EP3526040A1 - Packaging material - Google Patents

Packaging material

Info

Publication number
EP3526040A1
EP3526040A1 EP17783512.1A EP17783512A EP3526040A1 EP 3526040 A1 EP3526040 A1 EP 3526040A1 EP 17783512 A EP17783512 A EP 17783512A EP 3526040 A1 EP3526040 A1 EP 3526040A1
Authority
EP
European Patent Office
Prior art keywords
further preferred
film
ppm
packaging material
pouch according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP17783512.1A
Other languages
German (de)
French (fr)
Inventor
Sarah Van Mierloo
Bart VAN DEN ESSCHERT
Lucio Baccaro
Patrick Elisabeth Luc Voets
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SABIC Global Technologies BV
Original Assignee
SABIC Global Technologies BV
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 SABIC Global Technologies BV filed Critical SABIC Global Technologies BV
Publication of EP3526040A1 publication Critical patent/EP3526040A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1545—Six-membered rings
    • 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
    • B32B1/00—Layered products having a non-planar shape
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal 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
    • B32B15/085—Layered products comprising a layer of metal comprising metal 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 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal 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
    • B32B15/09—Layered products comprising a layer of metal comprising metal 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 comprising polyesters
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/718—Weight, e.g. weight per square meter
    • 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
    • B32B2307/72—Density
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/14—Copolymers of propene

Definitions

  • the invention relates to a film or a pouch comprising packaging material directly in contact with an item intended for human use and comprising a polyolefin and an a-tocopherol.
  • Suitable stabilisers known in the art are for example synthetic (poly)phenolic compounds such as tetrakis[methylene-3-(3',5')-di-t-butyl-4-hydroxyphenyl)propionate] methane;
  • octadecyl 3,5-di-t-butyl-4-hydroxyhydrocinnamate 1 ,1 ,3-tris(2-methyl-4-hydroxy-5-t- butylphenyl)butane; 1 ,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, bis- [3,3-bis-(4'-hydroxy-3'-t-butylphenyl butanoic acid]-glycol ester; tris(3,5-di-t-butyl-4-hydroxy benzyl)isocyanurate; 1 ,3,5-tris(4-t-butyl-2,6-dimethyl-3-hydroxy-benzyl)isocyanurate; 5-di-t- butyl-4-hydroxy hydrocinnamic acid triester with 1 ,3,5-tris(2-hydroxyethyl)-s-triazine- 2,4,6(1 H, 3
  • stabilizers selected from the group consisting of organic phosphites or phosphonites.
  • organic phosphites or phosphonites For example tris (2,4-di-t-butylphenyl) phosphite.
  • the stabilized polyolefins and/or the packaging material may be processed via for example injection moulding, blow moulding, extrusion moulding, compression moulding or thin-walled injection moulding techniques.
  • the obtained products may be applied in a huge amount of applications for example in food packaging applications, biomedical applications, health care applications or pharmaceutical applications.
  • antioxidants are already an issue in for example food- and water contact applications, in medical and pharmaceutical devices.
  • processors are looking for improved ways to protect their products.
  • the invention concerns a film or a pouch comprising packaging material directly in contact with an item for human use comprising
  • the packaging material may show improved processing stability and/or
  • the packaging material is efficiently stabilized, while limiting and/or avoiding the use of toxic substances. This may especially for example allow to improve processing stability,
  • polyolefin composition and/or the packaging material may be reduced.
  • Component A may be polyolefin, for example a polyethylene, especially low density polyethylene (LDPE) and/or high density polyethylene (HDPE), a polypropylene, a
  • LDPE low density polyethylene
  • HDPE high density polyethylene
  • polypropylene a polypropylene
  • copolymer of ethylene with at least one a-olefin preferably a linear low density polyethylene (LLDPE) and/or mixtures of two or more thereof.
  • a copolymer of ethylene with at least one ⁇ -olefin may thereby preferably be a copolymer comprising ethylene and at least one a- olefin or a copolymer of ethylene and only one a-olefin.
  • the packaging material according to the invention may comprise component A in an
  • the production processes of LDPE, HDPE and LLDPE are summarised in Handbook of Polyethylene by Andrew Peacock (2000; Dekker; ISBN 0824795466), especially for example at pages 43-66.
  • the catalysts used can include for example Ziegler Natta catalysts, Phillips catalysts and single site catalysts.
  • the latter class is a family of different classes of compounds, which comprises metallocene catalysts.
  • a polymer prepared using a Ziegler-Natta catalyst is obtained for example via the interaction of an organometallic compound or hydride of a Group l-lll metal with a derivative of a Group I - I 11 transition metal.
  • An example of a (modified) Ziegler-Natta catalyst may thereby be for example a catalyst based on titanium tetra chloride and the organometallic compound
  • linear low density polyethylene as used herein is meant an ethylene-alpha olefin copolymer comprising ethylene and a C3-C10 alpha-olefin comonomer.
  • Suitable alpha- olefin comonomers include 1 -butene, 1 -hexene, 4-methyl pentene and 1 -octene.
  • the preferred comonomer may be 1 -hexene or 1 -butene.
  • the alpha-olefin comonomer is present in an amount of for example from about 2.5 to 30 percent by weight of the ethylene-alpha olefin copolymer, preferably from 5 to about 20 percent by weight of the ethylene-alpha olefin copolymer, more preferably an amount of from about 7 to about 15 percent by weight of the ethylene-alpha olefin copolymer.
  • the Mw/Mn of the linear low density polyethylene may be between 4 and 12, preferably between 4.5 and 1 1 , further preferred between 4.7 and 10, further preferred between 5 and 8, further preferred between > 5 and ⁇ 7, further preferred between > 5.5 and ⁇ 6.5 and/or the Mz/Mw of the linear low density polyethylene between 4 and 12, preferably between 4.5 and 1 1 , further preferred between 4.7 and 10, further preferred between 5 and 8, further preferred between > 5 and ⁇ 7, further preferred between > 5.8 and ⁇ 6.8.
  • the linear low density polyethylene has a density of ⁇ 850 kg/m 3 and ⁇ 950 kg/m 3 , preferably ⁇ 910 kg/m 3 and ⁇ 940 kg/m 3 , further preferred between 913 kg/m 3 and 923 kg/m 3 , further preferred between > 915 kg/m 3 and ⁇ 921 kg/m 3 and/or a melt mass flow rate (MFR) as measured according to ISO 1 131 -1 (201 1 ) at 190°C and at a load of 2.16 kg of between 0.1 dg/min and 12 dg/min, preferably between 1 dg/min and 1 1 dg/min, further preferred between 3 dg/min and 10 dg/min, even further preferred 4 dg/min and 9 dg/min, even further preferred > 4 dg/min and ⁇ 9 dg/min.
  • MFR melt mass flow rate
  • Linear low density polyethylene used herein may thereby for example comprise between 3 and 200 CH 3 per 1000 carbon atoms, preferably between 4 and 100 CH 3 per 1000 carbon atoms, preferably between 5 and 40 CH 3 per 1000 carbon atoms, preferably between 10 and 30 CH 3 per 1000 carbon atoms, further prefer between 15 and 25 CH 3 per 1000 carbon atoms, as determined by NMR.
  • the technologies suitable for the LLDPE manufacture include but are not limited to gas- phase fluidized-bed polymerization, polymerization in solution, and slurry polymerization.
  • the LLDPE has been obtained by gas phase polymerization in the presence of a Ziegler-Natta catalyst.
  • the LLDPE may be obtained by gas phase polymerization in the presence of a metallocene catalyst.
  • polypropylene as used herein is meant for example a propylene homopolymer or a copolymer of propylene with an a-olefin, for example an a-olefin chosen from the group of a-olefin having 2 or 4 to 10 C-atoms, for example wherein the amount of ⁇ -olefin is less than 10wt% based on the total propylene copolymer.
  • Polypropylene and a copolymer of propylene with an ⁇ -olefin can be made by any known polymerization technique as well as with any known polymerization catalyst system.
  • the polypropylene used in the invention is a propylene co-polymer.
  • the copolymer of ethylene and at least one a-olefin, a polyethylene and/or the polypropylene and or mixtures of two or more thereof used in the invention is/are produced using one Ziegler-Natta catalyst.
  • a polypropylene may thereby especially be for example bi-axially oriented polypropylene (BOPP).
  • a polyolefin and/or copolymer of ethylene and at least one ⁇ -olefin may for example have a density as determined according to ISO 1 183-1 (2012), method A of ⁇ 850 kg/m 3 and ⁇ 950 kg/m 3 , preferably ⁇ 910 kg/m 3 and ⁇ 940 kg/m 3 , further preferred between 913 kg/m 3 and 923 kg/m 3 . This may lead to mechanical properties suitable for the use for film applications.
  • a polyolefin and/or a copolymer of ethylene and at least one ⁇ -olefin may for example have an MFI represented by the corresponding melt mass flow rate (MFR) as measured according to ISO 1 131 -1 (201 1 ) at 190°C and at a load of 2.16 kg of between 0.1 dg/min and 10 dg/min, preferably between 0.5 dg/min and 6 dg/min, further preferred between 0.5 dg/min and 4 dg/min, even further preferred between >0.5 dg/min and 3.5 dg/min or between >0.5 dg/min and ⁇ 2 dg/min. This may lead to a processability suitable for the use for film applications.
  • MFR melt mass flow rate
  • Component B may be ⁇ -tocopherol.
  • Component B may be added for example as a liquid and/or using a master batch comprising between 0.5 w.-% and 5 w.-%, preferably between 1 and 5 w.-% of ⁇ -tocopherol and/or between 5 and 40 w.-%, preferably between 5 and 25 w.-%, of an organometallic stearate as component C and the rest of the master batch up to 100 w.-% being a further polyolefin as component D, preferably low density polyethylene.
  • the ⁇ -tocopherol may be preferably synthetic ⁇ -tocopherol. This allows a good control over wat is actually added.
  • a suitable example of ⁇ -tocopherol and/or synthetic ⁇ -tocopherol according to the invention may be Irganox E 201 (supplied by BASF) which is a racemic mixture of equal amounts of all eight possible stereoisomers of ⁇ -tocopherol (RRR, SSS, RRS, RSR, SSR, SRS, SRR, RSS) and is referred to as D,L-a-tocopherol or all-rac-alpha-tocopherol.
  • ⁇ -tocopherol may for example allow to achieve efficient stabilization with relatively low loadings of a-tocopherol.
  • the packaging material may preferably not comprise other tocopherols and/or may preferably comprise no tocotrienol and/or no natural vitamin E and/or no other antioxidant and/or no other compound comprising at least one phenolic motif and/or wherein the packaging material comprises only ⁇ -tocopherol as antioxidant. This may allow an efficient stabilization of the packaging material, while reducing the risk associated with and/or the amount of compounds that may migrate out of the packaging material. This may thus reduce possible health hazards.
  • the amount of component B ranges between 25 ppm and 300 ppm by weight, preferably between 50 ppm and 200 ppm by weight, further preferred between > 50 ppm and ⁇ 180 ppm by weight, further preferred between > 75 ppm and ⁇ 175 ppm, further preferred between > 90 ppm and 170 or ⁇ 170 ppm relative to the component A. relative to the component A.
  • This may allow an efficient stabilization of the stabilized polyolefin composition and/or the packaging material, while reducing the risk associated with and/or the amount of compounds that may migrate out of the stabilized polyolefin composition and/or the packaging material. This may thus reduce possible health hazards.
  • the packaging material according to the invention may also comprise component C, which may be at least one acid scavenger , preferably at least one organometallic stearate such as for example magnesium stearate, aluminum stearate, sodium stearate and calcium stearate and/or at least one inorganic
  • hydrotalcites such as for example DHT4A , preferably calcium stearate. This may further contribute to improve processability.
  • the amount of optional component C may range between 100 ppm and 1000 ppm by weight, more preferably between 200 ppm and 800 ppm by weight, further preferred between 400 ppm and 600 ppm by weight, relative to the component A.
  • the weight ratio B:C may range for example between 0.05:1 and 0.6:1 , preferably 0.07:1 to 0.5:1 , further preferred between 0.1 :1 and 0.4:1 .
  • the packaging material according to the invention may also comprise component D, which may be at least one further polyolefin, preferably a low density polyethylene or a polypropylene.
  • component D may be at least one further polyolefin, preferably a low density polyethylene or a polypropylene.
  • the amount of compound D may be between 0 and 10 000 ppm, preferably between 2000 and 7000 ppm.
  • the further polyolefin may be different from component A.
  • the packaging material according to the invention may thereby for example have an extractable amount (in mg of compounds per kg of packaging material) measured by PTV- GC-MS in a NIAS study (as explained below) of 2,6-di-tert-butylbenzoquinone preferably below 0.8 mg/kg, preferably below 0.5 mg/kg, and/or of 7,9-di-tert-butyl-1 - oxaspiro[4.5]deca-6,9-diene-2,8-dione below 0.4 mg/kg, preferably below 0.2 mg/kg, and/or methyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate below 0.5 mg/kg and/or of 2,4 di-tert- butyl-phenol below 10 mg/kg, preferably below 1 mg/kg, further preferred below 0.5 mg/kg, and/or an extractable amount measured by LC-MS in a NIAS study (as explained below) of phosphate below 5 mg/
  • the packaging material according to the invention may thereby have an amount of compound migrating based on a migration study applying modelling software and/or a calculation of total migrating amount (as explained below) of ⁇ 1 mg/kg (in mg of compounds per kg of food).
  • a film or pouch according to the invention may preferably for example comprise and/or consist of:
  • A a copolymer of ethylene and at least one a-olefin, a copolymer of propylene with an a-olefin and/or mixtures of two or more thereof, and,
  • an acid scavenger for example a organometallic stearate, preferably calcium stearate, relative to the component A,
  • That the packaging material consists of the components listed above may thereby preferably mean that no other antioxidant and/or no other organometallic stearate or hydrotalcite and/or no other compound/component is present.
  • the packaging material according to the invention may be used in the production of specific packaging articles.
  • preferred articles are films and/or pouches, especially for applications such as food and/or beverage packaging applications, for health care applications and/or pharmaceutical applications and/or medical or biomedical applications, whereby the packaging material according to the invention is directly in contact with an item intended for human use, such as for
  • beverage a food item, a medicine, an implant, a patch or another item for nutritional and/or medical or biomedical use.
  • the present invention also concerns the use of packaging material according to the invention may be used in the production of specific articles.
  • packaging material are films and/or pouches, especially for applications such as food and/or
  • beverage packaging applications for health care applications and/or pharmaceutical applications and/or medical or biomedical applications, whereby the packaging material according to the invention is directly in contact with an item intended for human use, such as for example a beverage, a food item, a medicine, an implant, a patch or
  • An item intended for human use according to the present invention may thereby be for example a beverage, a food item, especially for example baby food, a medicine, an implant, a patch, a drug delivery device, a diagnostic device or another item for nutritional and/or medical or biomedical use.
  • the packaging material according to the invention may for example be part of a multilayer structure, especially for example a multi-layer structure that comprises at least one aluminum layer, preferably at least one aluminum intermediate layer, and/or at least one PET layer, preferably at least one PET outer layer, and/or a at least one inner layer of the packaging material according to the invention.
  • the packaging material according to the invention may for example be part of a multilayer structure, especially for example a multi-layer structure that comprises at least one PET layer, preferably at least one PET outer layer, and/or a at least one inner layer of the packaging material according to the invention.
  • a multi-layer structure may be used for example as lid film for trays, especially for example for food trays.
  • a film or pouch according to the invention may thereby comprise
  • a multi-layer structure that comprise at least one aluminum intermediate layer and/or at least
  • PET outer layer and/or a at least one inner layer of the packaging material.
  • the invention may further concern the use of a film or pouch according to the invention as lid for food trays and/or for films and/or pouches for food and/or beverage packaging applications.
  • the invention may also concern the use above, whereby an item intended for human use is a beverage or a food item or another item for nutritional use.
  • the invention may also concern the use of a film or pouch according to the invention
  • packaging material according to the invention is directly in contact with an item intended for human use, such as a medicine, an implant, a patch or another item for medical or biomedical use.
  • the film or pouch as well as the packaging material according to the invention may be any suitable packaging material.
  • blow-fill-seal applications and processes may thereby be applications and processes, used for
  • a container is formed, filled, preferably for example with a liquid, and sealed in one process, which preferably does require a
  • Table 1 shows the composition of a comparative packaging material and of a packaging material according to the present invention.
  • melt index (190 C, 2 kg) - MF dg/min 0.93 0.92
  • CaSt stands for calcium stearate and ZnSt stands for zinc stearate.
  • Irganox 1076 is octadecyl-3-(3,5-di-tert.butyl-4-hydroxyphenyl)-propionate.
  • Irgafos 168 is tris(
  • SABIC LDPE 2008N0 is LDPE, which has a density as determined according to ISO 1 183-1 (2012), method A of 920 kg/m 3 and an MFI represented by the corresponding melt mass flow rate (MFR) as measured according to ISO 1 131 -1 (201 1 ) at 190°C and at a load of 2.16 kg of 7.5 dg/min.
  • MFR melt mass flow rate
  • Received samples were 25 kg pellet bags and were transferred into cleaned glass bottles upon arrival at the laboratory. The bottles were cleaned for trace combinations in polymers.
  • TD-GC-MS which couples thermal desorption (TD), gas chromatography (GO) and mass spectroscopy (MS).
  • a thermal desorption unit Markes TD100 was thereby used together with a GO Agilent 7890A and Agilent 5975C Mass detector, further using OhemStation E.02.02.1431 software and a column Agilent HP-ULTRA 2 50m * 0.320mm, 0.52 ⁇ film.
  • the following temperature program was used: initial temperature of 40°C, hold for 2 min, ramp 3°C/min until 92°C, ramp 5°C/min until 160°C, ramp 10°C/min until 280°C, hold for 10 min.
  • Detection range in MS was 29 - 450 atomic mass units (AMU). Data collected during the first minute of the measurement were excluded Thermal desorption was performed for 40 minutes at 1 10 ° C in a flow of helium. The sample was weighed (100 mg granules) in empty thermal desorption tubes. Calculations were performed against an external standard of toluene.
  • Semi-volatiles were analyzed by PTV-GC-MS, which couples programmed temperature vaporization (PTV), GC and MS.
  • a GC Agilent 6890N was thereby used with a Agilent 5973 mass detector and an autosampler Agilent G2614, whereby further using ChemStation E.02.02.1431 software and an Agilent HP5MS 60M * 0.250mm Column, 1.0 ⁇ film .20 ⁇ were thereby injected at 50 ° C.
  • the following temperature program was used: initial temperature of 70°C, hold for 0.5 min, ramp 10°C/min until 300°C, hold for 45 min.
  • Detection range in MS was 30 - 500 atomic mass units (AMU).
  • Non-volatiles were analyzed by LC-MS, which couples liquid chromatography (LC) and MS.
  • LC-MS liquid chromatography
  • MS MS
  • a liquid chromatography unit LC Waters Acquity H Class was thereby used together with a Waters SQ Detector 2 detector and MassLynx V4.1 software as well as
  • the column temperature was 40°C and 5 ⁇ were injected.
  • the mobile phase comprised 0.1 % formic acid in water (A), methanol (B) and isopropanol (C) with a gradient from 20% A, 70% B and 10% C to 90% B and 10% C within 6 min and a hold for 1 min.
  • the flow was set to 0.4 ml/min.
  • the MS-screening was performed for the range of m/z 100-2000 with atmospheric pressure chemical ionization (APCI) in positive/negative mode.
  • 5 grams of cryogenically grounded pellets were extracted with 200 ml_ dichloromethane using 8 hours boiling under reflux conditions.
  • the extracts were concentrated by evaporating the solvent to dryness and dissolving in 1 ml 80/20 2-propanol/water.
  • the dichloromethane extracts were evaporated and dissolved in isopropanol/water (80/20).
  • the target components were quantitated using external standards of each component.
  • film LLDPE density 918 kg/m 3 , thickness 0.05 mm
  • film LLDPE density 918 kg/m 3 , thickness 0.05 mm
  • 150 ppm a-tocopherol stabilizers complete migration into 1 kg food according to above equation is 0.41 mg/kg
  • film LLDPE density 918 kg/m 3 , thickness 0.05 mm
  • film LLDPE density 918 kg/m 3 , thickness 0.05 mm
  • 150 ppm a-tocopherol stabilizer calculated migration using the Migratest EXP2013 software is 0.41 mg/kg.
  • Table 2 shows the results (in mg of compound per kg of packaging material) obtained for a non-intentionally added substances (NIAS) extractable study for both the comparative and the inventive packaging materials of Table 1 .
  • Table 3 shows the results (in mg of compounds per kg of food) obtained for a migration study for both the comparative and the inventive packaging materials of Table 1 .

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Abstract

A film or a pouch comprising packaging material directly in contact with an item for human use comprising - A. a copolymer of ethylene and at least one α-olefin and/or a copolymer of propylene with an α-olefin and/or mixtures of two or more thereof, and - B. between 50 and 200 ppm by weight of α-tocopherol relative to the component A.

Description

Packaging material
The invention relates to a film or a pouch comprising packaging material directly in contact with an item intended for human use and comprising a polyolefin and an a-tocopherol.
The stabilization of polyolefins is known in the art.
Suitable stabilisers known in the art are for example synthetic (poly)phenolic compounds such as tetrakis[methylene-3-(3',5')-di-t-butyl-4-hydroxyphenyl)propionate] methane;
octadecyl 3,5-di-t-butyl-4-hydroxyhydrocinnamate; 1 ,1 ,3-tris(2-methyl-4-hydroxy-5-t- butylphenyl)butane; 1 ,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, bis- [3,3-bis-(4'-hydroxy-3'-t-butylphenyl butanoic acid]-glycol ester; tris(3,5-di-t-butyl-4-hydroxy benzyl)isocyanurate; 1 ,3,5-tris(4-t-butyl-2,6-dimethyl-3-hydroxy-benzyl)isocyanurate; 5-di-t- butyl-4-hydroxy hydrocinnamic acid triester with 1 ,3,5-tris(2-hydroxyethyl)-s-triazine- 2,4,6(1 H, 3H, 5H)trione; p-cresol/dicyclopentadiene butylated reaction product and 2,6- bis(2'-bis-hydroxy-3'-t-butyl-5'-methyl-phenyl-4-methyl-phenol). Also known in the art are stabilizers selected from the group consisting of organic phosphites or phosphonites. For example tris (2,4-di-t-butylphenyl) phosphite. The stabilized polyolefins and/or the packaging material may be processed via for example injection moulding, blow moulding, extrusion moulding, compression moulding or thin-walled injection moulding techniques. The obtained products may be applied in a huge amount of applications for example in food packaging applications, biomedical applications, health care applications or pharmaceutical applications.
However, most of the synthetic (poly)phenolic antioxidants used are strictly regulated by governments because they are suffering from serious limitations. Synthetic antioxidants can thereby for example diffuse into the surrounding medium. This can in turn lead to contamination of food and/or other products with potentially toxic or at least concerning substances or by-products as well as degradation products. This problem may arise simply because some antioxidants, by-products and/or degradation products are toxic above a certain level of concentration or are just perceived as concerning.
Accordingly, the use of such antioxidants is already an issue in for example food- and water contact applications, in medical and pharmaceutical devices. With increased consumer concerns about the amount of chemicals in their foods, processors are looking for improved ways to protect their products.
There is a continuous need to provide improved packaging material having no
dangerous effects and which also fulfill all requirements related to processing or short term heat stabilization.
1 . The invention concerns a film or a pouch comprising packaging material directly in contact with an item for human use comprising
- A. a copolymer of ethylene and at least one a-olefin, a copolymer of propylene
with an α-olefin and/or mixtures of two or more thereof, and
B. between 50 and 200 ppm by weight of a-tocopherol relative to the component A. Furthermore the packaging material may show improved processing stability and/or
improved organoleptic properties.
The packaging material is efficiently stabilized, while limiting and/or avoiding the use of toxic substances. This may especially for example allow to improve processing stability,
especially for example by reducing cross-linking or chain scission during extrusion and/or multiple extrusions.
A further advantage is that the film or pouch as well as the packaging material
according to the invention shows improved organoleptic properties. Moreover, the risk
related to and/or the amount of compound(s) possibly migrating out of the stabilized
polyolefin composition and/or the packaging material may be reduced.
Component A may be polyolefin, for example a polyethylene, especially low density polyethylene (LDPE) and/or high density polyethylene (HDPE), a polypropylene, a
copolymer of ethylene with at least one a-olefin, preferably a linear low density polyethylene (LLDPE) and/or mixtures of two or more thereof. A copolymer of ethylene with at least one α-olefin may thereby preferably be a copolymer comprising ethylene and at least one a- olefin or a copolymer of ethylene and only one a-olefin. The packaging material according to the invention may comprise component A in an
amount of for example between 50 and 100 wt. % preferably between 60 and > 99.5 wt. %, further preferred between 70 and >99.7 wt. %, further preferred between 80 and > 99.8 wt. %, further preferred between 90 and >99.9 wt. % based on the total weight of the material.
The production processes of LDPE, HDPE and LLDPE are summarised in Handbook of Polyethylene by Andrew Peacock (2000; Dekker; ISBN 0824795466), especially for example at pages 43-66. The catalysts used can include for example Ziegler Natta catalysts, Phillips catalysts and single site catalysts. The latter class is a family of different classes of compounds, which comprises metallocene catalysts. A polymer prepared using a Ziegler-Natta catalyst is obtained for example via the interaction of an organometallic compound or hydride of a Group l-lll metal with a derivative of a Group I - I 11 transition metal. An example of a (modified) Ziegler-Natta catalyst may thereby be for example a catalyst based on titanium tetra chloride and the organometallic compound
triethylaluminium. With linear low density polyethylene as used herein is meant an ethylene-alpha olefin copolymer comprising ethylene and a C3-C10 alpha-olefin comonomer. Suitable alpha- olefin comonomers include 1 -butene, 1 -hexene, 4-methyl pentene and 1 -octene. The preferred comonomer may be 1 -hexene or 1 -butene. Preferably, the alpha-olefin comonomer is present in an amount of for example from about 2.5 to 30 percent by weight of the ethylene-alpha olefin copolymer, preferably from 5 to about 20 percent by weight of the ethylene-alpha olefin copolymer, more preferably an amount of from about 7 to about 15 percent by weight of the ethylene-alpha olefin copolymer.
According to the invention, the Mw/Mn of the linear low density polyethylene may be between 4 and 12, preferably between 4.5 and 1 1 , further preferred between 4.7 and 10, further preferred between 5 and 8, further preferred between > 5 and < 7, further preferred between > 5.5 and < 6.5 and/or the Mz/Mw of the linear low density polyethylene between 4 and 12, preferably between 4.5 and 1 1 , further preferred between 4.7 and 10, further preferred between 5 and 8, further preferred between > 5 and < 7, further preferred between > 5.8 and < 6.8.
According to the invention, the linear low density polyethylene has a density of≥ 850 kg/m3 and < 950 kg/m3, preferably≥ 910 kg/m3 and < 940 kg/m3, further preferred between 913 kg/m3 and 923 kg/m3, further preferred between > 915 kg/m3 and < 921 kg/m3 and/or a melt mass flow rate (MFR) as measured according to ISO 1 131 -1 (201 1 ) at 190°C and at a load of 2.16 kg of between 0.1 dg/min and 12 dg/min, preferably between 1 dg/min and 1 1 dg/min, further preferred between 3 dg/min and 10 dg/min, even further preferred 4 dg/min and 9 dg/min, even further preferred > 4 dg/min and < 9 dg/min.
Linear low density polyethylene used herein may thereby for example comprise between 3 and 200 CH3 per 1000 carbon atoms, preferably between 4 and 100 CH3 per 1000 carbon atoms, preferably between 5 and 40 CH3 per 1000 carbon atoms, preferably between 10 and 30 CH3 per 1000 carbon atoms, further prefer between 15 and 25 CH3 per 1000 carbon atoms, as determined by NMR.
The technologies suitable for the LLDPE manufacture include but are not limited to gas- phase fluidized-bed polymerization, polymerization in solution, and slurry polymerization. According to a preferred embodiment of the present invention the LLDPE has been obtained by gas phase polymerization in the presence of a Ziegler-Natta catalyst. According to another preferred embodiment, the LLDPE may be obtained by gas phase polymerization in the presence of a metallocene catalyst.
With polypropylene as used herein is meant for example a propylene homopolymer or a copolymer of propylene with an a-olefin, for example an a-olefin chosen from the group of a-olefin having 2 or 4 to 10 C-atoms, for example wherein the amount of α-olefin is less than 10wt% based on the total propylene copolymer.
Polypropylene and a copolymer of propylene with an α-olefin can be made by any known polymerization technique as well as with any known polymerization catalyst system.
Regarding the techniques, reference can be given to slurry, solution or gasphase polymerizations; regarding the catalyst system reference can be given to Ziegler-Natta, metallocene or single-site catalyst systems. All are, in themselves, known in the art.
Preferably, the polypropylene used in the invention, is a propylene co-polymer.
Preferably, the copolymer of ethylene and at least one a-olefin, a polyethylene and/or the polypropylene and or mixtures of two or more thereof used in the invention is/are produced using one Ziegler-Natta catalyst. A polypropylene, may thereby especially be for example bi-axially oriented polypropylene (BOPP). A polyolefin and/or copolymer of ethylene and at least one α-olefin may for example have a density as determined according to ISO 1 183-1 (2012), method A of≥ 850 kg/m3 and < 950 kg/m3, preferably≥ 910 kg/m3 and < 940 kg/m3, further preferred between 913 kg/m3 and 923 kg/m3. This may lead to mechanical properties suitable for the use for film applications.
A polyolefin and/or a copolymer of ethylene and at least one α-olefin may for example have an MFI represented by the corresponding melt mass flow rate (MFR) as measured according to ISO 1 131 -1 (201 1 ) at 190°C and at a load of 2.16 kg of between 0.1 dg/min and 10 dg/min, preferably between 0.5 dg/min and 6 dg/min, further preferred between 0.5 dg/min and 4 dg/min, even further preferred between >0.5 dg/min and 3.5 dg/min or between >0.5 dg/min and < 2 dg/min. This may lead to a processability suitable for the use for film applications. Component B may be α-tocopherol. Component B may be added for example as a liquid and/or using a master batch comprising between 0.5 w.-% and 5 w.-%, preferably between 1 and 5 w.-% of α-tocopherol and/or between 5 and 40 w.-%, preferably between 5 and 25 w.-%, of an organometallic stearate as component C and the rest of the master batch up to 100 w.-% being a further polyolefin as component D, preferably low density polyethylene.
According to the invention the α-tocopherol may be preferably synthetic α-tocopherol. This allows a good control over wat is actually added.
A suitable example of α-tocopherol and/or synthetic α-tocopherol according to the invention may be Irganox E 201 (supplied by BASF) which is a racemic mixture of equal amounts of all eight possible stereoisomers of α-tocopherol (RRR, SSS, RRS, RSR, SSR, SRS, SRR, RSS) and is referred to as D,L-a-tocopherol or all-rac-alpha-tocopherol.
The use of α-tocopherol may for example allow to achieve efficient stabilization with relatively low loadings of a-tocopherol.
The packaging material may preferably not comprise other tocopherols and/or may preferably comprise no tocotrienol and/or no natural vitamin E and/or no other antioxidant and/or no other compound comprising at least one phenolic motif and/or wherein the packaging material comprises only α-tocopherol as antioxidant.. This may allow an efficient stabilization of the packaging material, while reducing the risk associated with and/or the amount of compounds that may migrate out of the packaging material. This may thus reduce possible health hazards.
The amount of component B ranges between 25 ppm and 300 ppm by weight, preferably between 50 ppm and 200 ppm by weight, further preferred between > 50 ppm and <180 ppm by weight, further preferred between > 75 ppm and <175 ppm, further preferred between > 90 ppm and 170 or <170 ppm relative to the component A. relative to the component A. This may allow an efficient stabilization of the stabilized polyolefin composition and/or the packaging material, while reducing the risk associated with and/or the amount of compounds that may migrate out of the stabilized polyolefin composition and/or the packaging material. This may thus reduce possible health hazards.
Besides components A and B, the packaging material according to the invention may also comprise component C, which may be at least one acid scavenger , preferably at least one organometallic stearate such as for example magnesium stearate, aluminum stearate, sodium stearate and calcium stearate and/or at least one inorganic
hydrotalcites, such as for example DHT4A , preferably calcium stearate. This may further contribute to improve processability. The amount of optional component C may range between 100 ppm and 1000 ppm by weight, more preferably between 200 ppm and 800 ppm by weight, further preferred between 400 ppm and 600 ppm by weight, relative to the component A.
The weight ratio B:C may range for example between 0.05:1 and 0.6:1 , preferably 0.07:1 to 0.5:1 , further preferred between 0.1 :1 and 0.4:1 .
Besides components A, B and C, the packaging material according to the invention may also comprise component D, which may be at least one further polyolefin, preferably a low density polyethylene or a polypropylene. The amount of compound D may be between 0 and 10 000 ppm, preferably between 2000 and 7000 ppm. Preferably, the further polyolefin may be different from component A.
The packaging material according to the invention may thereby for example have an extractable amount (in mg of compounds per kg of packaging material) measured by PTV- GC-MS in a NIAS study (as explained below) of 2,6-di-tert-butylbenzoquinone preferably below 0.8 mg/kg, preferably below 0.5 mg/kg, and/or of 7,9-di-tert-butyl-1 - oxaspiro[4.5]deca-6,9-diene-2,8-dione below 0.4 mg/kg, preferably below 0.2 mg/kg, and/or methyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate below 0.5 mg/kg and/or of 2,4 di-tert- butyl-phenol below 10 mg/kg, preferably below 1 mg/kg, further preferred below 0.5 mg/kg, and/or an extractable amount measured by LC-MS in a NIAS study (as explained below) of phosphate below 5 mg/kg, preferably below 1 mg/kg. The substances above may thereby be undesired. Phosphate as used herein may thereby especially for example refer to tris(2,4-di-tert-butylphenyl)phosphate.
The packaging material according to the invention may thereby have an amount of compound migrating based on a migration study applying modelling software and/or a calculation of total migrating amount (as explained below) of < 1 mg/kg (in mg of compounds per kg of food).
A film or pouch according to the invention may preferably for example comprise and/or consist of:
A. a copolymer of ethylene and at least one a-olefin, a copolymer of propylene with an a-olefin and/or mixtures of two or more thereof, and,
- B. between 50 and 200 ppm by weight of a-tocopherol relative to the component
A and
- C. between 100 ppm and 1000 ppm by weight of an acid scavenger, for example a organometallic stearate, preferably calcium stearate, relative to the component A,
- D. optionally a further polyolefin.
That the packaging material consists of the components listed above may thereby preferably mean that no other antioxidant and/or no other organometallic stearate or hydrotalcite and/or no other compound/component is present.
The packaging material according to the invention may be used in the production of specific packaging articles. Examples of preferred articles are films and/or pouches, especially for applications such as food and/or beverage packaging applications, for health care applications and/or pharmaceutical applications and/or medical or biomedical applications, whereby the packaging material according to the invention is directly in contact with an item intended for human use, such as for
example beverage, a food item, a medicine, an implant, a patch or another item for nutritional and/or medical or biomedical use.
The present invention also concerns the use of packaging material according to the invention may be used in the production of specific articles. Examples of preferred articles are films and/or pouches, especially for applications such as food and/or
beverage packaging applications, for health care applications and/or pharmaceutical applications and/or medical or biomedical applications, whereby the packaging material according to the invention is directly in contact with an item intended for human use, such as for example a beverage, a food item, a medicine, an implant, a patch or
another item for nutritional and/or medical or biomedical use. An item intended for human use according to the present invention may thereby be for example a beverage, a food item, especially for example baby food, a medicine, an implant, a patch, a drug delivery device, a diagnostic device or another item for nutritional and/or medical or biomedical use. The packaging material according to the invention may for example be part of a multilayer structure, especially for example a multi-layer structure that comprises at least one aluminum layer, preferably at least one aluminum intermediate layer, and/or at least one PET layer, preferably at least one PET outer layer, and/or a at least one inner layer of the packaging material according to the invention.
The packaging material according to the invention may for example be part of a multilayer structure, especially for example a multi-layer structure that comprises at least one PET layer, preferably at least one PET outer layer, and/or a at least one inner layer of the packaging material according to the invention. Such a multi-layer structure may be used for example as lid film for trays, especially for example for food trays.
Preferably, a film or pouch according to the invention may thereby comprise
a multi-layer structure that comprise at least one aluminum intermediate layer and/or at least
PET outer layer, and/or a at least one inner layer of the packaging material.
The invention may further concern the use of a film or pouch according to the invention as lid for food trays and/or for films and/or pouches for food and/or beverage packaging applications.
The invention may also concern the use above, whereby an item intended for human use is a beverage or a food item or another item for nutritional use.
The invention may also concern the use of a film or pouch according to the invention
for health care applications and/or pharmaceutical applications and/or medical or biomedical applications, whereby the packaging material according to the invention is directly in contact with an item intended for human use, such as a medicine, an implant, a patch or another item for medical or biomedical use.
The film or pouch as well as the packaging material according to the invention may
especially be used in so called blow-fill-seal applications and processes. Blow-fill-seal applications and processes may thereby be applications and processes, used for
example in the pharmaceutical industry, where a container is formed, filled, preferably for example with a liquid, and sealed in one process, which preferably does require a
little human interaction as possible and/or is carried out inside a machine and/or in a
sterile enclosed environment. This may improve antiseptic processing.
The invention will now be elucidated by way of the following examples without however being limited thereto.
Examples
Table 1 shows the composition of a comparative packaging material and of a packaging material according to the present invention.
Table 1 :
Packaging material Units Comparative Inventive polyolefin LLDPE LLDPE
catalyst n.a. Ziegler-Natta Ziegler-Natta comonomer n.a.
1-butene 1-butene
density kg/m3 918 918
melt index (190 C, 2 kg) - MF dg/min 0.93 0.92
D,L-alpna-tocopherol ppm 0 150
Irganox 1076 ppm 200 0 Irgafos ppm 800 0 CaSt ppm 0 500
ZnSt ppm 500 0
SABIC LDPE 2008N0 ppm 0 4350
CaSt stands for calcium stearate and ZnSt stands for zinc stearate. Irganox 1076 is octadecyl-3-(3,5-di-tert.butyl-4-hydroxyphenyl)-propionate. Irgafos 168 is tris(
2,4-di-tert-butylphenyl)phosphite.
SABIC LDPE 2008N0 is LDPE, which has a density as determined according to ISO 1 183-1 (2012), method A of 920 kg/m3 and an MFI represented by the corresponding melt mass flow rate (MFR) as measured according to ISO 1 131 -1 (201 1 ) at 190°C and at a load of 2.16 kg of 7.5 dg/min.
A study regarding non-intentionally added substances (NIAS) has been carried out on the packaging materials of Table 1 (comparative and inventive).
The analytic methods used for the NIAS study are described in the following.
Received samples were 25 kg pellet bags and were transferred into cleaned glass bottles upon arrival at the laboratory. The bottles were cleaned for trace combinations in polymers.
Volatiles were analyzed by TD-GC-MS, which couples thermal desorption (TD), gas chromatography (GO) and mass spectroscopy (MS).
A thermal desorption unit Markes TD100 was thereby used together with a GO Agilent 7890A and Agilent 5975C Mass detector, further using OhemStation E.02.02.1431 software and a column Agilent HP-ULTRA 2 50m*0.320mm, 0.52 μηι film.
The following temperature program was used: initial temperature of 40°C, hold for 2 min, ramp 3°C/min until 92°C, ramp 5°C/min until 160°C, ramp 10°C/min until 280°C, hold for 10 min. Detection range in MS was 29 - 450 atomic mass units (AMU). Data collected during the first minute of the measurement were excluded Thermal desorption was performed for 40 minutes at 1 10 °C in a flow of helium. The sample was weighed (100 mg granules) in empty thermal desorption tubes. Calculations were performed against an external standard of toluene. Semi-volatiles were analyzed by PTV-GC-MS, which couples programmed temperature vaporization (PTV), GC and MS.
A GC Agilent 6890N was thereby used with a Agilent 5973 mass detector and an autosampler Agilent G2614, whereby further using ChemStation E.02.02.1431 software and an Agilent HP5MS 60M*0.250mm Column, 1.0 μηι film .20 μΙ were thereby injected at 50° C.
The following temperature program was used: initial temperature of 70°C, hold for 0.5 min, ramp 10°C/min until 300°C, hold for 45 min. Detection range in MS was 30 - 500 atomic mass units (AMU).
5 grams of cryogenically grounded pellets of each material were extracted with 200 ml_ dichloromethane using 8 hours boiling under reflux conditions. The extracts were concentrated by evaporating the solvent to 1 ml. The dichloromethane extracts were injected without further treatment. Calculations were performed against an external standard of naphthalene.
Non-volatiles were analyzed by LC-MS, which couples liquid chromatography (LC) and MS. A liquid chromatography unit LC Waters Acquity H Class was thereby used together with a Waters SQ Detector 2 detector and MassLynx V4.1 software as well as
Column Waters Acquity UPLC BEH Phenyl, 2.1 x 100mm, 1 .7 μηι film.
The column temperature was 40°C and 5 μΙ were injected. The mobile phase comprised 0.1 % formic acid in water (A), methanol (B) and isopropanol (C) with a gradient from 20% A, 70% B and 10% C to 90% B and 10% C within 6 min and a hold for 1 min. The flow was set to 0.4 ml/min.
The MS-screening was performed for the range of m/z 100-2000 with atmospheric pressure chemical ionization (APCI) in positive/negative mode. 5 grams of cryogenically grounded pellets were extracted with 200 ml_ dichloromethane using 8 hours boiling under reflux conditions. The extracts were concentrated by evaporating the solvent to dryness and dissolving in 1 ml 80/20 2-propanol/water. The dichloromethane extracts were evaporated and dissolved in isopropanol/water (80/20). The target components were quantitated using external standards of each component.
The methods used for the migration study are described in the following. Calculation of complete migration of the substance from plastic material into food: Complete migration calculation:
6 dm2* density polyethylene * thickness of film * additive concentration = migration into 1 kg food
For the comparative example, film LLDPE (density 918 kg/m3, thickness 0.05 mm) containing 200 ppm Irganox 1076 and 800 ppm Irgafos 168 stabilizers, complete migration into 1 kg food according to above equation is 2.75 mg/kg
For the inventive example, film LLDPE (density 918 kg/m3, thickness 0.05 mm) containing 150 ppm a-tocopherol stabilizers, complete migration into 1 kg food according to above equation is 0.41 mg/kg
Validation of the level of migration by a modelling program:
Migration of additives was validated using the Migratest EXP2013 software (Fabes) based on generally recognised migration models as permitted in the latest version of the Plastics Directive (2002/72/EC, as amended). The migration from packaging was thereby calculated for 10 days contact with fatty food at 60 °C (only diffusion in the packaging determines migration, no partitioning limitation).
For below mentioned examples following additional parameters were included:
For the comparative example, film LLDPE (density 918 kg/m3, thickness 0.05 mm) containing 200 ppm Irganox 1076 and 800 ppm Irgafos 168 stabilizers, calculated migration using the Migratest EXP2013 software is 2.75 mg/kg. For the inventive example, film LLDPE (density 918 kg/m3, thickness 0.05 mm) containing 150 ppm a-tocopherol stabilizer, calculated migration using the Migratest EXP2013 software is 0.41 mg/kg.
Table 2 below shows the results (in mg of compound per kg of packaging material) obtained for a non-intentionally added substances (NIAS) extractable study for both the comparative and the inventive packaging materials of Table 1 .
Table 2:
Extractable study (NIAS) Comparative Inventive
2,6-Di-tert-butylbenzoquinone (PTV-GC-MS) mg/kg 0.8 <0.1 mg/kg
7,9-Di-tert-butyl-l-oxaspiro[4.5]deca- 0.4 <0.1
6,9-diene-2,8-dione (PTV-GC-MS)
mg/kg
Methyl 3-(3,5-di-tert-butyl-4- 0.9 <0.1 hydroxyphenyl)propionate (PTV-GC-MS)
2,4 di-tert-butyl-phenol (PTV-GC-MS) mg/kg 22 <0.3
Phosphate (LC-MS) mg/kg 7.4 <1
Table 3 below shows the results (in mg of compounds per kg of food) obtained for a migration study for both the comparative and the inventive packaging materials of Table 1 .
Table 3:
Migration study Comparative Inventive
Migration experiments: complete migration mg/kg
2.75 0.41 calculation
mg/kg
Migration experiments: Modelling software: 2.75 0.41 Migratest EXP 2013
As appears from the obtained results, especially the extractable amounts of 2,6-di-tert- butylbenzoquinone, 7,9-di-tert-butyl-1 -oxaspiro[4.5]deca-6,9-diene-2,8-dion, methyl 3-(3,5- di-tert-butyl-4-hydroxyphenyl)propionate, 2,4 di-tert-butyl-phenol and/or phosphate are significantly reduced. Phosphate as used herein may especially for example refer to tris(2,4-di-tert- butylphenyl)phosphate.
Similarly the amount of compounds migrating can significantly be reduced.

Claims

A film or a pouch comprising packaging material, directly in contact with an item for human use, comprising
A. a copolymer of ethylene and at least one a-olefin and/or a copolymer of
propylene with an a-olefin and/or mixtures of two or more thereof, and
B. between 50 and 200 ppm by weight of a-tocopherol relative to the component A.
A film or pouch according to Claims 1 , wherein the composition further comprises:
C. an acid scavenger, preferably an organometallic stearate.
A film or pouch according to any of Claims 1 -2, wherein the copolymer of ethylene and at least one α-olefin and/or a copolymer of propylene with an α-olefin and/or mixtures of two or more thereof is/are produced using one Ziegler-Natta catalyst.
A film or pouch according to any one of Claims 1 -3, wherein the amount of
component B ranges between > 50 ppm and <180 ppm by weight, further preferred between > 75 ppm and <175 ppm, further preferred between > 90 ppm and 170 or <170 ppm relative to the component A.
A film or pouch according to any one of Claims 2-4, wherein the amount of
component C ranges between 100 ppm and 1000 ppm by weight relative to the component A.
A film or pouch according to any one of Claims 1 -5, wherein the amount of
component A is between 50 and <100 wt. % preferably between 60 and > 99.5 wt.
%, further preferred between 70 and >99.7 wt. %, further preferred between 80 and > 99.8 wt. %, further preferred between 90 and >99.9 wt. % based on the total weight of the material.
A film or pouch according to any one of Claims 1 -6, wherein the Mw/Mn of the linear low density polyethylene is between 4 and 12, preferably between 4.5 and 1 1 ,
further preferred between 4.7 and 10, further preferred between 5 and 8, further preferred between > 5 and < 7, further preferred between > 5.5 and < 6.5 and/or the Mz/Mw of the linear low density polyethylene between 4 and 12, preferably between
4.5 and 1 1 , further preferred between 4.7 and 10, further preferred between 5 and 8, further preferred between > 5 and < 7, further preferred between > 5.8 and < 6.8.
A film or pouch according to any one of Claims 1 -7, wherein the linear low density polyethylene has a density of≥ 850 kg/m3 and < 950 kg/m3, preferably≥ 910 kg/m3 and < 940 kg/m3, further preferred between 913 kg/m3 and 923 kg/m3, further preferred between > 915 kg/m3 and < 921 and/or a melt mass flow rate (MFR) as measured according to ISO 1 131 -1 (201 1 ) at 190°C and at a load of 2.16 kg of between 0.1 dg/min and 12 dg/min, preferably between 1 dg/min and 1 1 dg/min, further preferred between 3 dg/min and 10 dg/min, even further preferred 4 dg/min and 9 dg/min, even further preferred > 4 dg/min and < 9 dg/min.
A film or pouch according to any one of Claims 1 -8, wherein the packaging material does not comprise other tocopherols and/or comprises no tocotrienol and/or no natural vitamin E and/or no other antioxidant and/or no other compound comprising at least one phenolic motif and/or wherein the packaging material comprises only a- tocopherol as antioxidant.
A film or pouch according to any one of Claims 1 -9, wherein the packaging material comprises LLDPE as component A in an amount between 50 and <100 wt- % of the packaging material, whereby the LLDPE comprises between 3 and 200 CH3 per 1000 carbon atoms, preferably between 4 and 100 CH3 per 1000 carbon atoms, preferably between 5 and 40 CH3 per 1000 carbon atoms, preferably between 10 and 30 CH3 per 1000 carbon atoms, further prefer between 15 and 25 CH3 per 1000 carbon atoms, as determined by NMR.
A film or pouch according to any one of Claims 1 -10, wherein he packaging material has an extractable amount measured by PTV-GC-MS in a NIAS study of 2,6-di-tert- butylbenzoquinone preferably below 0.8 mg/kg and/or of 7,9-di-tert-butyl-1 - oxaspiro[4.5]deca-6,9-diene-2,8-dione below 0.4 mg/kg and/or methyl 3-(3,5-di-tert- butyl-4-hydroxyphenyl)propionate below 0.5 mg/kg and/or of 2,4 di-tert-butyl-phenol below 10 mg/kg, preferably below 1 mg/kg, further preferred below 0.5 mg/kg, and/or an extractable amount measured by LC-MS in a NIAS study of phosphate below 5 mg/kg, preferably below 1 mg/kg. A film or pouch according to any one of Claims 1 -1 1
comprising a multi-layer structure that comprise at least one aluminum intermediate layer and/or at least PET outer layer, and/or a at least one inner layer of the packaging material.
Use of a film or pouch according to any one of Claims 1 -12
as lid for food trays and/or for films and/or pouches for food and/or beverage packaging applications.
Use according to claim 13 of a film or pouch according to any one of Claims 1 -12, whereby an item intended for human use is a beverage or a food item or another item for nutritional use.
Use of a film or pouch according to any one of Claims 1 -12
for health care applications and/or pharmaceutical applications and/or medical or biomedical applications, whereby the packaging material according to the invention is directly in contact with an item intended for human use, such as a medicine, an implant, a patch or another item for medical or biomedical use.
EP17783512.1A 2016-10-14 2017-10-13 Packaging material Withdrawn EP3526040A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP16193915 2016-10-14
PCT/EP2017/076158 WO2018069488A1 (en) 2016-10-14 2017-10-13 Packaging material

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EP3526040A1 true EP3526040A1 (en) 2019-08-21

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EP0878502A2 (en) * 1997-05-05 1998-11-18 Ciba SC Holding AG Formulations of Vitamin E for stabilisation of polymeric organic materials
JP2001081250A (en) * 1999-07-14 2001-03-27 Mitsui Chemicals Inc Polyolefin resin composition
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MALLEGOL J ET AL: "Antioxidant effectiveness of vitamin E in HDPE and tetradecane at 32^oC", POLYMER DEGRADATION AND STABILITY, BARKING, GB, vol. 73, no. 2, 1 January 2001 (2001-01-01), pages 269 - 280, XP004250550, ISSN: 0141-3910, DOI: 10.1016/S0141-3910(01)00087-8 *
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