EP2326743A1 - Produit en plastique à bon effet barrière après traitement de stérilisation - Google Patents

Produit en plastique à bon effet barrière après traitement de stérilisation

Info

Publication number
EP2326743A1
EP2326743A1 EP09814086A EP09814086A EP2326743A1 EP 2326743 A1 EP2326743 A1 EP 2326743A1 EP 09814086 A EP09814086 A EP 09814086A EP 09814086 A EP09814086 A EP 09814086A EP 2326743 A1 EP2326743 A1 EP 2326743A1
Authority
EP
European Patent Office
Prior art keywords
plastic film
barrier layer
packaging
barrier
layer
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Withdrawn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
EP09814086A
Other languages
German (de)
English (en)
Inventor
Lutz Koerner
Axel Sonnenfeld
Philipp Rudolf Von Rohr
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.)
Amcor Flexibles Kreuzlingen AG
Original Assignee
Amcor Flexibles Kreuzlingen 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 Amcor Flexibles Kreuzlingen AG filed Critical Amcor Flexibles Kreuzlingen AG
Priority to EP09814086A priority Critical patent/EP2326743A1/fr
Publication of EP2326743A1 publication Critical patent/EP2326743A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/048—Forming gas barrier coatings
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/123—Treatment by wave energy or particle radiation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02—Pretreatment of the material to be coated
    • C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/34—Nitrides
    • C23C16/347—Carbon nitride
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/401—Oxides containing silicon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/56—After-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D2565/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D2565/38—Packaging materials of special type or form
    • B65D2565/381—Details of packaging materials of special type or form
    • B65D2565/387—Materials used as gas barriers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/80—Packaging reuse or recycling, e.g. of multilayer packaging

Definitions

  • the invention relates to a plastic film for packaging or a molded plastic packaging part, with good penetration barrier action against gases, water vapor and flavorings after a sterilizing treatment, wherein the plastic film or the packaging part of a plasma-enhanced chemical vapor deposition (PECVD) generated barrier layer of amorphous hydrogenated and with Nitrogen (N) doped carbon (aC: N: H).
  • PECVD plasma-enhanced chemical vapor deposition
  • N Nitrogen
  • aC Nitrogen doped carbon
  • Known sterilizable packaging materials having a good barrier effect after sterilization treatment consist of single-layered or multi-layered plastic films and a water vapor-tight and gas-impermeable barrier layer in the form of an aluminum foil.
  • Metal foils are excellently suited for sterilizable packaging materials and also have excellent barrier properties. For various reasons, however, today increasingly transparent packaging is required, which can not be achieved with metal foils as barrier layers.
  • Known transparent packaging materials with barrier properties consist of multilayer plastic films, wherein one of the plastic films has an oxide layer, for example in the form of SiO x , as a barrier layer.
  • Other known transparent packaging films used for food packaging have as a barrier layer a film of polyvinylidene chloride (PVDC) or ethylene-vinyl alcohol copolymer (EVOH).
  • PVDC polyvinylidene chloride
  • EVOH ethylene-vinyl alcohol copolymer
  • the thermal stress of these transparent packaging materials during sterilization usually leads to a deterioration of the Barriereeigen- shafts. Especially under extreme sterilization conditions a massive, irreversible impairment of the barrier effect can occur. For example, the Increase the oxygen permeability of a conventional sterilizable packaging film under extreme sterilization conditions by a factor of 3 to 20.
  • a plasma-enhanced chemical vapor deposition PECVD, plasma enhanced chemical vapor deposition
  • PECVD plasma enhanced chemical vapor deposition
  • the barrier layer of SiO x is provided with a protective layer of amorphous hydrogenated carbon (aC: H).
  • the hydrogenated carbon film serves to prevent the microcracks in the SiO x barrier layer occurring in the case of deformations of the polymer substrate.
  • the deposition of the protective layer of aC: H is carried out by PECVD a hydrocarbon compound, preferably acetylene.
  • the deposition of the barrier layer from SiO x is carried out by PECVD of an organic silicon compound in the presence of excess oxygen.
  • an intermediate layer of a mixture of silicon, carbon, oxygen, nitrogen and hydrogen can be deposited on the polymer substrate.
  • Starting materials are, for example, disiloxanes, such as hexamethyldisiloxane (HMDSO) or tetramethyldisiloxane (TMDSO).
  • a carrier gas, preferably nitrogen, may be used.
  • the coated polymer substrate relates in particular to polyethylene terephthalate (PET) bottles. The inside coated bottles are used to package oxygen-sensitive products such as beer, fruit juices and carbonated drinks.
  • JP 2008/094447 A discloses a plastic container having excellent gas barrier properties.
  • a first, deposited by PECVD film of aC: H is arranged on the plastic surface.
  • a second layer of silicon oxide is deposited on this first layer.
  • the process gas for forming the carbon film acetylene is preferably used.
  • nitrogen-containing carbon compounds can also be used to form the carbon film.
  • To form the Silicon oxide film is a mixture of hexamethydisiloxane and oxygen is preferred as the process gas.
  • the described plastic container is an internally coated bottle and is used for the packaging of drinks.
  • a packaging laminate consisting of two PET films with an intermediate film of hydrogenated carbon (a-C: H) having excellent gas barrier properties.
  • the hydrogenated carbon film is deposited by PECVD with acetylene as a process gas on a first plastic film.
  • the coated first plastic film is laminated with a second, coated with an adhesive PET film.
  • the second plastic film protects the hydrogenated carbon film from damage and delamination.
  • the plastic films may consist of a polyester, a polyamide or a polyolefin. It has been observed that the oxygen permeability of the amorphous carbon film decreases with increasing doping of the carbon film with oxygen and nitrogen.
  • the packaging laminate provided with a gas barrier should i.a. Be suitable for packaging of drinks, food, medicines cosmetics.
  • a plastic film of the type mentioned is known from JP 2006 289836 A.
  • thermoforming of multilayer flat films containing an oxygen barrier layer inside e.g. from EVOH
  • Transparent barrier packaging can be realized with this technology.
  • these packages have the disadvantage that they are very limited in their design freedom due to the Thermoformvorgan-.
  • the gas barrier mediated by the EVOH collapses in the meantime, which allows the access of oxygen through the wall of the package in the food for a certain period of time.
  • Similar analogous limitations apply to "bottle-like" containers with EVOH barrier layers which can be produced by a combination of injection molding and injection blow molding or extrusion and blow molding.
  • EP-B-1 048 746 also describes the production of barrier-effect containers by means of vacuum coating.
  • Barrier packaging is produced there by molding the container (injection molding, thermoforming, blow molding) and then vacuum coating with a barrier layer of a material suitable for this purpose.
  • the packaging is closed by means of a flexible barrier film as a cover film.
  • the extremely thin vacuum coating is susceptible to mechanical abrasion and corrosion, e.g. in which the handling necessary for automated filling can lead to the loss of the barrier effect.
  • the packaging can not be resealed or opened only insufficiently after it has been opened for the first time.
  • the invention is based on the object to provide a plastic film or a packaging part of the type mentioned with improved temperature resistance for Sterilisieranassemble.
  • packaging parts such as containers and closure covers, should not have the disadvantages inherent in the packaging parts according to the prior art.
  • a second barrier layer made of a metal, a metal oxide or a metal nitride is arranged on the barrier layer of amorphous hydrogenated nitrogen (N) doped with carbon ( ⁇ -C: N: H).
  • the barrier layer of amorphous hydrogenated and nitrogen (N) doped carbon (aC: N: H) serves as a coupling agent for the second barrier layer.
  • This second barrier layer is, for example, a ceramic thin layer, in particular a silicon oxide of the formula SiO x , where x is a number from 1 to 2, or an aluminum oxide of the formula Al y O z , where y / z is a number from 0.2 to 1, 5, or a mixture thereof.
  • the ceramic thin film can also contain, in addition to the silicon and aluminum oxides mentioned, oxides and / or nitrides of metals and / or semimetals, for example those of iron, nickel, chromium, tantalum, molybdenum, hafnium, titanium, yttrium, zirconium, magnesium and mixtures thereof Contain or consist of substances. Further possible second barrier layers can be deposited as metal on the substrate.
  • Preferred metals are aluminum, steel, copper, tin, zinc, silver or mixtures thereof.
  • metal oxide barrier layers in addition to the abovementioned silicon and aluminum oxides, it is also possible to use the oxides of the metals mentioned further, for example SnO 2 , ZnO or mixtures thereof, also with SiO x .
  • the above-mentioned barrier layer of SiO x which can also be deposited by PECVD from a mixture of HMDSO and O 2 .
  • the second barrier layer can be applied, for example, by a thin film vacuum method, such as physical coating (PVD) or chemical (CVD) coating, with or without plasma assist, or by sputtering.
  • a thin film vacuum method such as physical coating (PVD) or chemical (CVD) coating, with or without plasma assist, or by sputtering.
  • a metal oxide or a metal nitride may be another barrier layer amorphous hydrogenated and with nitrogen and silicon (Si) doped carbon (aC: N: Si: H) may be arranged as an intermediate layer.
  • the second barrier layer may be overcoated for protection against abrasion and corrosion and for improving mechanical stability.
  • Suitable overcoats are generally paint systems based on natural binders, polycondensation resins, polyaddition resins, polymerization resins or other binders such.
  • the binders can also be mixed with various crosslinker resins, such as. As isocyanates, melamine or urea resins, silanes or metal alkoxides are crosslinked.
  • lacquers based on EVOH, PVDC, cationic or free-radically UV-curing lacquers or sol-gel lacquers based on alkoxysilanes and / or metal alkoxides and / or inorganic particles are preferred.
  • These paints can also be mixed with various crosslinking resins such. As isocyanates, melamine or urea resins, silanes or metal alkoxides are crosslinked.
  • Lacquers which, in addition to the oxygen barrier, also have sterilization-resistant properties, are, in particular, paints based on EVOH, PVDC, cationic or free-radically UV-curing lacquers or sol-gel lacquers based on alkoxysilanes and / or metal alkoxides and / or inorganic particles , These paints can with different crosslinking resins, such. As isocyanates, melamine or urea resins, silanes or metal alkoxides are crosslinked.
  • sol-gel coating systems and UV-curing coatings based on acrylates or cationically crosslinking epoxides Curing takes place thermally or by radiation curing. Curing by UV light or electron beams is particularly preferred.
  • a metal layer of chromium, aluminum, nickel, titanium, iron, molybdenum or an alloy composed of at least two of these metals can be arranged as adhesion promoter on the second barrier layer.
  • Preferred metals are chromium and aluminum, with chromium being particularly preferred.
  • a preferred alloy is V2A steel.
  • Monoatomar does not mean that the atoms must be arranged in a monoatomic position. Rather, as with all condensation processes, clusters of atoms form.
  • a monoatomic layer is understood to mean a surface occupation which would lead to an approximately monoatomic position if the atoms were distributed uniformly over the substrate surface.
  • a layer thickness of 0.1 to 0.5 nm (nanometers) corresponding to a monatomic coverage is preferred.
  • a layer thickness of 0.2 nm results in the same adhesive strength, as it is observed in thicker layers of a thickness of 1 nm and larger.
  • the 0.2 nm thick layers almost do not affect the optical transparency, so they are invisible to the human eye.
  • the overcoating of the vacuum-coated packaging part is carried out, for example, by dip coating, flood painting, curtain coating, spray painting, pad printing or by means of inkjet.
  • dip coating for example, by dip coating, flood painting, curtain coating, spray painting, pad printing or by means of inkjet.
  • spray painting pad printing or by means of inkjet.
  • inkjet to reduce the applied paint thickness or for better distribution of the paint on the packaging part can follow the painting a Abschleudervorgang.
  • the molding of the packaging part may be by thermoforming of flat film material, by injection molding or by a combination of injection molding and Blow molding (blow molding) or extrusion and blow molding (extrusion blowmolding) take place.
  • the coating and overpainting of the container and optionally of the closure can be carried out on the inside or outside.
  • the coating on the outside makes it possible to apply the barrier layer and the overcoat layer to the already filled and sealed package.
  • a barrier packaging produced according to the invention with a container for receiving a filling material can be closed, for example, as follows:
  • screw cap which can be made of metal or plastic.
  • the screw cap can, as described above, be provided by a combination of vacuum coating and overcoating with a corresponding gas barrier.
  • Packaging parts according to the invention can also be closures of packaging made of glass, cardboard or other materials, such.
  • a barrier layer of amorphous hydrogenated nitrogen doped with nitrogen (N) is produced from a mixture of a gaseous carbon and a gaseous nitrogen source as the process gas by PECVD.
  • a mixture of acetylene (C 2 H 2 ) and nitrogen (N2) is used as the process gas.
  • the volumetric mixing ratio of nitrogen (N 2 ) to acetylene (C 2 H 2 ) in the process gas is set to a value of 3 to 19, preferably 6 to 8.
  • a second barrier layer of a metal, a metal oxide or a metal nitride is produced on the barrier layer of amorphous hydrogenated and nitrogen (N) doped carbon (aC: N: H).
  • the second barrier layer preferably a barrier layer of silicon oxide (SiO x ), can also be produced from a mixture of hexamethyldisiloxane (HMDSO) and oxygen (O 2 ) as the process gas by PECVD.
  • a metal oxide or a metal nitride can be prepared from a mixture of hexamethyldisiloxane (HMDSO), acetylene (C 2 H 2 ) and nitrogen (N 2 ) as the process gas, a further barrier layer of amorphous hydrogenated and nitrogen (N) and silicon (Si) doped carbon (aC: N: Si: H) are produced as an intermediate layer.
  • plastic films all single or multi-layer plastic films suitable for packaging can be used. These are in particular films of polyolefins, such as polypropylene (PP) and polyethylene (PE), polyamide (PA), polyesters, in particular polyethylene terephthalate (PET), in the form of mono- or multilayer films.
  • polyolefins such as polypropylene (PP) and polyethylene (PE), polyamide (PA), polyesters, in particular polyethylene terephthalate (PET), in the form of mono- or multilayer films.
  • Preferred fields of application of the plastic film according to the invention are packaging, in particular in the form of containers and bags of all kinds, for oxygen-sensitive products from the food and non-food sector.
  • the packaging parts can be made from a large number of starting materials.
  • Particularly useful are transparent plastics with good forming properties such as polyethylene (PE) 1 polypropylene (PP), cycloolefin copolymer (COC), cycloolefin polymer (COP), polyvinyl chloride (PVC), polyethylene terephthalate (PET), polyamide (PA) and from the materials mentioned laminates.
  • Compostable and biodegradable polymers and / or renewable raw materials based polymers can also be used as starting material for the production of packaging parts.
  • Suitable compostable polymers are in particular EN 13432 certified and renewable and / or non-renewable raw materials based polymers, such as starch based polymers (high blends), PLA (polylactide), PHA (polyhydroxyalcanoate), e.g. PHB (polyhydroxybutyrate), PHV (polyhydroxyvaleate), cellulosic materials of chemically modified cellulose, other materials made of chemically modified cellulose, and specific synthetic polyesters made from crude oil or natural gas.
  • starch based polymers high blends
  • PLA polylactide
  • PHA polyhydroxyalcanoate
  • PHB polyhydroxybutyrate
  • PHV polyhydroxyvaleate
  • cellulosic materials of chemically modified cellulose other materials made of chemically modified cellulose
  • specific synthetic polyesters made from crude oil or natural gas.
  • Renewable based polymers are e.g. made of sugar, starch, vegetable oils or cellulose. Cereals, potatoes, cereals, sugar cane and wood are the most commonly used starting materials.
  • Suitable renewable resource based polymers are especially specific polyesters, e.g. based on PDO (biopropanediol), specific polyamides, e.g. made from castor oil, as well as PE (polyethylene), polypropylene (PP) and PVC (polyvinyl chloride), on bioethanol from e.g. Sugarcane based.
  • PDO biopropanediol
  • specific polyamides e.g. made from castor oil
  • PE polyethylene
  • PP polypropylene
  • PVC polyvinyl chloride
  • the vacuum coating with overcoating allows the production of Packaging parts made from renewable raw materials with a high barrier effect and a certified compostability in accordance with the criteria of standard EN 13432.
  • biopolymers such as PHA or renewable raw materials-based polypropylene.
  • the preparation of the packaging parts, the coating and the overcoating is preferably carried out in a line.
  • FIG. 1 shows ATR / FTIR spectra of various carbon coatings on a polypropylene substrate
  • Figure 1 shows ATR / FTIR spectra of different coatings of a-C: N: H on a polypropylene substrate.
  • the coatings were deposited on the substrate by PECVD.
  • As the process gas mixtures of acetylene (C 2 H 2 ) and nitrogen (N 2 ) having a volumetric mixing ratio of nitrogen to acetylene (N 2 : C 2 H 2 ) in the process gas of 3 to 19 were used.
  • the spectra can be interpreted as follows:
  • the strong absorption bands at the wavenumbers 1360 cm “1 , 1450 cm “ 1 , 2913 cm “1 and 2966 cm “ 1 can be attributed to CH absorption bands of the polypropylene substrate.
  • N 2 mixing ratio
  • C 2 H 2 in the process gas
  • a narrower band attributed to the nitrile groups is observed, which also increases with increasing nitrogen content.
  • Another broader absorption band in the range of 3300-3500 cm -1 is characteristic of the NH stretching vibration, the latter two being terminal groups and reducing the degree of overcoordination in the amorphous carbon network and therefore reducing the internal stress in the coating.
  • PECVD plasma assisted gas phase deposition
  • a first layer of aC: N: H, a second layer of aC: N: Si: H and a third layer of SiO x were vapor-deposited on the polypropylene film by PECVD.
  • the process gases used were a mixture of acetylene and nitrogen for the first layer, and a mixture of acetylene, nitrogen and HMDSO for the second layer serving as the intermediate layer.
  • the process parameters are shown in Table 1. Table 1: Process parameters for example 1
  • the measured at 25 ° C Oxygen permeability of the coated substrate was 5 cm 3 / m 2 / 24h / bar. Comparatively, the corresponding value for the uncoated substrate is about 3000 cm 3 / m 2 / 24h / bar.
  • a first layer of aC: N: H and a second layer of SiO x were vapor deposited on the polypropylene film by PECVD on top of each other.
  • the process parameters are shown in Table 2.
  • the substrate coated with two layers under dry sterilization conditions at 120 ° C. and 140 ° C. for 30 minutes shows significantly better barrier properties compared to the barrier properties of a substrate coated only with SiO x of the same thickness.
  • the layer was about five times thicker than the first layer of a-C: N: H in Example 1 and showed considerable brown coloration, so that this coated substrate can not be used for all packaging applications.
  • the substrate coated with only one layer under dry sterilization conditions at 140 ° C. for 30 minutes shows significantly better barrier properties compared to the barrier properties of a substrate coated only with SiO x of the same thickness.
  • Table 4 shows the barrier effect of polypropylene packaging parts (PP) uncoated and coated with silver (Ag), steel (V2A) and tin (Sn), without overcoat layer.
  • Table 5 shows the barrier effect of packaging parts made of polypropylene (PP) coated with silver (Ag) and steel (V2A), with an overcoat layer of different coating systems.
  • Table 6 shows the barrier effect of packaging parts made of polylactide (PLA) coated with silver (Ag) and steel (V2A), without overcoat layer.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Laminated Bodies (AREA)
  • Chemical Vapour Deposition (AREA)

Abstract

L'invention concerne un film plastique pour emballage ou une pièce d'emballage en matière plastique moulée, bloquant efficacement le passage aux gaz, à la vapeur d'eau et aux substances aromatiques après un traitement de stérilisation, qui présente une couche d'arrêt en carbone (a-C:N:H) amorphe hydrogéné et dopé à l'azote (N), produite par dépôt chimique en phase vapeur assisté par plasma (PECVD) comme base d'adhérence pour une deuxième couche d'arrêt composée de métaux, d'oxydes métalliques ou de nitrures métalliques.
EP09814086A 2008-09-17 2009-07-27 Produit en plastique à bon effet barrière après traitement de stérilisation Withdrawn EP2326743A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP09814086A EP2326743A1 (fr) 2008-09-17 2009-07-27 Produit en plastique à bon effet barrière après traitement de stérilisation

Applications Claiming Priority (3)

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EP20080405229 EP2166130A1 (fr) 2008-09-17 2008-09-17 Film de matière plastique ayant un effet de barrière efficace après un traitement de stérilisation
EP09814086A EP2326743A1 (fr) 2008-09-17 2009-07-27 Produit en plastique à bon effet barrière après traitement de stérilisation
PCT/EP2009/005405 WO2010031461A1 (fr) 2008-09-17 2009-07-27 Produit en plastique à bon effet barrière après traitement de stérilisation

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EP2326743A1 true EP2326743A1 (fr) 2011-06-01

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EP20080405229 Withdrawn EP2166130A1 (fr) 2008-09-17 2008-09-17 Film de matière plastique ayant un effet de barrière efficace après un traitement de stérilisation
EP09814086A Withdrawn EP2326743A1 (fr) 2008-09-17 2009-07-27 Produit en plastique à bon effet barrière après traitement de stérilisation

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Family Cites Families (8)

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Publication number Priority date Publication date Assignee Title
FR2812666B1 (fr) 2000-08-01 2003-08-08 Sidel Sa Revetement barriere comportant une couche protectrice, procede d'obtention d'un tel revetement et recipient muni d'un tel revetement
US20040227197A1 (en) * 2003-02-28 2004-11-18 Shinji Maekawa Composition of carbon nitride, thin film transistor with the composition of carbon nitride, display device with the thin film transistor, and manufacturing method thereof
JP4282360B2 (ja) 2003-04-15 2009-06-17 北海製罐株式会社 ガスバリア性プラスチックフィルム
EP1787796B1 (fr) * 2004-08-17 2013-02-13 Dai Nippon Printing Co., Ltd. Film multicouche formant barrière contre les gaz et procédé de production
JP2006116731A (ja) * 2004-10-19 2006-05-11 Dainippon Printing Co Ltd バリア性フィルムおよびそれを使用した積層材
JP2006289836A (ja) * 2005-04-12 2006-10-26 Mitsubishi Heavy Ind Ltd アモルファスカーボン膜及び容器
JP5084182B2 (ja) * 2006-06-07 2012-11-28 麒麟麦酒株式会社 被覆プラスチック製品及び被膜
JP2008094447A (ja) 2006-10-13 2008-04-24 Toppan Printing Co Ltd 薄膜被覆されたプラスチック容器

Non-Patent Citations (1)

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Title
See references of WO2010031461A1 *

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EP2166130A1 (fr) 2010-03-24
WO2010031461A1 (fr) 2010-03-25

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