WO2017219152A1 - Film polymère servant de barrière contre la vapeur d'eau - Google Patents

Film polymère servant de barrière contre la vapeur d'eau Download PDF

Info

Publication number
WO2017219152A1
WO2017219152A1 PCT/CH2016/000095 CH2016000095W WO2017219152A1 WO 2017219152 A1 WO2017219152 A1 WO 2017219152A1 CH 2016000095 W CH2016000095 W CH 2016000095W WO 2017219152 A1 WO2017219152 A1 WO 2017219152A1
Authority
WO
WIPO (PCT)
Prior art keywords
polymeric film
film according
layer
cyclic olefin
olefin copolymer
Prior art date
Application number
PCT/CH2016/000095
Other languages
English (en)
Inventor
Stefan Bokorny
Tobias Maienfisch
Samuel C. HESS
Corinne J. HOFER
Wendelin J. Stark
Original Assignee
Perlen Converting Ag
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 Perlen Converting Ag filed Critical Perlen Converting Ag
Priority to PCT/CH2016/000095 priority Critical patent/WO2017219152A1/fr
Publication of WO2017219152A1 publication Critical patent/WO2017219152A1/fr

Links

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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/325—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polycycloolefins
    • 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
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/102—Oxide or hydroxide
    • 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
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • 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
    • B32B2307/702—Amorphous
    • 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
    • B32B2307/738—Thermoformability
    • 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
    • B32B2439/70—Food packaging
    • 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

Definitions

  • the invention relates to a polymeric film useful as water vapor barrier according to the preamble of claim 1.
  • halogen free polymers such as cyclic olefin copolymers exhibiting a similar low water vapor transmission rate (WVTR) as PVdC have been developed. Since no polymer so far was able to block moisture completely, chemical desiccants have been applied broadly to create an effective zero relative humidity atmosphere.
  • WVTR water vapor transmission rate
  • the present invention provides a film material which creates an effective zero relative humidity within a package for the duration of a specific lag time, is deep drawable, transparent or translucent and has desirable mechanical properties in dry and soaked condition for applications as blister packaging material of pharmaceuticals.
  • Many desiccants are known in the art ranging from silica gels, salts (magnesium sulfate, calcium chloride, sodium phosphate di-basic, ammonium chloride, potassium carbonate, potassium aluminum disulfate, magnesium chloride etc.) to zeolites.
  • the present invention uses a multiple layer film consisting of one single polymer for avoiding delamination complications while deep drawing.
  • the active ingredient incorporated into the polymer matrix is preferably calcium oxide (CaO) and the polymer matrix is preferably a cyclic olefin copolymer.
  • the polymeric film according to the invention is designed as an at least two layer system, where the outer "shielding' -layer protects the desiccant contained within the second film.
  • the outer "shielding' -layer protects the desiccant contained within the second film.
  • Particle size distribution may be in the range of .01 pm - 5 pm. Surprisingly it was found that the small particle size leads to a better dispergation and homogenization of the particles, an improved transparency and an over all better efficiency regarding the water vapor barrier function.
  • the cyclic olefin copolymer is a copolymer of norbornene and ethylene.
  • the cyclic olefin copolymer may purposefully have a heat deflection temperature (HDT/B) of at most 200°C, preferably at most 100°C and most preferably of at most
  • HDT/B heat deflection temperature
  • the melt temperature of the cyclic olefin copolymer may purposefully be at least 190°C, preferably at least 230°C.
  • the melt temperature of the cyclic olefin copolymer may purposefully be at most 320°C, preferably at most 250°C.
  • the glass transition temperature of the cyclic olefin copolymer is purposefully in the range of 30° to 200°.
  • the ratio T-i :T 2 of the thickness Ti of the first layer to the thickness T 2 of the second layer is preferably in the range of 1 :2 to 2: 1 .
  • the first layer may consist essentially of polypropylene or polyethylene.
  • the polymeric film may be placed between two outer layers of a polymeric material.
  • a polymeric material In case of single layers consisting of different types of polymers they may be connected to each other with suitable commercially available primers or adhesives.
  • the outer layers may be made of polyethylene and have a thickness each in the range of 10 - 50 pm.
  • the third layer of the polymeric film may comprise ethylene vinyl alcohol (EVOH) or polyvinyl alcohol (PVA).
  • EVOH ethylene vinyl alcohol
  • PVA polyvinyl alcohol
  • the average thickness of the first and second layer is purposefully each in the range of 20 and 1000 pm , preferably in the range of 50 to 500 pm.
  • a further embodiment comprises a method of manufacture of the polymeric film according to the invention in which the first layer of the polymeric film is attached to the second layer of the polymer film by the solvent casting technique, whereby the first layer preferably consist essentially of a cyclic olefin polymer.
  • the first layer of the polymeric film may also be attached to a third layer by the solvent casting technique.
  • a further embodiment comprises a method of manufacture based on the extrusion technique for attaching the first layer of the polymeric film according to the invention to the second layer or third layer.
  • a further embodiment comprises a method of manufacture based on the calandering technique for attaching the first layer of the polymeric film according to the invention to the second layer or third layer, whereby the first layer consists essentially of polypropylene.
  • the polymeric film according to the invention is useful for pharmaceutical and medical packaging, in particular blister packaging.
  • Fig. 1 is a SEM image of a polymeric film according to the invention consisting of a three-layered sandwich film;
  • Fig. 2 is a graph of the water vapor transmission rate (WVTR) of a polymeric film
  • Fig. 3 is a schematic section through a polymeric film according to the invention. The following examples clarify the invention further in more detail.
  • Example 1
  • CaO particles with an average diameter of 400 nm (with a minimal diameter of 90 nm and a maximal diameter of 1170 nm) were dispersed in a cyclic olefin copolymer solution (10 wt % in xylene) with a weight ratio of 1 to 1 by ultra-sonication for 6 hours.
  • a pure cyclic olefin copolymer film (10 wt % in xylene) was casted on a glass substrate by a spiral film applicator. After drying, this cyclic olefin copolymer layer was covered with a CaO-cyclic olefin copolymer dispersion having a weight ratio (CaO to cyclic olefin copolymer) of 1 :1.
  • a third layer of pure cyclic olefin copolymer solution (10 wt % in xylene) was applied after the second film had been dried. This resulted in a sandwich structure comprising following layer thicknesses:
  • Second layer of cyclic olefin copolymer comprising CaO: 32 pm
  • the polymeric films were deep drawable at temperatures between 70°C and 180°C.
  • the top and bottom layers of the polymeric film consist of cyclic olefin copolymer; the intermediate layer consists of calcium oxide particles which are dispersed in a cyclic olefin copolymer matrix.
  • the intermediate layer consists of calcium oxide particles which are dispersed in a cyclic olefin copolymer matrix.
  • a magnification of the intermediate layer of the polymeric film is shown.
  • Fig. 2 shows the water vapor transmission rate (WVTR) of the polymeric film measured with a MOCON device at 40 °C and a relative humidity of 75% in dependence of time over 120 hours
  • the graph shows two individually measured three-layered samples obtained according to example 1.
  • the WVTR measured for 120 hours remained essentially constant after 1 0 hours.
  • the first layer (1 ) of the polymeric film consists essentially of a polymer chosen from the group of: cyclic olefin copolymer, polypropylene and polyethylene and a second layer (2) placed on the lower surface of the first layer (1 ), the second layer (2) comprising the same polymer as the first layer (1 ) as a matrix in which a plurality of desiccant particles (4) is embedded.
  • the polymeric film is placed between two outer layers (3) of a polymer preferably a polyethylene.
  • CaO particles with an average particle diameter of 400 nm, with a minimal diameter of 90 nm and a maximal diameter of 1 170 nm were dispersed in a cyclic olefin copolymer solution ( 5 wt % in xylene) with a weight ratio of 1 to 2 by ultra sonication for 6 hours.
  • a pure ethylene norbornene copolymer film (20 wt % in xylene) was casted on a glass substrate by a spiral film applicator. After drying, this ethylene norbornene copolymer layer was covered with a CaO-ethylene norbornene copolymer dispersion in a weight ratio of 1 to 2.
  • a third layer of pure ethylene norbornene copolymer solution (20 wt % in xylene) was applied after the second film had been dried.
  • CaO particles with an average particle diameter of 400 nm, with a minimal diameter of 90 nm and a maximal diameter of 1 170 nm were dispersed in cyclic olefin copolymer solution (20 wt % in xylene) with a weight ratio of 3 to 4. Because of the increased viscosity, the dispersion was vigorously steered for 24 hours, followed by ultra sonication for 6 hours to reach the required homogenization, leading to films with good barrier properties.
  • CaO powder with an average diameter of 100 pm was compounded into a cyclic olefin copolymer granulate with a CaO to polymer ratio of 2:5 by weight. Because of the increased melt flow index, the mixed compound was extruded with a single-screw extruder and a kneader-system to reach the required homogenization. The result was a film with good barrier properties.
  • a pure cyclic olefin copolymer film or other olefin polymer was extruded in a multi slit die extrusion line or was laminated in a second stage process by a laminator line.
  • an adhesive layer is needed by coating or extrusion.

Landscapes

  • Laminated Bodies (AREA)

Abstract

La présente invention concerne un film polymère servant de barrière contre la vapeur d'eau. Le film comprend (i) une première couche constituée essentiellement d'un polymère choisi dans le groupe constitué par : un copolymère d'oléfine cyclique, du polypropylène et du polyéthylène; et (ii) une seconde couche placée sur l'une des surfaces de la première couche, la seconde couche comprenant un polymère choisi dans le groupe constitué par : un copolymère d'oléfine cyclique, du polypropylène et du polyéthylène, en tant que matrice dans laquelle une pluralité de particules déshydratantes est intégrée. Les polymères de la première et de la seconde couche sont du même type. Le film polymère selon l'invention est utile pour des emballages pharmaceutiques et médicaux, en particulier des emballages-coques.
PCT/CH2016/000095 2016-06-22 2016-06-22 Film polymère servant de barrière contre la vapeur d'eau WO2017219152A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/CH2016/000095 WO2017219152A1 (fr) 2016-06-22 2016-06-22 Film polymère servant de barrière contre la vapeur d'eau

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CH2016/000095 WO2017219152A1 (fr) 2016-06-22 2016-06-22 Film polymère servant de barrière contre la vapeur d'eau

Publications (1)

Publication Number Publication Date
WO2017219152A1 true WO2017219152A1 (fr) 2017-12-28

Family

ID=56296442

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CH2016/000095 WO2017219152A1 (fr) 2016-06-22 2016-06-22 Film polymère servant de barrière contre la vapeur d'eau

Country Status (1)

Country Link
WO (1) WO2017219152A1 (fr)

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004000541A1 (fr) 2002-06-20 2003-12-31 Pechiney Emballage Flexible Europe Films presentant un materiau deshydratant et procedes d'utilisation et de production
JP2004136479A (ja) * 2002-10-16 2004-05-13 Toppan Printing Co Ltd 低溶出接着剤を用いたバリア性包装材及び包装体
WO2004080808A2 (fr) 2003-03-10 2004-09-23 Pechiney Emballage Flexible Europe Films à substance déshydratante incorporée et ses procédés d'utilisation et de production
JP2006255996A (ja) * 2005-03-16 2006-09-28 Mitsui Chemicals Inc シート
JP2006335394A (ja) * 2005-05-31 2006-12-14 Fuji Seal International Inc 吸湿包装材からなる包装袋
JP2009040439A (ja) * 2007-08-07 2009-02-26 Dainippon Printing Co Ltd 酸素水分吸収性パウチ、およびそれを使用した包装製品
EP2075013A2 (fr) * 2007-12-14 2009-07-01 Nitto Denko Corporation Structure d'emballage de patch
US20090294319A1 (en) * 2005-06-15 2009-12-03 Naegeli Hans R Blister base part and blister pack
JP2010228309A (ja) * 2009-03-27 2010-10-14 Toppan Printing Co Ltd バリア性ｐｔｐ底材及びその製造方法

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004000541A1 (fr) 2002-06-20 2003-12-31 Pechiney Emballage Flexible Europe Films presentant un materiau deshydratant et procedes d'utilisation et de production
JP2004136479A (ja) * 2002-10-16 2004-05-13 Toppan Printing Co Ltd 低溶出接着剤を用いたバリア性包装材及び包装体
WO2004080808A2 (fr) 2003-03-10 2004-09-23 Pechiney Emballage Flexible Europe Films à substance déshydratante incorporée et ses procédés d'utilisation et de production
JP2006255996A (ja) * 2005-03-16 2006-09-28 Mitsui Chemicals Inc シート
JP2006335394A (ja) * 2005-05-31 2006-12-14 Fuji Seal International Inc 吸湿包装材からなる包装袋
US20090294319A1 (en) * 2005-06-15 2009-12-03 Naegeli Hans R Blister base part and blister pack
JP2009040439A (ja) * 2007-08-07 2009-02-26 Dainippon Printing Co Ltd 酸素水分吸収性パウチ、およびそれを使用した包装製品
EP2075013A2 (fr) * 2007-12-14 2009-07-01 Nitto Denko Corporation Structure d'emballage de patch
JP2010228309A (ja) * 2009-03-27 2010-10-14 Toppan Printing Co Ltd バリア性ｐｔｐ底材及びその製造方法

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