EP3084075A1 - Packaging material with barrier properties to the migration of mineral oils and process preparation thereof - Google Patents

Packaging material with barrier properties to the migration of mineral oils and process preparation thereof

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Publication number
EP3084075A1
EP3084075A1 EP14833222.4A EP14833222A EP3084075A1 EP 3084075 A1 EP3084075 A1 EP 3084075A1 EP 14833222 A EP14833222 A EP 14833222A EP 3084075 A1 EP3084075 A1 EP 3084075A1
Authority
EP
European Patent Office
Prior art keywords
coating
polymer
process according
cyclic olefin
packaging material
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.)
Granted
Application number
EP14833222.4A
Other languages
German (de)
French (fr)
Other versions
EP3084075B1 (en
Inventor
Athanasia ATHANASIOU
Uttam C. PAUL
Elisa MELE
Despina FRAGOULI
Ilker S. Bayer
Roberto Cingolani
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.)
Fondazione Istituto Italiano di Tecnologia
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Fondazione Istituto Italiano di Tecnologia
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Publication of EP3084075A1 publication Critical patent/EP3084075A1/en
Application granted granted Critical
Publication of EP3084075B1 publication Critical patent/EP3084075B1/en
Active legal-status Critical Current
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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/10—Packing paper
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/14—Secondary fibres
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/58—Polymers or oligomers of diolefins, aromatic vinyl monomers or unsaturated acids or derivatives thereof
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/80—Paper comprising more than one coating
    • D21H19/82—Paper comprising more than one coating superposed
    • D21H19/824—Paper comprising more than one coating superposed two superposed coatings, both being non-pigmented
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/16—Sizing or water-repelling agents

Definitions

  • Packaging material with barrier properties to the migration of mineral oils and process for preparation thereof
  • the present invention relates to a process for the production of cellulose-based substrates that have barrier properties against the migration of mineral oils and/or of their volatile components, particularly for the production of packaging materials suitable for contact with foodstuffs such as paper, cardboard or paperboard, having the aforementioned barrier properties.
  • packaging has an important role for maintaining the freshness of foodstuffs and for providing protection against atmospheric agents.
  • the impurities present in packaging materials may adulterate the quality of the foodstuffs.
  • packaging materials obtained from recycled cellulosic products may contain mineral oils consisting of colourless hydrocarbons (C 1 s-C 40 ) mainly originating from printing inks.
  • Mineral oils are complex mixtures of saturated hydrocarbons (MOSH) (linear and cyclic saturated aliphatic hydrocarbons) and of aromatic hydrocarbons (MOAH).
  • MOSH saturated hydrocarbons
  • MOAH aromatic hydrocarbons
  • Recent proposals for regulations impose specific restrictions for Ci 0 -C 25 aromatic hydrocarbons (cf. Mineral Oil Regulation - 22, Modification of the Food Contact Materials, German Federal Ministry of Food, Agriculture and Consumer Protection, 16 May 2013).
  • the aforementioned substances are volatile and can permeate through the packaging material to the foodstuffs.
  • the need to prevent the migration of mineral oils into foodstuffs arises from the their adverse effect on human health; in fact, foodstuffs containing migrated mineral oils may cause health problems, such as in particular liver damage and in some cases cancer.
  • US 2012/0305436 describes packaging materials consisting of paper or paperboard, provided with a barrier layer obtainable by application of an aqueous polymer dispersion comprising a copolymer obtained by emulsion polymerization of C 1-C alkyl(meth)acrylates, acrylic or methacrylic acid and optionally acrylonitrile and other monomers.
  • the present invention relates to an improvement that makes it possible to prevent the migration of mineral oils as defined above, as well as of aqueous or oily substances, at the same time obtaining products that are highly resistant to water.
  • the invention relates to a process for preventing the migration of mineral oils in a packaging material, a process for the production of packaging material and the material thus obtained, as defined in the appended claims, which constitute an integral part of the present description.
  • the cellulosic substrate is treated with acrylic polymers and then with cyclic olefin copolymers (COCs), creating a functional barrier that prevents foodstuffs (particularly dry foodstuffs), when put in contact with this substrate, from being contaminated with MOSH and MOAH released from the substrate.
  • COCs cyclic olefin copolymers
  • acrylic-based polymers for example polymethylmethacrylate (PMMA) or polyethylmethacrylate (PEMA) are biocompatible, transparent, thermoplastic polymers, of low density and resistant to fracture.
  • PMMA also known as acrylic glass
  • PBA polybisphenol-A
  • PC polycarbonate
  • the acrylic polymers usable in the context of the invention comprise film-forming polymers and copolymers obtained from acrylic or methac ' rylic monomers, for example Ci-C 6 alkyl(meth)acrylates.
  • the acrylic polymers or copolymers are applied to the substrates by dissolution in a solvent.
  • solutions of the polymers may be prepared in common solvents, such as chloroform, toluene, ethyl acetate or acetone, obtaining solutions of controlled viscosity.
  • Application may be carried out by various techniques, such as dip coating, drop casting, roll coating (blade coating, pad coating) and spray coating.
  • the polymer material may also be deposited by extrusion processes.
  • the acrylic or aery late polymers are bound to the cellulosic fibres of the substrate by hydrogen bonds via the carbonyl groups of the acrylates and the hydroxyl groups of the cellulose, forming a first protective layer around the fibres.
  • the concentration of the acrylic polymer or copolymer in the solvent may vary over a wide range depending on the molecular weight of the polymer used, so as to obtain suitable viscosity for the aforementioned application techniques.
  • acrylic polymer e.g. PMMA
  • COC copolymer it is possible to use solutions, in the aforementioned solvents, having a concentration from 0.5 to 40 wt%.
  • the process according to the invention envisages application of a second protective coating of cyclic olefin copolymer (COC).
  • COCs usable comprise the copolymers marketed with the trademark TOPAS®, as described in TOPAS (Cyclic Olefin Copolymer) Brochure, March 2006.
  • Amorphous biocompatible polymers derived from the polymerization of ethylene and norbornene, are preferred. These are transparent, water-repellent and heat-resistant polymers having high barrier properties against moisture, gases and aromas, which make them particularly useful for numerous applications, for example for the production of films for food packaging and in the production of lenses, vials and medical devices.
  • the COC coating is preferably applied by dissolving the polymer in a solvent, using the common solvents, such as chloroform and toluene mentioned above, or other environmentally friendly solvents (green solvents), such as limonene. It is possible to use the same application techniques mentioned above for the acrylic coating polymer.
  • concentrations of COC in the solvent that make it possible to achieve a suitable viscosity for application are generally from 5 to 30 wt%; higher concentrations make it possible to obtain thicker coatings.
  • the first and the second polymer coating consist respectively of the acrylic polymer alone or a mixture thereof and respectively of the cyclic olefin polymer alone or a mixture thereof.
  • the substrates on which the process is applied are mainly packaging materials, such as paper, cardboard or paperboard, obtained using recycled paper, contaminated with mineral oils used for printing inks; however, other substrates comprising cellulosic fibres are also included, for example wooden panels and textile products.
  • the polymers selected for the process according to the invention are approved for contact with foodstuffs and do not have an adverse effect on the subsequent recyclability of the materials thus treated, as the total amount of polymer making up the two coatings is generally less than 50 g/m,, preferably between 15 and 50 g/m 2 ; the acrylic coating preferably has a weight from 5 to 15 g/m 2 and the COC coating has a weight from 10 to 35 g/m 2 .
  • the two polymer coatings may be applied to one or to both surfaces of the substrate.
  • a pretreatment of the samples by dipping in solvents, such as chlorinated solvents (chloroform and dichloromethane), toluene, hexane for a suitable length of time (1-20 hours) at room temperature, followed by rinsing and drying under a hood.
  • solvents such as chlorinated solvents (chloroform and dichloromethane), toluene, hexane
  • the pretreatment with solvents may also be carried out directly on the cellulose pulp prior to production of the sheets of paper or cardboard. This is followed by application of just one or of both polymer coatings.
  • Fig. 1 is a schematic representation of a process for application of the coating with barrier effect
  • Figs. 2A and 2B show photographs acquired by scanning electron microscopy (SEM) of the surface of untreated paper (A) and, respectively, paper treated (B) with solutions at 5% w/v of an acrylic polymer and 20% w/v of COC in chloroform;
  • - Fig. 3 is a histogram showing, on the ordinate, the water vapour transmission rate for a cardboard treated by the process according to the invention compared with an untreated cardboard and cardboard treated with only one of the polymers of PMMA and COC;
  • Fig. 4 is a histogram corresponding to Fig. 3, in which the organic vapour transmission rate is shown on the ordinate;
  • - Fig. 5 is an FTIR-ATR spectrum relating to untreated cardboard (a), and cardboard treated with PMMA (b), treated with COC (c) and with PMMA and COC (d);
  • Fig. 6 is a histogram showing, on the ordinate, the Young's modulus determined on an untreated paper, and paper treated with PMMA, with COC, and PMMA and COC.
  • Acrylic polymer of PMMA, commercially available, and cyclic olefin copolymers (TOPAS®) were used as prototype polymers for carrying out the invention. Both polymers were dissolved in commercial chloroform. Initially, a recycled cardboard was treated by dip coating in a solution at 5% w/v of PMMA in chloroform, by dipping for 2 minutes and then drying under a hood at room temperature.
  • the same sample was coated with COC (TOPAS 8007, 20% w/v) using a laboratory coating device (EC 200-USA), operating at a speed of 1 m/minute.
  • the laboratory coating device used comprised a speed controller, a sample fixing device and a coating bar for coating the substrate.
  • the viscosity of the solutions could easily be controlled by altering the concentration of the polymer in the solvent.
  • the thickness of the TOPAS® coating may be controlled by altering the diameter of the coating bar and the deposition rate.
  • the resultant cardboard thus treated is characterized by excellent hydrophobic properties both on the surface, and on the internal face of the cardboard, with a high barrier to the migration of mineral oils and organic vapours, used for simulating the barrier to mineral oils.
  • the PMMA had optimum bonding to the cellulose as well as excellent bonding to the COC used.
  • the combination of the two polymers on cellulose surfaces forms a coating that is transparent, compact and hydrophobic, which has a significant degree of barrier properties to moisture, to mineral oil and to gases.
  • the coatings thus obtained have excellent adhesion to the underlying substrate.
  • the papers treated with PMMA/TOPAS® prove to be hydrophobic not only at the surface, but also internally. Using PMMA alone or COC alone does not allow the desired barrier properties to be obtained.
  • the migration of mineral oil was studied using TENAX (modified polyphenylene oxide), to simulate a dry foodstuff.
  • the treatments that have been developed completely block the migration of aromatic hydrocarbons (MOSH ⁇ C 25 and MO AH ⁇ C 25 ), indicating a 100% barrier to MO AH in the sample treated with PMMA and then with COC (TOP AS®), by the procedure described above.
  • the coatings of PMMA and COC had a coating weight of 7 g/m and 20 g/m respectively.
  • the samples treated In addition to the barrier properties to mineral oils, the samples treated also had excellent hydrophobicity, barrier properties to moisture and to gases, and adequate mechanical properties. Analysis of the hydrophobic properties
  • the treatment according to the invention significantly improves the barrier properties to water and to organic vapours, as can be seen from the histograms in Figs. 3 and 4; moreover, the increase is synergistic, as the reduction is significantly greater than that obtainable by the additive effect of the two coatings. The improvement is probably due to an effect of increase in surface density of the fibres.
  • FTIR-ATR analysis was undertaken to verify the bond of PMMA/COC to the cellulose.
  • the FTIR spectra of recycled cellulose cardboard, untreated and treated, respectively, were recorded at room temperature, as illustrated in Fig. 5.
  • the absorption peaks in the 3300- 3400 cm “1 region are attributed to stretching of the hydroxyl group; 2008-3000 cm “1 to C-H stretching and 1600-1800 cm “1 to the ester group.
  • Fig. 6 is a histogram that illustrates Young's modulus of treated and untreated samples.
  • the sample treated with 5% PMMA and 20% COC shows an increase in Young's modulus compared with the untreated sample. This is probably due to the strong interaction between the polymers and the fibres, making it possible to withstand higher stresses.
  • the process according to the invention may moreover envisage the incorporation of fluorinated polymers, approved for contact with foodstuffs in the solutions for treatment with acrylic polymer and/or COC, for the purpose of endowing cellulosic fibres with oleophobic properties and resistance to fats.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Wrappers (AREA)
  • Paper (AREA)
  • Packages (AREA)

Abstract

Process for inhibiting the migration to the exterior of mineral oils consisting of saturated and/or aromatic hydrocarbons and/or of their volatile components, having from 10 to 25 carbon atoms included in packaging materials comprising recycled cellulosic fibres, characterized in that it comprises the operations of surface treatment of said packaging material to form a first polymer coating comprising an acrylic polymer, in contact with said fibres, and a second surface treatment by application of a second polymer coating comprising a cyclic olefin polymer on said first coating, where the total amount of acrylic polymer and of cyclic olefin polymer of the first and second coating is between 15 and 50 g/m2.

Description

Packaging material with barrier properties to the migration of mineral oils and process for preparation thereof
The present invention relates to a process for the production of cellulose-based substrates that have barrier properties against the migration of mineral oils and/or of their volatile components, particularly for the production of packaging materials suitable for contact with foodstuffs such as paper, cardboard or paperboard, having the aforementioned barrier properties. In the food industry, packaging has an important role for maintaining the freshness of foodstuffs and for providing protection against atmospheric agents. However, the impurities present in packaging materials may adulterate the quality of the foodstuffs. For example, packaging materials obtained from recycled cellulosic products may contain mineral oils consisting of colourless hydrocarbons (C1s-C40) mainly originating from printing inks.
Mineral oils are complex mixtures of saturated hydrocarbons (MOSH) (linear and cyclic saturated aliphatic hydrocarbons) and of aromatic hydrocarbons (MOAH). Current regulations relating to the presence of mineral oil impurities in paper and cardboard material for contact with foodstuffs stipulate that the possibility of migration of MOSH and MOAH having a number of carbon atoms less than 25 into dry foodstuffs in contact with said materials should be excluded. Recent proposals for regulations impose specific restrictions for Ci0-C25 aromatic hydrocarbons (cf. Mineral Oil Regulation - 22, Modification of the Food Contact Materials, German Federal Ministry of Food, Agriculture and Consumer Protection, 16 May 2013).
The aforementioned substances are volatile and can permeate through the packaging material to the foodstuffs. The need to prevent the migration of mineral oils into foodstuffs arises from the their adverse effect on human health; in fact, foodstuffs containing migrated mineral oils may cause health problems, such as in particular liver damage and in some cases cancer. There is therefore a need to limit and in particular to exclude the migration of these mineral oils (MOSH and MO AH, as defined above) having from 10 to 25 carbon atoms, contained in recycled packaging materials, into foodstuffs, in order to protect consumers against health risks (see Scientific Opinion on Mineral Oil Hydrocarbons in Food, EFSA Journal 2012, 10(6): 2704, pages 1-185).
There is thus a need to find solutions that are simple, versatile, of low cost and easily scalable to the industrial scale, for preventing the migration of mineral oils and of their volatile components, in particular having a number of carbon atoms between 10 and 25, from cellulosic packaging materials obtained from recycled paper.
In this context, US 2012/0305436 describes packaging materials consisting of paper or paperboard, provided with a barrier layer obtainable by application of an aqueous polymer dispersion comprising a copolymer obtained by emulsion polymerization of C 1-C alkyl(meth)acrylates, acrylic or methacrylic acid and optionally acrylonitrile and other monomers.
The present invention relates to an improvement that makes it possible to prevent the migration of mineral oils as defined above, as well as of aqueous or oily substances, at the same time obtaining products that are highly resistant to water.
Therefore the invention relates to a process for preventing the migration of mineral oils in a packaging material, a process for the production of packaging material and the material thus obtained, as defined in the appended claims, which constitute an integral part of the present description.
According to the invention, for the purpose of preventing the migration of mineral oils, i.e. for impeding their migration out of the substrate containing them, the cellulosic substrate is treated with acrylic polymers and then with cyclic olefin copolymers (COCs), creating a functional barrier that prevents foodstuffs (particularly dry foodstuffs), when put in contact with this substrate, from being contaminated with MOSH and MOAH released from the substrate. It is known that acrylic-based polymers, for example polymethylmethacrylate (PMMA) or polyethylmethacrylate (PEMA) are biocompatible, transparent, thermoplastic polymers, of low density and resistant to fracture. In particular, PMMA (also known as acrylic glass) does not contain polybisphenol-A (PBA), which is harmful to health, and it constitutes an economical alternative to polycarbonate (PC). The acrylic polymers usable in the context of the invention comprise film-forming polymers and copolymers obtained from acrylic or methac'rylic monomers, for example Ci-C6 alkyl(meth)acrylates.
In the preferred embodiment, the acrylic polymers or copolymers are applied to the substrates by dissolution in a solvent. For this purpose, solutions of the polymers may be prepared in common solvents, such as chloroform, toluene, ethyl acetate or acetone, obtaining solutions of controlled viscosity. Application may be carried out by various techniques, such as dip coating, drop casting, roll coating (blade coating, pad coating) and spray coating. The polymer material may also be deposited by extrusion processes.
After evaporation of the solvent, the acrylic or aery late polymers are bound to the cellulosic fibres of the substrate by hydrogen bonds via the carbonyl groups of the acrylates and the hydroxyl groups of the cellulose, forming a first protective layer around the fibres.
The concentration of the acrylic polymer or copolymer in the solvent may vary over a wide range depending on the molecular weight of the polymer used, so as to obtain suitable viscosity for the aforementioned application techniques. As an example, using acrylic polymer (e.g. PMMA) or COC copolymer, it is possible to use solutions, in the aforementioned solvents, having a concentration from 0.5 to 40 wt%.
After removal of the solvent by evaporation, the process according to the invention envisages application of a second protective coating of cyclic olefin copolymer (COC). The COCs usable comprise the copolymers marketed with the trademark TOPAS®, as described in TOPAS (Cyclic Olefin Copolymer) Brochure, March 2006.
Amorphous biocompatible polymers, derived from the polymerization of ethylene and norbornene, are preferred. These are transparent, water-repellent and heat-resistant polymers having high barrier properties against moisture, gases and aromas, which make them particularly useful for numerous applications, for example for the production of films for food packaging and in the production of lenses, vials and medical devices.
The COC coating is preferably applied by dissolving the polymer in a solvent, using the common solvents, such as chloroform and toluene mentioned above, or other environmentally friendly solvents (green solvents), such as limonene. It is possible to use the same application techniques mentioned above for the acrylic coating polymer. The concentrations of COC in the solvent that make it possible to achieve a suitable viscosity for application are generally from 5 to 30 wt%; higher concentrations make it possible to obtain thicker coatings. In one embodiment, the first and the second polymer coating consist respectively of the acrylic polymer alone or a mixture thereof and respectively of the cyclic olefin polymer alone or a mixture thereof.
The substrates on which the process is applied are mainly packaging materials, such as paper, cardboard or paperboard, obtained using recycled paper, contaminated with mineral oils used for printing inks; however, other substrates comprising cellulosic fibres are also included, for example wooden panels and textile products. The polymers selected for the process according to the invention are approved for contact with foodstuffs and do not have an adverse effect on the subsequent recyclability of the materials thus treated, as the total amount of polymer making up the two coatings is generally less than 50 g/m,, preferably between 15 and 50 g/m2; the acrylic coating preferably has a weight from 5 to 15 g/m2 and the COC coating has a weight from 10 to 35 g/m2.
Depending on the application technique used, the two polymer coatings may be applied to one or to both surfaces of the substrate.
In order to reduce the migration of mineral oil from the cardboard, it is also possible to carry out a pretreatment of the samples by dipping in solvents, such as chlorinated solvents (chloroform and dichloromethane), toluene, hexane for a suitable length of time (1-20 hours) at room temperature, followed by rinsing and drying under a hood. The pretreatment with solvents may also be carried out directly on the cellulose pulp prior to production of the sheets of paper or cardboard. This is followed by application of just one or of both polymer coatings.
Further features and advantages of the process according to the invention and of the coated materials thus obtained will become clear from the embodiment examples given below and from the tests performed on the materials thus obtained, which provide evidence of the barrier properties to migration of oils, the hydrophobic properties and the barrier properties to water vapour and to organic vapours, as well as the mechanical properties.
In the appended drawings:
- Fig. 1 is a schematic representation of a process for application of the coating with barrier effect;
Figs. 2A and 2B show photographs acquired by scanning electron microscopy (SEM) of the surface of untreated paper (A) and, respectively, paper treated (B) with solutions at 5% w/v of an acrylic polymer and 20% w/v of COC in chloroform;
- Fig. 3 is a histogram showing, on the ordinate, the water vapour transmission rate for a cardboard treated by the process according to the invention compared with an untreated cardboard and cardboard treated with only one of the polymers of PMMA and COC;
Fig. 4 is a histogram corresponding to Fig. 3, in which the organic vapour transmission rate is shown on the ordinate;
- Fig. 5 is an FTIR-ATR spectrum relating to untreated cardboard (a), and cardboard treated with PMMA (b), treated with COC (c) and with PMMA and COC (d);
Fig. 6 is a histogram showing, on the ordinate, the Young's modulus determined on an untreated paper, and paper treated with PMMA, with COC, and PMMA and COC. Example
Acrylic polymer of PMMA, commercially available, and cyclic olefin copolymers (TOPAS®) were used as prototype polymers for carrying out the invention. Both polymers were dissolved in commercial chloroform. Initially, a recycled cardboard was treated by dip coating in a solution at 5% w/v of PMMA in chloroform, by dipping for 2 minutes and then drying under a hood at room temperature.
After evaporation of the solvent, the same sample was coated with COC (TOPAS 8007, 20% w/v) using a laboratory coating device (EC 200-USA), operating at a speed of 1 m/minute. The laboratory coating device used comprised a speed controller, a sample fixing device and a coating bar for coating the substrate. The viscosity of the solutions could easily be controlled by altering the concentration of the polymer in the solvent. Moreover, the thickness of the TOPAS® coating may be controlled by altering the diameter of the coating bar and the deposition rate.
The resultant cardboard thus treated is characterized by excellent hydrophobic properties both on the surface, and on the internal face of the cardboard, with a high barrier to the migration of mineral oils and organic vapours, used for simulating the barrier to mineral oils. The PMMA had optimum bonding to the cellulose as well as excellent bonding to the COC used. The combination of the two polymers on cellulose surfaces forms a coating that is transparent, compact and hydrophobic, which has a significant degree of barrier properties to moisture, to mineral oil and to gases. Moreover, the coatings thus obtained have excellent adhesion to the underlying substrate. The papers treated with PMMA/TOPAS® prove to be hydrophobic not only at the surface, but also internally. Using PMMA alone or COC alone does not allow the desired barrier properties to be obtained.
Further tests were carried out using recycled cardboards, treated with solutions of PMMA in chloroform with variable concentration from 2% to 5% w/v for times from 30 to 120 seconds and drying under a hood. Similarly, the TOPAS® polymer was used with variable concentrations from 10% to 20% w/v in chloroform. The SEM photographs in Fig. 2 demonstrate that in the presence of a porous surface, such as the surface of samples of untreated cardboard, the PMMA/COC coating penetrates into the pores of the paper and fills them. It can be seen from Fig. 2B that the porosity of the surface of the paper is reduced considerably after the treatment, even if the network structure of the cellulose fibres is still visible. The individual cellulosic fibres are coated with the films of the two polymers as a result of the treatment by dip coating and coating with the bar coating device. Migration of mineral oil
The migration of mineral oil was studied using TENAX (modified polyphenylene oxide), to simulate a dry foodstuff. The treatments that have been developed completely block the migration of aromatic hydrocarbons (MOSH < C25 and MO AH < C25), indicating a 100% barrier to MO AH in the sample treated with PMMA and then with COC (TOP AS®), by the procedure described above. The coatings of PMMA and COC had a coating weight of 7 g/m and 20 g/m respectively.
Treatment of recycled paperboards treated with PMMA alone (weight 7 g/m2) or TOP AS® alone (weight 13 g/m ) results in migration of mineral oil from 20% to 50%.
The results obtained demonstrate that the combination of the two polymers makes it possible to satisfy the current, more stringent proposals for regulations on migration of mineral oils from packaging materials to foodstuffs.
In addition to the barrier properties to mineral oils, the samples treated also had excellent hydrophobicity, barrier properties to moisture and to gases, and adequate mechanical properties. Analysis of the hydrophobic properties
The simple test of depositing droplets of water on surfaces treated according to the invention and untreated surfaces demonstrates that there is no absorption of water by the treated paper. This is found not only for the surface of cardboard, but also for the internal layers. It may therefore be assumed that the treatment uniformly covers the individual fibres of the whole volume of the cardboard, including the internal fibres.
Analysis of the water vapour transmission rate (WVTR) and organic vapour transmission rate (OVTR)
_
The transmission rates of water vapour (WVTR) and of organic vapours (OVTR) were measured, as they are important properties for food packaging materials.
The treatment according to the invention significantly improves the barrier properties to water and to organic vapours, as can be seen from the histograms in Figs. 3 and 4; moreover, the increase is synergistic, as the reduction is significantly greater than that obtainable by the additive effect of the two coatings. The improvement is probably due to an effect of increase in surface density of the fibres. FTIR-ATR analysis
FTIR-ATR analysis was undertaken to verify the bond of PMMA/COC to the cellulose. The FTIR spectra of recycled cellulose cardboard, untreated and treated, respectively, were recorded at room temperature, as illustrated in Fig. 5. The absorption peaks in the 3300- 3400 cm"1 region are attributed to stretching of the hydroxyl group; 2008-3000 cm"1 to C-H stretching and 1600-1800 cm"1 to the ester group.
The displacement of these peaks in the treated cardboards confirms the success of bonding of PMMA/COC to the recycled cellulose cardboard.
Analysis of the mechanical properties Fig. 6 is a histogram that illustrates Young's modulus of treated and untreated samples.
The sample treated with 5% PMMA and 20% COC shows an increase in Young's modulus compared with the untreated sample. This is probably due to the strong interaction between the polymers and the fibres, making it possible to withstand higher stresses.
This is further confirmed by the increase in modulus that occurs in the sample treated with PMMA alone; this indicates that this polymer interacts strongly with the entire volume of the fibres and not only with the surface of the sheet.
The process according to the invention may moreover envisage the incorporation of fluorinated polymers, approved for contact with foodstuffs in the solutions for treatment with acrylic polymer and/or COC, for the purpose of endowing cellulosic fibres with oleophobic properties and resistance to fats.
Moreover, incorporation of functional micro- and nanofillers may be envisaged, for further increasing the barrier properties. It is to be understood that although the tests were carried out with the specific use of PMMA and the cyclic olefin copolymer TOP AS 8007®, the process extends to the use of other acrylic polymers and copolymers, as defined above, and to other cyclic olefin copolymers, for example TOP AS 9505®, TOP AS 6013®, TOP AS 6015®, TOPAS 6017® and TOPAS 5013.

Claims

1. Process for inhibiting the migration to the exterior of mineral oils consisting of saturated and/or aromatic hydrocarbons and/or of their volatile components, having from 10 to 25 carbon atoms included in packaging materials comprising recycled cellulosic fibres, characterized in that it comprises the operations of surface treatment of said packaging material to form a first polymer coating comprising an acrylic polymer, in contact with said fibres and a second surface treatment by application of a second polymer coating comprising a cyclic olefin polymer on said first coating, where the total amount of acrylic polymer and of cyclic olefin polymer of the first and second coating is between 15 and 50 g/m2.
2. Process according to Claim 1, characterized in that said first coating comprises a film-forming polymer or copolymer obtained from acrylic or methacrylic monomers, particularly C i -C6 alkyl(meth)acrylates.
3. Process according to Claim 1 or 2, characterized in that said second coating comprises a cyclic olefin copolymer of ethylene and norbornene.
4. Process according to any one of Claims 1 to 3, wherein the packaging material is selected from paper, cardboard or paperboard.
5. Process for the production of a packaging material, obtained with the use of recycled cellulosic fibres, having barrier properties against migration of mineral oils consisting of saturated and/or aromatic hydrocarbons and/or their volatile components having from 10 to 25 carbon atoms, characterized in that it comprises a first surface treatment of said packaging material for the formation of an acrylic polymer coating and. a second surface treatment for the application of a cyclic olefin copolymer coating on said first coating of acrylic polymer, the total amount of said first and second coating being between 15 and 50 g/m2.
6. Process according to Claim 5, characterized in that said acrylic polymer is selected from film-forming polymers and copolymers obtained from acrylic or methacrylic monomers, particularly Ci-C6 alkyl(meth)acrylates.
7. Process according to Claim 5 or 6, characterized in that said second coating comprises a cyclic olefin copolymer of ethylene and norbornene.
8. Process according to any one of Claims 5 to 7, characterized in that said acrylic copolymer is applied with the use of a solution of acrylic polymer in a solvent selected from chloroform, toluene, ethyl acetate or acetone.
9. Process according to any one of Claims 5 to 8, characterized in that said cyclic olefin copolymer is applied with the use of a solution of said cyclic olefin polymer in a solvent selected from chloroform, toluene and environmentally-friendly solvents (green solvents), particularly limonene.
10. Process according to any of Claims 5 to 9, characterized in that said first or second coatings are applied by dip coating, drop casting, roll coating or by extrusion.
11. Process according to Claim 8 or 9, characterized in that said solution of acrylic polymer or, respectively, cyclic olefin copolymer has a concentration of polymer or copolymer from 0.5 to 40% by weight.
12. Process according to any of Claims 5 to 1 1, characterized in that said packaging material or the cellulosic pulp used for the production of said packaging material is pretreated with a solvent selected from chlorinated solvents, toluene or hexane, so as to reduce their content of mineral oils.
13. Packaging material comprising cellulose fibres, particularly recycled cellulose fibres, having barrier properties against migration of mineral oils and/or their volatile components, characterized in that it comprises at least one first surface coating, in contact with said fibres, of acrylic polymer and at least one second coating, applied on said first coating, of cyclic olefin copolymer obtained by a process according to any one of Claims 5 to 12.
EP14833222.4A 2013-12-18 2014-12-17 Packaging material with barrier properties to the migration of mineral oils and process preparation thereof Active EP3084075B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT001036A ITTO20131036A1 (en) 2013-12-18 2013-12-18 PACKAGING MATERIAL WITH BARRIER PROPERTIES FOR MIGRATION OF MINERAL OILS AND PROCEDURE FOR THEIR PREPARATION
PCT/IB2014/067030 WO2015092714A1 (en) 2013-12-18 2014-12-17 Packaging material with barrier properties to the migration of mineral oils and process preparation thereof

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EP3084075B1 EP3084075B1 (en) 2018-09-19

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IT201600072535A1 (en) * 2016-07-12 2018-01-12 Univ Degli Studi Del Piemonte Orientale A Avogadro USE OF SILICA MESOPOROSA
US11549216B2 (en) 2020-11-11 2023-01-10 Sappi North America, Inc. Oil/grease resistant paper products

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CA2739987C (en) * 2008-10-10 2017-01-03 Dow Global Technologies Llc Multilayer paper coating comprising biopolymer and water vapor barrier layers
US20120058332A1 (en) * 2010-09-03 2012-03-08 Basf Se Barrier coating made of cycloolefin copolymers
US8771812B2 (en) 2011-05-30 2014-07-08 Basf Se Paper and cardboard packaging with barrier coating

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