WO2000076765A1 - Barrier material made of extruded microlayers - Google Patents
Barrier material made of extruded microlayers Download PDFInfo
- Publication number
- WO2000076765A1 WO2000076765A1 PCT/IB2000/000934 IB0000934W WO0076765A1 WO 2000076765 A1 WO2000076765 A1 WO 2000076765A1 IB 0000934 W IB0000934 W IB 0000934W WO 0076765 A1 WO0076765 A1 WO 0076765A1
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- WIPO (PCT)
- Prior art keywords
- film
- microlayers
- microlayer
- evoh
- adhesive
- Prior art date
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
-
- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2009/00—Layered products
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
- B32B2307/7242—Non-permeable
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
- B32B2307/7242—Non-permeable
- B32B2307/7244—Oxygen barrier
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
- B32B2307/7242—Non-permeable
- B32B2307/7248—Odour barrier
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
- B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
- B32B37/153—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state at least one layer is extruded and immediately laminated while in semi-molten state
Definitions
- the present invention relates to a barrier material for a flexible film or tape constructed of multilayer materials. Specifically, the present invention relates to a multilayer material constructed of extruded microlayers capable of being a barrier to gases and vapor such as, for example, oxygen, water vapor and/or flavors.
- the multilayer film may be useful in packaging to limit the exchange of gas or vapor molecules between two discrete volumes such as, for example, between the outside air and an inside atmosphere of a package. Specifically, humidity and oxygen tend to degrade the quality of a packaged product, such as, for example, foods by diffusing across the packaging film. Further, flavors can be lost if diffused through the packaging film to the outside air.
- polyolefin material as barrier layers in film packaging products. Typical polyolefins may consist of polyethylene (“PE”), polypropylene (“PP”) and polyethylene terephthalate (“PET").
- barrier layers in film packaging products may include ethylene-vinyl alcohol (“ENOH”), polyvinylidene chloride (“PVDC”), polyamides ("nylon", “PA6” or “MXD6”), polyketones and other like polymeric material.
- ENOH ethylene-vinyl alcohol
- PVDC polyvinylidene chloride
- PA6 polyamides
- MXD6 polyamides
- polyketones polyketones and other like polymeric material.
- many of these barrier materials may have certain drawbacks. For example, in the case of ENOH, it is known that these polymers are sensitive to humidity and must be protected therefrom. However, protecting ENOH from humidity may cause a reduction in the barrier properties of the ENOH material.
- the typical multilayer films based on ENOH thus contain at least three or more layers (usually five) including one barrier layer of ENOH, two external layers "A” and “C", and two layers of adhesive ("Adh”), to ensure the connection between the EVOH and the external layers.
- This arrangement of film layers may be represented symbolically by the following structure: A/Adh/EVOH/Adh C with "/" representing the division between the layers.
- a polyamide layer such as, for example, a layer consisting of PA6 to protect the barrier layer from damaging water vapor.
- Such a film can be represented by the structure A/Adh/PA6/EVOH/PA6/Adh/C.
- This article describes the technique for creating ultraviolet (“UN”) reflective films made up of coextruded microlayers consisting of a polypropylene (“PP”) and a polycarbonate (“PC”), each microlayer having the configuration "PP/PC”.
- the article describes ultra-narrow films of PC that can function as a dielectric layer in capacitors.
- the article describes the mechanical properties and the impact stability of films made from coextruded microlayers that alternate a layer of ductile material (PC) and a layer of brittle material such as, for example styrene-acrylonitrile copolymer (“SA ⁇ ").
- PC ductile material
- SA ⁇ styrene-acrylonitrile copolymer
- the '135 patent describes a film having improved bending properties made from an alternation of co-extruded microlayers of a ductile material (polyamide) and a brittle material (polystyrene).
- the present invention relates to a barrier layer for flexible film packaging or tape made from a plurality of extruded microlayers. Specifically, the invention relates to . combinations of structural materials, barrier materials for water vapor and humidity, and/or barrier materials for oxygen-proofing by a process of extrusion of microlayers. While many materials may be utilized in the creation of the barrier layer using microlayers, the present invention highlights the possibility of making a film from a single barrier material formed from coextruded microlayers. In fact, by increasing the number of layers of barrier material and by reducing the thickness of the layers to preserve a constant total thickness of the barrier layer, an increase in the mechanical properties, such as, for example, flex cracking, was observed with little to no reduction in the barrier properties.
- the structural materials that may be utilized for the barrier layer may include, for example, polyolefines such as low density polyethylene (“LDPE”), linear low density polyethylene (“LLDPE”), high density polyethylene (“HDPE”), metallocene polymers, PP, copolymers or mixtures of polyolefins, polystyrene and/or copolymers, polyesters or copolyesters, polyamides, acrylic and methacrylic polymers and copolymers, polycarbonates, thermoplastic polyurethanes, liquid crystalline polymers (“LCP”), and other technical polymers.
- polyolefines such as low density polyethylene (“LDPE”), linear low density polyethylene (“LLDPE”), high density polyethylene (“HDPE”), metallocene polymers, PP, copolymers or mixtures of polyolefins, polystyrene and/or copolymers, polyesters or copolyesters, polyamides, acrylic and methacrylic polymers and copolymers, polycarbonates
- barrier materials that may be utilized specifically against humidity or water vapor may include polymers or copolymers based on: EVOH, PVDC, PA6, MXD6, polyketones, LCP, or other like materials. Of course, any material may be utilized as a barrier material that may be apparent to those skilled in the art.
- an advantage of the present invention to provide a multilayer film and a method of manufacturing the film that provide a large variety of films having diverse properties and further have good to excellent mechanical and barrier properties. Further, it is an advantage of the present invention to provide a multilayer film and a method of manufacturing the film that increase greatly the supply of a variety of different films for particular needs. Still further, it is an advantage of the present invention to provide a multilayer film and a method of manufacturing the film that are economical but have the same or similar barrier and/or mechanical properties relative to known barrier layers.
- an advantage of the present invention is to provide a multilayer film and a method of manufacturing the film that reduce the materials needed for the production of the multilayer material by removing layers or reducing layers' thicknesses without a significant increase in costs of manufacturing.
- an advantage of the present invention is to provide a multilayer film and a method of manufacturing the film that can be utilized on standard extrusion or coextrusion equipment.
- an advantage of the present invention is to provide a multilayer film and a method of manufacturing the film that may improve optical properties including, but not limited to filters (UV or visible), waveguides, iridescent materials and materials having controlled opaqueness.
- an advantage of the present invention is to provide a multilayer film and a method of manufacturing the film that may improve mechanical properties, including, but not limited to, deadfold, chemical delamination, resistance to puncture, the ability for improved thermoforming, improved thermal stability to sterilization and heat filling and biaxial or uniaxial orientation.
- an advantage of the present invention is to provide a multilayer film and a method of manufacturing the film that may improve barrier properties including, but not limited to, loading of inserts, control of the structure in the solid state, effect of controlled diffusion, exfoliation of submicron mineral filler and a controlled absorption.
- an advantage of the present invention is to provide a multilayer film and a method of manufacturing the film that may improve electrical properties such as, for example, conducting charges and/or creating polymer conductors leading to anisotropic conductance and antistatic properties.
- an advantage of the present invention is to provide a multilayer film and a method of manufacturing the film that may improve surface properties to make active systems with reactive layers, controlled diffusion ensuring supply of an additive or a medication, activation by irradiation or thermal treatment and properties of adsorption and or trapping of molecules.
- an advantage of the present invention is to provide a multilayer film and a method of manufacturing the film that may be shaped into three-dimensional applications such as, for example, tubes, laminates, laminated sheets, stamped containers, trays, boxes and/or products molded by laminar injection.
- Figure 4 is a diagram showing resistance to flex cracking measured by the number of holes after bending as a function of the number p of microlayers (represented logarithmically).
- "I” corresponds to a film made up of microlayers of EVOH.
- "II” corresponds to a film made of microlayers of PA6.
- "Ill” corresponds to a film of PA6/EVOH 50/50 by volume, and made of an alternation of microlayers of PA6 and microlayers of ENOH of the same thickness.
- Figure 5 is a diagram showing, for the same films as those tested in Figure 4, the progress of oxygen permeability as a function of the number p of microlayers.
- Figure 6 is a diagram showing, for the same films as those tested in Figures 4 and 5, the progression of resistance to puncture in MPa as a function of the number p of microlayers.
- the four parameter include: 1) the enthalpy of fusion of PA6; 2) the enthalpy of fusion of EVOH; 3) the percentage by weight of the interface compound between each microlayer of PA6 and each microlayer EVOH determined from IR spectra; and 4) the oxygen permeability of the film having microlayers PA6/EVOH-50/50 by volume.
- Figures 8 is a stress vs. strain diagram showing the effect of the composition of the mixture PA6+EVOH on the mechanical characteristics of the film made up of a single layer of the mixture.
- Figure 9 shows a stress vs. percent by volume of PA6 diagram further indicating the effect of the composition of the mixture of PA6+EVOH on the mechanical characteristics of the film made up of a single layer of the mixture.
- Figure 10 shows a strain vs. percent by volume of PA6 diagram further indicating the effect of the composition of the mixture of PA6+EVOH on the mechanical characteristics of the film made up of a single layer of the mixture.
- Figure 11 shows a diagram of a differential scanning calorimetry ("DSC"), with the enthalpy H shown as a function of the temperature T in °C for EVOH and PA6.
- Figure 11 further shows a variable volume percentage of EVOH and PA6, from 100/0.
- the present invention relates to a multilayer film and a method of manufacturing the same that may be utilized as a barrier layer against gas and vapors.
- the present invention relates to a barrier layer film or tape that may be constructed from a plurality of microlayers, each of the microlayers coextruded thereby providing increases in mechanical properties while having little to no loss in performance of barrier properties.
- (X) p may represent the thickness of the stack having the structure "X/X/X" with p times the same unit X and each unit of the structure being symbolically separated from the adjacent layer by the sign " / ". While n can be any whole number, favorable results tend to occur when n is at least 4 or 5. Further, the material may form a film or a tape having a total thickness of between 10 and 2500 ⁇ m.
- Each unit X may consist of one or more microlayers. If more than one microlayer is contained within each unit, then the microlayers may be coextruded together.
- each barrier microlayer within each unit X may be represented by "b" and may be a barrier against oxygen and/or water vapor. Alternatively, the barrier microlayer b may consist of a mixture of barrier materials.
- film may be used to denote material that consists of microlayers according to the invention or that comprises microlayers according to the invention.
- film may refer to film in the narrow sense.
- other thicker materials typically above 300 ⁇ m
- film may include films having standard layers that are produced using a coextrusion or lamination technique that does not utilize microlayers.
- such a “film” may contain a barrier layer, consisting of the plurality of microlayers, having a thickness that is relatively equal to the thickness of a standard film containing a single barrier layer.
- the thermoplastic material may be a barrier material against oxygen molecules.
- tests using EVOH as a barrier material against oxygen and arranged so that a plurality of microlayers of EVOH are coextruded as a barrier layer indicate, surprisingly, that the film made therefrom has a resistance to puncture that increases sharply for a number p of microlayers greater than around 25. This corresponds to a number n at least equal to 5 (See Figure 6).
- each layer “b” may be replaced by a "colayer” having two microlayers “a/b” arranged so as to obtain a stack of units “(a/b) p ".
- Microlayer a may be selected from among PA6, PE, PP or any other material that may be apparent to those skilled in the art.
- microlayer "a” may be chosen so as to add an additional property such as, for example, a mechanical characteristic or a different barrier property.
- films that may be utilized according to this variation may consist of stacks of units of the following: (PE/EVOH) p , (PP/EVOH) p , (PA6/EVOH) p , (PET/ ⁇ VOH) P , (PVC/EVOH) p and any other microlayer combination that may be apparent to those skilled in the art to obtain the particular characteristics of the barrier layer desired.
- a material that has a good barrier property against water vapor may be used.
- each unit may have three microlayers "a/b/c" arranged in a manner so as to obtain a stack of units "(a/b/c) p ", in which "c" is selected from among PA6, PE, PP or any other like polymeric material.
- the microlayer c can be made of a material that is different or the same as the microlayer a. However, in a preferred embodiment, the microlayer c may be different from the microlayer a.
- the microlayer c may be the same as the microlayer a so that the barrier layer may consist of three microlayers "(a/b/a)".
- EVOH is sensitive to humidity so it may be preferable to coextrude blocks of the type (a/b/a) p , where a designates a material such as PE, PP, PA6, PET, PVC, or any other like material, and b is a layer of EVOH that may then stay inserted between two microlayers a.
- (EVOH) p microlayers may be tested in a laboratory by preserving them in a dry atmosphere, such as, for example, in a dessicator, and then testing them quickly before hydration of the film.
- FIG. 1 The EVOH microlayers of Figure 6 (curve 1) were tested in this manner.
- Figures 3 to 6 show the properties of the films having units of PA6/EVOH PA6, for different volume ratios.
- Figures 4-6 show properties for PA6/EVOH— 90/10 by volume (curve IV) signifying that the microlayers of PA6 are 9 times thicker than the EVOH microlayers.
- the mechanical properties (stress and strain) of the PA6/EVOH-50/50 by volume are superior to those of each of the individual components PA6 and EVOH, as shown in Figures 1 and 2.
- the film having alternating microlayers may have a positive synergistic effect. A same positive synergy may also be seen on standard films consisting of simple mixtures PA6+EVOH (whereby equal volumes of PA6 are mixed with EVOH before coextrusion of the barrier layer) as shown in Figures 8 to 10.
- Figures 3 and 8 shows the significant difference of the properties between a standard film and a film having microlayers according to the present invention, each having equal volumes of PA6 and EVOH.
- an elongation of 200% for a standard film with a composition of EVOH/PA6--50/50 by volume ( Figure 10) and of 235% for a film according to the invention having 2048 microlayers is seen.
- each unit having two microlayers "a/b” may include an adhesive microlayer arranged in a manner to obtain a stack of units of type "(a/d/b) p ".
- the adhesive microlayers are partially soluble at the same time to the microlayers surrounding the adhesive microlayers.
- each unit having three microlayers "a/b/c” may include one or two adhesive microlayers arranged in a manner to obtain stacks of units either having five microlayers "(a/d/b/e/c) p ", or having four layers “(a/d/b/c) p ", or "(a/b/e/c) p ", in which "d” and "e” are microlayers of the aforementioned adhesives. Specifically, extrudable adhesives may be desired.
- This variation of the present invention may be useful in the case of films for which delamination between the microlayers is particularly not desired.
- the film may consist of microlayers that may be delaminable by including the adhesive layers.
- a film (a/b) p made up of microlayers according to the invention generally has much less delamination than the standard barrier formed from two layers.
- a film having a recurring unit of five microlayers (a/d/b/e/c) p may be created, whereby the microlayer b may be EVOH, and microlayers d and e may be made of an extrudable adhesive, and microlayers a and c may typically be made of PE or PP.
- the microlayer b may be EVOH
- microlayers d and e may be made of an extrudable adhesive
- microlayers a and c may typically be made of PE or PP.
- other materials may be used as each individual microlayer a, b, c, d or e as may be apparent to those skilled in the art. This invention should not be limited as herein described.
- each of the previous films can be modified in the following manner: each unit may be a microlayer "a+b” made of a mixture of the two materials such as, for example, EVOH and PA6.
- a film thus, may be represented by a stack of units "(a+b) p ".
- a film having a recurring unit of three microlayers "a/b/c” may be converted into a film with a recurring unit of two microlayers, such as "a+b/c".
- two extruders may be sufficient rather than the three that would be needed for "a/b/c”.
- the unit "a+b" of a mixture of two materials may consist of PA6 and EVOH, with a volumetric content of PA6 preferably going from 30 to 90%, and typically equal to 50%.
- the film produced by the microlayer barrier layer may include at least one external layer "A” and/or "C", arranged in a manner so as to obtain a structural material "A/(X)p/C” or "A/(X) P " or "(X) p /C” in which "(X)p" represents the stack of microlayers and is selected from among "b", "a/b", “a+b”, “a/b/c", “a+b/c", "a/d/b”, “a/d/a+b”, “a/d/b/c", "a/d/a+b/c", "a/b/e/c", "a+b/e/c", "a/d/b/e/c", "a/d/a+b/e/c" or any other configuration that may be apparent to those skilled in the art.
- the external layers A and C may be selected from among PA6, PE, PP or other like material. Further, the layer C can be the same or different from the layer A. The layers A and C may be selected for the purpose of fulfilling certain specific functions such as, for example, sealing. In this embodiment, the layers A and/or C in the films "A/(X) P /C" or "A/(X) P " or
- (X) p /C may not be microlayers, but standard layers.
- these films that are made from the stack of microlayers (X) p that have layers A and/or C laminated or extruded thereon in the traditional manner thus have a "standard” thickness than can typically go from 5 to 50 ⁇ m.
- the thicknesses of the microlayers may typically be less than 1 ⁇ m.
- the film may comprise an adhesive layer "D” that may be disposed between the outside layer “A” and the stack (X) p .
- an adhesive layer “E” may be disposed between the stack (X) p and the external layer C and arranged in a manner so as to form a structural material "A/D/(X) P /E/C", "A/D/(X) p /C", "A/(X)p/E/C”, "A/D/(X)p” or "(X) p /E/C” in which D and/or E may be extrudable adhesives.
- a film having the structure "A/D/(b) p /E/C" where the stack of microlayers "b” includes microlayers of EVOH may be constructed.
- This film may retain roughly the same barrier properties against oxygen and have the mechanical characteristics that may correspond to those of the film "A/D/PA6/EVOH/PA6/E/C", the EVOH barrier layer being a standard single layer material.
- the section "PA6/EVOH/PA6” of this film may be replaced by a stack (b)neig of microlayers consisting of EVOH, having the same thickness of the standard layer of EVOH of the standard film.
- there may be a significant economic advantage in using the EVOH microlayers in that there is a removal of the PA6 layers. This may reduce the amount and number of materials to be extruded and thus the complexity of the extrusion equipment.
- the films created by the microlayer barriers may further be constructed of a barrier material against water vapor.
- This material may be selected from among the polyolefins, such as, for example, PE, PP, the thermoplastic polyesters, PVC, PVDC, PET and/or other like polymeric material.
- certain films may comprise layers or microlayers selected from among adhesives, typically extrudable adhesives.
- adhesives may contain polyolefins grafted by acid and/or anhydride groups, such as, for example PE or PP grafted by acrylic or maleic groups or other polymers or copolymers.
- PA6 may be a barrier to oxygen.
- PA6 may also be utilized for its mechanical characteristics.
- a further object of the present invention may consist of a process for manufacturing a material or film,
- the structural film "A/(X C", “A/(X) p n , "(XyC”, “A/D/(X),JE/C”, “A/D/(X) P /C”, “A/(X)p/E/C”, “A/D/(X) P " or "(X)p/E/C” may be manufactured by the bonding to the stack (X) p of the layers, most of them being external layers, made by lamination or extrusion of the materials A, C, D, E according to the structure desired. It may be advantageous for the films to not cool rapidly so that the microlayers, specifically the microlayers of EVOH, are allowed to recrystallize and thus improve the mechanical and barrier properties.
- the films were manufactured having a thickness of 100 ⁇ m.
- the films were made of a stack (X) p having p recurring units of X with:
- Figure 1 corresponds to a film (PA6) P
- Figure 2 to a film (EVOH) p
- Figure 3 to a film (PA6/EVOH/PA6) having a 50/50 PA6/EVOH volumetric composition.
- the different values of n are also shown in the Figures 1-3.
- the resistance to puncture was measured on a traction machine (Instron model 4204) on samples conditioned in an atmosphere at 50% relative humidity.
- the sample film was fixed on a circular support of 2.54 mm in diameter.
- the girder consisted of a hemispherical head having a diameter of 0.65 mm and displaced at a speed of 2.54 mm- min "1 .
- Figure 6 shows the resistance to puncture (in MPa) of the films as a function of the number of microlayers.
- the films tested were of the type (EVOH) p , (PA6) P , (PA6/EVOH/PA6) p having a volumetric composition of 50-50 and 90-10.
- the resistance to flex cracking test is useful for comparing the resistance of the film to usual manipulation and transport and was implemented according to the ASTM E- 392 standard.
- the test is conducted as follows. Using a film sample, a cylinder is formed that is 20.32 cm long and 8.9 cm in diameter and is subjected to a torsion of 360° and a compression up to a length of 3.84 cm. This torsion and compression is done 250 times in 5 minutes to cause flex lines in the material. The film is then examined using coloring agents that reveal holes and cracks which are then counted.
- Figure 4 shows the number of holes as a function of the number of microlayers, for four films: film I of the type (EVOH) p , film II of the type (PA6) P and two films III and IV of the type (PA6/EVOH/PA6) p having volumetric compositions of 50-50 and 90- 10, respectively.
- a measurement of the oxygen permeability of the films was made on an OxTran 1000 gas permeability device according to the ASTM D-3985 standard. The tests were done with gas (nitrogen and oxygen) at roughly no relative humidity.
- Figure 5 shows the permeability of oxygen (cm -cm/m -day-atm) as a function of the number of microlayers for the same four films as shown in Figure 4 as I-IN.
- the following films were manufactured having a thickness of 300 ⁇ m: a) a film having 5 layers PE/Adh/EVOH/Adh/PE with the relative thicknesses of PE, adhesive (Adh) and EVOH corresponding respectively to 77%, 15%, and 8% of the total thickness; b) a material (a/b/a) p according to the invention where a/b/a is equal to PE/EVOH/PE and p equals 256.
- Film b exhibits mechanical characteristics that are noticeably superior as compared to Film a.
- the resistance to fracture was measured as 17 MPa for Film b versus 15 MPa for Film a.
- Film b had an elongation of 300% versus 270% for Film a.
- Other properties are roughly similar. However, it was observed that even without the adhesive in Film b, there was no tendency to delaminate.
- Films having a thickness of 30 ⁇ m were made from a stack (X) p of microlayers using EVOH with the goal of making films corresponding to the type "A/D/(X) P /E/C". These films had a thickness of 60 ⁇ m with the layers A and B being layers of PE having thicknesses of 12.5 ⁇ m and the layers D and E being layers of adhesive deposited by coating having thicknesses of 2.5 ⁇ m.
- the standard films consist of, at the location of the stack (X) p , three layers of PA6/EVOH/PA6.
- the thickness of the layer of EVOH is 30 ⁇ m and the thickness of each layer of PA6 is 12 ⁇ m.
- Films having microlayers have a number of advantageous properties as compared to standard materials.
- the stress-strain curves show a significant improvement of the mechanical characteristics of the films with an increasing number of identical microlayers when the microlayers are made of EVOH, PA6 or some mixture of the two.
- the results indicate that there is a positive synergistic effect between PA6 and EVOH when microlayers are made using those two materials.
- there are increases in the resistances to puncture and flex cracking for the mixed EVOH/PA6 materials which may also be caused by positive synergistic effects between the two materials.
- the permeability of the materials varies only slightly for PA6 and actually increases slightly for EVOH.
- the invention makes it possible to obtain more economical films or materials because of the removal of certain layers (for example, by replacing PA6/EVOH/PA6 by a stack (X) p of microlayers of ENOH), or the layers' replacement by a layer of an already used and less costly material such as, for example, removing the adhesive layers of PE/Adh/EVOH/Adh/PE and replacing them by the material (a/b/a) p .
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU54220/00A AU5422000A (en) | 1999-06-11 | 2000-06-06 | Barrier material made of extruded microlayers |
MXPA01012629A MXPA01012629A (en) | 1999-06-11 | 2000-06-06 | Barrier material made of extruded microlayers. |
CA002374642A CA2374642A1 (en) | 1999-06-11 | 2000-06-06 | Barrier material made of extruded microlayers |
BR0011509-6A BR0011509A (en) | 1999-06-11 | 2000-06-06 | Multilayer film, and method of manufacturing a film having a plurality of microlayers |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR99/07641 | 1999-06-11 | ||
FR9907641A FR2794682B1 (en) | 1999-06-11 | 1999-06-11 | BARRIER MATERIAL WITH EXTRUDED MICRO-LAYERS |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2000076765A1 true WO2000076765A1 (en) | 2000-12-21 |
Family
ID=9546890
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/IB2000/000934 WO2000076765A1 (en) | 1999-06-11 | 2000-06-06 | Barrier material made of extruded microlayers |
Country Status (6)
Country | Link |
---|---|
AU (1) | AU5422000A (en) |
BR (1) | BR0011509A (en) |
CA (1) | CA2374642A1 (en) |
FR (1) | FR2794682B1 (en) |
MX (1) | MXPA01012629A (en) |
WO (1) | WO2000076765A1 (en) |
Cited By (36)
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EP1905581A1 (en) | 2003-10-27 | 2008-04-02 | ExxonMobil Chemical Patents Inc. | Microlayered composites and processes for making the same |
US7357890B2 (en) | 2005-10-18 | 2008-04-15 | Cryovac, Inc. | Apparatus and method for extruding a multilayered structure |
US7513766B2 (en) | 2005-10-11 | 2009-04-07 | Cryovac, Inc. | Extrusion apparatus having a driven feed segment |
WO2009046196A1 (en) * | 2007-10-02 | 2009-04-09 | Baxter International Inc. | Films containing microlayer structures |
WO2009086393A1 (en) * | 2007-12-27 | 2009-07-09 | Baxter International Inc. | Barrier films containing microlayer structures |
WO2009095231A2 (en) | 2008-01-31 | 2009-08-06 | Cryovac, Inc. | Gas-barrier films and sheets |
US20100028661A1 (en) * | 2006-12-01 | 2010-02-04 | Huhtamaki Ronsberg, Zweigniederlassung Der Huhtama | Method for the production of a multilayer laminate, and multilayer laminate |
WO2010015402A1 (en) * | 2008-08-07 | 2010-02-11 | Cryovac, Inc. | Multilayer structures comprising a microlayer sequence |
EP1346116B2 (en) † | 2000-12-29 | 2010-12-29 | WPT GmbH Windmöller Polymer Technologie | Sound-proof composite system for space limiting surfaces |
US8012572B2 (en) | 2009-03-06 | 2011-09-06 | Cryovac, Inc. | Multilayer, heat-shrinkable film comprising a plurality of microlayers |
WO2011115961A1 (en) * | 2010-03-18 | 2011-09-22 | Cryovac, Inc. | Multilayer active oxygen barrier film comprising a plurality of microlayers |
US20120208039A1 (en) * | 2009-10-29 | 2012-08-16 | Sartorius Stedim Biotech S.A. | Multilayer film of a wall of a bag having seams and intended for a biopharmaceutical product |
WO2012139637A1 (en) * | 2011-04-13 | 2012-10-18 | Dow Global Technologies Llc | Microlayer barrier films |
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WO2013101699A1 (en) | 2011-12-29 | 2013-07-04 | Dow Global Technologies Llc | Coextruded multilayer cyclic olefin polymer films or sheet having improved moisture vapor barrier |
US20130266749A1 (en) * | 2012-04-05 | 2013-10-10 | Weyerhaeuser Nr Company | Paperboard assembly with co extruded microlayered polymer barrier film |
US8821145B2 (en) | 2008-09-23 | 2014-09-02 | Cryovac, Inc. | Die for coextruding a plurality of fluid layers |
US8876512B2 (en) | 2008-09-23 | 2014-11-04 | Cryovac, Inc. | Die for coextruding a plurality of fluid layers |
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AU2013251239B2 (en) * | 2009-03-06 | 2016-05-05 | Cryovac, Llc | Multilayer, heat-shrinkable film comprising a plurality of microlayers and method for its fabrication |
EP3072686A1 (en) | 2015-03-26 | 2016-09-28 | The Procter and Gamble Company | Multi-layer polymeric films |
US20170361582A1 (en) * | 2014-12-05 | 2017-12-21 | Macro Technology Inc. | Multilayer plastic film |
WO2018180858A1 (en) * | 2017-03-30 | 2018-10-04 | 住友ベークライト株式会社 | Multilayer film and package |
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US10160186B2 (en) | 2014-08-26 | 2018-12-25 | Dow Global Technologies Llc | Coextruded multilayer film with filler in transport layer |
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US10259154B2 (en) | 2014-05-27 | 2019-04-16 | Dow Global Technologies Llc | Coextruded multilayer film with beta-propylene-based barrier layer |
US10336041B2 (en) | 2013-06-28 | 2019-07-02 | Dow Global Technologies Llc | Coextruded multilayer film with propylene-based polymer and ethylene-based polymer |
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US11220035B2 (en) | 2019-06-14 | 2022-01-11 | Henry G. Schirmer | Complex films made from modular disk coextrusion die with opposing disk arrangement |
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Also Published As
Publication number | Publication date |
---|---|
AU5422000A (en) | 2001-01-02 |
FR2794682A1 (en) | 2000-12-15 |
CA2374642A1 (en) | 2000-12-21 |
BR0011509A (en) | 2002-03-26 |
FR2794682B1 (en) | 2002-06-21 |
MXPA01012629A (en) | 2002-11-04 |
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