating resins; PU systems and / or epoxy resins; or mixtures of the above substances, preferably anhydride-modified polymers, solvent-free 1-component resins or isocyanate-free 2-component adhesives, in particular anhydride-grafted polyolefins and polyurethane systems,
• the gas barrier layer can also contain polyamide in addition to ethylene / vinyl alcohol copolymer (EVOH).
• EVOH ethylene / vinyl alcohol copolymer
• a preferred possibility is that a core layer consisting of EVOH is surrounded on one side or, particularly preferably, on both sides by a layer based on polyamide.
• the layered materials according to the invention are preferably transparent or translucent multilayer films.
• the total thickness of the layered material is in many cases at least 100 ⁇ m.
• the adhesion promoter layer (s) and their thickness are of crucial importance not only for the adhesion of the adjacent layers, such as the gas barrier layer c) to the adjacent layers b) and d), but also has an unexpectedly high impact on the barrier and processing properties of the layered material.
• Polymers modified with anhydrides, solvent-free 1-component resins or isocyanate-free 2-component adhesives, in particular anhydride-grafted polyolefins are particularly preferred.
• initiation of the layered materials containing oxygen absorbers with low-dose UV light is readily possible when using the layer structure according to the invention.
• the layer systems according to the invention with integrated oxygen absorbers with UV light low dose can be easily activated for oxygen absorption.
• the capacity of the packaging materials according to the invention is surprisingly high (corresponds to 60-99% of theory), especially at low relative humidity (e.g. RH less than about 50%, especially less than about 25%), especially when using anhydride-modified adhesive - intermediaries.
• the oxygen absorption kinetics is also comparable to the expected theory, which cannot be expected with multi-layer systems.
• the layered material according to the invention preferably has a further layer (f), in particular a cover layer, towards the inside of the packaging (packaged goods side), which e.g. is in contact with the packaged product (contact layer).
• This cover or contact layer is preferably selected from polyvinyl chloride, polyethylene or polypropylene.
• the relatively cheap BOPP films can also advantageously be processed in one process step with the other layers to form the multilayer packaging material according to the invention.
• there is very good adhesion of the PVC film to the polymeric oxygen absorber layer with high oxygen consumption preferably without using the customary 1-component adhesives.
• the layered material according to the invention can be processed particularly advantageously, and without the problems of delamination or detachment which occur in conventional multilayers at layer interfaces, in the form of a blister film or packaging, in particular for pharmaceutical products.
• the multilayer film can be deep-drawn very well using common deep-drawing tools. How to look of microtome sections can be verified, the network remains completely intact.
• the deep-drawn film has very good transparency and stability with excellent barrier properties.
• the film thickness of each layer of the materials described can be chosen as required.
• the thickness of the individual (sub) layers after production is preferably less than about 100 ⁇ m.
• the functionality of the layers, e.g. the capacity of the oxygen absorber can be set.
• a cover layer thickness before thermoforming of 20-200 ⁇ m, in particular a (PE) layer of 30-150 ⁇ m including adhesive agent, is preferably produced.
• a gas barrier thickness of 0 to 80 ⁇ m is preferably set, particularly preferably 5 to 70 ⁇ m.
• the adhesive layer (HV) between the gas barrier and the oxygen absorber comprises 3 to 20 ⁇ m and between the oxygen absorber and the contact layer on the packaged goods side comprises 0 to 20 ⁇ m, in particular 5 to 15 ⁇ m.
• the absorber layer should be 5-100 ⁇ m, preferably 5-70 ⁇ m, and the thickness of the contact layer (cover layer) on the packaging side is 0-100 ⁇ m, in particular 10-80 ⁇ m.
• the packaging material comprises one of the layer sequences below.
• the present invention also relates to a method for producing composite films.
• This multi-layer extrusion or coextrusion produces films that have properties that cannot be achieved by a single plastic.
• the plastic melt is processed into a composite film via a wide outlet nozzle and then a smoothing unit.
• the film is preferably stretched uniaxially after the nozzle exit.
• the plastic melt is processed with cooling air rings to form a film bubble which, after cooling, is fixed locally and laid flat and wound up using a winder.
• the film is preferably stretched biaxially, which affects the mechanical properties of the film. If the layers have poor adhesion, the permanent bond must be established with intermediate layers on adhesion promoters.
• the film thicknesses obtained can vary from 10-500 ⁇ m.
• composite materials e.g. Composite films.
• a dispersion or laminating adhesive is applied between the materials to be joined and combined in a laminating unit.
• the materials to be joined are pretreated (e.g. Corona) to improve adhesion.
• the composite is sent to a drying process or UV curing.
• the layer thicknesses of laminated films range between 60 - 600 ⁇ m.
• At least one gas barrier layer is built into the structure.
• the adhesion of this layer is realized with the help of adhesion promoters. based, especially through the use of anhydride functionalized adhesion promoter polymers.
• the structure of the composite film contains at least one oxygen absorber layer, with at least one oxygen absorber.
• non-compatible cover layers or contact layers such as PVC and the usual sealing media such as the non-polar polyolefins must be used in the current state of the art on adhesion promoters.
• such composites can be produced with PVC by producing the adjacent layers with adhesion promoter by coextrusion in a first processing step.
• the PVC contact layer is generally applied to the composite in a second processing step by lamination with laminating adhesives or laminating resin.
• the PVC layer running from the roll or the polyolefin layers f) can be connected to the adjacent coextruded layer e) in one step by extrusion coating and without an adhesion promoter ,
• the plastic melt of the coextrusion preferably flows out of a slot die connected downstream of the extruder and meets the supplied carrier web. The meeting takes place in a nip.
• the calender and the pressure roller were heated.
• the opposing rollers press the melt onto the carrier web and connect the two together under pressure.
• opposing rollers press the melt onto the carrier web and connect under pressure from e.g. approx. 4 bar the multi-layer system.
• the present invention therefore relates to a method for producing a layered material.
• a thermoformable film or a blister pack as described or claimed herein, comprising the following steps: a) providing a gas barrier layer based on EVOH; b) providing an adhesive layer based on at least one anhydride-modified polymer; c) providing an oxygen absorber layer based on at least one polymeric, non-particulate oxygen absorber; d) connecting or applying the gas barrier layer, the adhesive layer and the oxygen absorber layer to one another.
• one aspect of the present invention relates to a method for producing a layered material or packaging material as defined herein, the multilayer film with the layers a) to e) being produced in only one process step by coextrusion.
• the layer f) adjoining the layer e) is preferably coextruded in the same process step, provided that this is based on a polyolefin.
• layer f) is based on polyvinyl chloride (PVC)
• PVC polyvinyl chloride
• a more cost-effective, calendered PVC film can be applied in one process step by a combination of coextrusion (PE-HV-EVOH-HV absorber) and extrusion coating (PVC).
• PE-HV-EVOH-HV absorber coextrusion
• PVC extrusion coating
• the multilayer film can be produced by coextrusion in one process step.
• production in combination with an extrusion coating from a supplied PE film is also possible.
• an inexpensive BOPP film can be applied in one process step by combining coextrusion and extrusion coating.
• the following examples show that it has surprisingly been possible to combine in particular polyolefins such as PE or PP and PVC in one processing step with high-barrier materials to form deep-drawable, oxygen-absorbing high-barrier materials, particularly when using anhydride-functionalized HV polymers.
• a flat film line from Diamant consisting of three single-screw extruders and an incoming PVC or polyolefin film, as well as the flat film line from Dr. Collin GmbH (5-layer coextrusion box, Chill-Roll CR 136/350), consisting of 4 single-screw extruders and an incoming PVC or polyolefin film.
• the results of the oxygen absorption measurement on the finished multilayer film according to the invention show that UV activation of the absorber system used is possible through the contact layer on the packaged goods side, with only a very small dose (for example between 0.5 and 1.5 J / cm 2 ) for activation is required.
• the films on which the invention is based can protect products from oxygen regardless of the air humidity.
• the oxygen content could be reduced within 2 to 7 days, starting from atmospheric oxygen content below 2% oxygen in the measuring cell at low humidity, preferably ⁇ 50% RH, in particular ⁇ 25% RH.
• the permeability to oxygen before irradiation which is a measure of the barrier to atmospheric oxygen during storage of the packaging, is better with 0.5 - 0.03 cm 3 0 2 / m 2 d bar than common high barrier materials for oxygen (> 1 cm 3 0 2 / m 2 d bar).
• the barrier bond can be produced on the basis of the preferred adhesion promoters.
• the contact layer made of polymers such as PVC or polyolefins such as PE / PP on the packaging side can be realized by means of extrusion coating. This greatly simplifies FDA approval.
• thermoformable film produced from a material that comprises a layered material according to the invention.
• Both the layered material and the film can generally have any size and shape. Depending on the area of application, any dimensions can be produced and used. In many cases, the layered material according to the invention will be produced in long lines.
• thermoformable film is sealable with a metal film, such as an aluminum film, to which a sealing medium has been applied.
• Another aspect of the invention relates to a blister pack comprising a layered material according to the invention, in particular in a deep-drawn form, and optionally a metal foil sealed therewith.
• Another aspect of the invention relates to the use of the material according to the invention or the film or blister packaging.
• a preferred use relates to use in a gas barrier layer with an oxygen permeability of ⁇ 1 cm 3 / m 2 d bar, in particular ⁇ 0.1 cm 3 / m 2 d bar.
• An important use according to the invention relates generally to the packaging of pharmaceutical and non-pharmaceutical products.
• Preferred uses include, for example, reducing the oxygen concentration in a container or packaging for a preferably oxygen sensitive product or packaging a solid, liquid or gas product.
• the product can be a pharmaceutical product, in particular in solid form, for example a tablet, capsule, dragee, powder or suppository, or else a liquid pharmaceutical product.
• the packaging can be, for example, an outer packaging of several packaging units for (pharmaceutical) products.
• the packaging can, for example, be in the form of a bag, a bottle, a tray, a single-dose packaging, a blister packaging or a container.
• the product to be packaged can also be a non-pharmaceutically used chemical, a foodstuff, technical components, in particular electrotechnical and electronic components, cosmetics, non-pharmaceutically used, biotechnologically produced products, in particular enzymes or proteins, or the like.
• Example 1 (PE / HV / EVOH / HV / Absorber / PE)
• the gas permeability (0 2 ) of the composite systems was examined in accordance with DIN 53380, Part 3 with a MOCON (Modern Control Inc.) at 23 ° C.
• the results of the oxygen permeability (OTR in cm 3 0 2 / m 2 d bar) are summarized in Table 1.
• the gas permeability for C0 2 was investigated with the manometric measuring method according to DIN 53380 T2 at 23 ° C. Corresponding results were obtained when Example 1 was repeated on the flat film system from Comparative Example 1.
• Table 1 Barrier composite with PE contact layer on the packaged goods side
• the excellent barrier values, ie the extremely low gas permeability of the composite film of example 1 according to the invention, is further surprising since, according to the theoretical calculation of the corresponding barrier of PE / EVOH / absorber / PE or PVC, a total gas permeability (0 2 , C0 2 ) of> 0, 2 cm 3 / m 2 d bar would be expected.
• the expected total permeability can be estimated from the sum of the individual permeabilities of the materials used and layer thicknesses ("Plastic Packaging Materials for Food", O.-G. Piringer, AL Baner, Wiley-VCH 2000).
• the expected barrier in the composite is generally determined by the layer thickness of the barrier material.
• the C0 2 permeability corresponds approximately to 4 times the value of the 0 2 permeability.
• Example 1 was repeated, with the exception that the adhesion promoter layers were each 2 ⁇ m thick, significantly higher gas permeabilities (0 2 , C0 2 ) were observed.
• Example 3 (PE / HV / EVOH / HV / absorber / KK / PP)
• the 50 ⁇ m PVC film was removed on the laminating system of the Fraunhofer IW and the coextrusion film was laminated with a 100 ⁇ m PP film and laminating adhesive (Lamal type, from Rohm and Haas).
• laminating adhesive Lamal type, from Rohm and Haas.
• the oxygen permeability of the composite systems was examined in accordance with DIN 53380, Part 3 with a MOCON (Modern Control Inc.) at 23 ° C.
• the results of the oxygen permeability and the C0 2 permeability (in cm 3 / m 2 d bar) are summarized in Table 2.
• a flat film line from Diamant (DE 45/30/30/800) consisting of three single-screw extruders and an incoming PVC or polyolefin film as well as the flat film line from Dr. Collin GmbH (5-layer coextrusion box, Chill-Roll CR 136/350), consisting of 4 single-screw extruders, and an incoming PVC or polyolefin film.
• Blown film lines are also suitable for producing the multilayer composite materials (layered materials) inexpensively in one step.
• a blown film line used for tubular film production from Kiefel AG, DE, consisting of three single-screw extruders and blow head.
• a pharmaceutical-compatible 150 ⁇ m PVC film with a layer of 100 ⁇ m absorber (OSP TM systems, Chevron Phillips Chemical Company) was extrusion-coated on the flat film system of the Fraunhofer IW (Freising) at a take-off speed of 3 m / min.
• the absorber side was laminated on the lamination system of the Fraunhofer IW with a 20 ⁇ m PVC film and laminating adhesive (layer thickness: 8 ⁇ m) (Lamal type, from Rohm and Haas).
• laminating adhesive layer thickness: 8 ⁇ m
• the film roll was wrapped in aluminum foil, sealed in aluminum bags under a nitrogen atmosphere and stored at 23 ° C. for 7 days.
• the surface energy of the PVC film was 38 dynes
• the surface energy of the absorber layer was 36 dynes.
• the 50 ⁇ m PVC film was removed at the Fraunhofer IW laminating system and the coextrusion film was laminated with a 50 ⁇ m corona-treated PVC film and laminating adhesive (Lamal type, from Rohm and Haas).
• laminating adhesive Lamal type, from Rohm and Haas.
• the film roll was made of aluminum wrapped in a mini foil, sealed in a plastic bag under a nitrogen atmosphere and stored at 5 ° C for 7 days. Comparable results were obtained when using Bynel ® series 4200, DuPont, as an adhesion promoter.
• Example 9 (PE / HV / PA / EVOH / HV / Absorber / PE)
• the results of the bond adhesion measurement are summarized in Table 3 below.
• the samples were separated manually for the bond adhesion measurements.
• the measurements were carried out on an electromechanical universal testing machine at a take-off speed of 100 mm / min in the longitudinal and transverse directions.
• the pull-off angle was 90.
• the person skilled in the art is familiar with the fact that the adhesive force of composites suitable for deep-drawing should be> 1.5 N / 15 mm.
• the films were produced by the methods described above. To activate the oxygen absorption, the film was irradiated with a UVA dryer from Hönle (UVA-Print 200; radiation dose 1.0-2.5 J / cm2). The oxygen absorption of the films was carried out with the Clark electrode after UV initiation at 23 ° C, 50-60% relative humidity (RH) and at 21% oxygen concentration in the measuring cell. The results show that the oxygen absorption can be activated from both sides of the multilayer composites. In particular, the UV-absorbing PVC layer can be initiated with a relatively low radiation dose of 1.0 J / cm 2 . Unless stated otherwise, the initiation from both sides of the composite film gave comparable absorption values.
• Example 7 (PE-HV / EVOH / Absorber-HV / PVC)
• a pharmaceutical-grade 50 ⁇ m PVC film with a layer of 50 ⁇ m absorber-adhesive blend (OSP TM Systems, Chevron Phillips Chemical Company, Admer, Mitsui, 3 : 1), 35 ⁇ m EVOH (Eval, Mitsui) and 80 ⁇ m PE bonding agent blend (Lupolen, Basell; Admer, Mitsui, 1: 1) extrusion-coated.
• OSP TM Systems Chevron Phillips Chemical Company, Admer, Mitsui, 3 : 1
• 35 ⁇ m EVOH Eval, Mitsui
• 80 ⁇ m PE bonding agent blend (Lupolen, Basell; Admer, Mitsui, 1: 1) extrusion-coated.
• Example 3 (PE / HV / EVOH / HV / absorber / KK / PP)
• Example 8 (PE / HV / EVOH / KK /, PE / absorber / PE)
• the two coextrusion composites were laminated on the Fraunhofer IW lamination system with laminating adhesive (2-component system from Rohm and Haas). To harden the laminating adhesive, the film roll was sealed in aluminum under a nitrogen atmosphere and stored at 23 ° C. for 7 days.
• a film consisting of a layer of lOO ⁇ m PE (LDPE, Basell), lO ⁇ m PE adhesion promoter (Bynel series, DuPont), 50 ⁇ m EVOH (Eval, Fa. Mitsui), 10 ⁇ m PE adhesion promoter (Bynel series, DuPont), 20 ⁇ m PE (Lupolen, Basell), 20 ⁇ m absorber (OSP TM Systems, Chevron Phillips Chemical Company) and 30 ⁇ m PE (Lupolen, Basell) co-extruded.

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