EP3642270A1 - Procédé de production d'un film multicouche à l'aide de particules polymères coeur-écorce - Google Patents

Procédé de production d'un film multicouche à l'aide de particules polymères coeur-écorce

Info

Publication number
EP3642270A1
EP3642270A1 EP17761314.8A EP17761314A EP3642270A1 EP 3642270 A1 EP3642270 A1 EP 3642270A1 EP 17761314 A EP17761314 A EP 17761314A EP 3642270 A1 EP3642270 A1 EP 3642270A1
Authority
EP
European Patent Office
Prior art keywords
core
shell
polymeric particles
coating
shell polymeric
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.)
Pending
Application number
EP17761314.8A
Other languages
German (de)
English (en)
Inventor
Keltoum Ouzineb
Thimothy MC KENNA
Barbara REZENDE LARA
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.)
Centre National de la Recherche Scientifique CNRS
Universite Claude Bernard Lyon 1 UCBL
CPE Lyon FCR SAS
Toray Films Europe SAS
Original Assignee
Centre National de la Recherche Scientifique CNRS
Universite Claude Bernard Lyon 1 UCBL
CPE Lyon FCR SAS
Toray Films Europe SAS
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 Centre National de la Recherche Scientifique CNRS, Universite Claude Bernard Lyon 1 UCBL, CPE Lyon FCR SAS, Toray Films Europe SAS filed Critical Centre National de la Recherche Scientifique CNRS
Publication of EP3642270A1 publication Critical patent/EP3642270A1/fr
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/002—Priming paints
    • 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
    • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
    • C08J7/0423—Coating with two or more layers, where at least one layer of a composition contains a polymer binder with at least one layer of inorganic material and at least one layer of a composition containing a polymer binder
    • 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
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • 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
    • C08J7/04—Coating
    • C08J7/056—Forming hydrophilic coatings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/081—Oxides of aluminium, magnesium or beryllium
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/20—Metallic material, boron or silicon on organic substrates
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/54—Controlling or regulating the coating process
    • C23C14/542—Controlling the film thickness or evaporation rate
    • C23C14/545—Controlling the film thickness or evaporation rate using measurement on deposited material
    • C23C14/547—Controlling the film thickness or evaporation rate using measurement on deposited material using optical methods
    • 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
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • 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
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical

Definitions

  • the field of the invention is that of plastic films.
  • the invention relates to a method for producing a multilayer film.
  • the invention relates to a method for producing a multilayer film comprising at least one polymer support, at least one bonding primer layer and at least one coating, using a primer dispersion comprising core-shell polymeric particles.
  • Plastic films and in particular polyester films are well known for their excellent properties of thermal stability, dimensional stability, chemical resistance and relatively high surface energy.
  • These are supports that are very strong and particularly desirable for various film-forming coatings resulting in composite materials that find numerous applications: food or non-food packaging, support protection, films or sheets for graphic art (printing or drawing) and metallized films.
  • these supports have the drawback of insufficient adhesion of said film-forming coatings on the supports, in particular on polyester films, thus making their use ineffective and/or unreliable and therefore unsuitable.
  • metallic coatings of PET film do not adhere properly to the film, especially under wet conditions and at high temperature, as it is the case in processes for hot filling, pasteurization and sterilization. This lack or loss of adhesion means that the coating's expected barrier effect to oxygen and water vapour is lost, which causes deterioration of the food contents and a health risk.
  • This intermediate coating also commonly called priming coat or bonding primer layer, is designed to have, on the one hand, good adhesion to the substrate and, on the other hand, good adhesion to the coating.
  • Numerous polymers or copolymers have been proposed for producing this coating, in particular acrylic polymers.
  • patent application WO2014/102487 describes a method for coating a support with a primer layer using an aqueous dispersion.
  • This aqueous dispersion comprises (i) particles of at least one acrylic and/or methacrylic polymer having either a gel content of less than 50 wt. % and an acrylic and/or methacrylic acid copolymer content of at least 10 wt. %, or a gel content of at least 50 wt. %, and (ii) at least one cross-linking agent.
  • patent application EP0260203A1 describes a modified polymer obtained by aqueous-phase radical polymerization of at least one monomer of an acrylic nature in the presence of an effective quantity of a water-dispersible polyester, derived from at least one aromatic dicarboxylic acid and at least one aliphatic diol and comprising a plurality of sulphonyloxy groups. Although the results for adhesion obtained with these formulations are good, further improvement is desirable.
  • the invention aims to achieve at least one of the essential aims listed below.
  • One of the essential aims of the present invention is to provide a method for producing a multilayer film by coating a polymer support with a primer dispersion, making it possible to obtain distinctly enhanced adhesion properties between the support and the final coating, together with enhanced barrier properties, in particular barrier properties towards oxygen and water.
  • Another essential aim of the present invention is to provide a method for producing a multilayer film comprising a polymer support covered with a layer of metal and/or of metal oxide having enhanced adhesion properties between the support and the metal coating.
  • Another essential aim of the present invention is to provide a method for producing a multilayer film comprising a polymer support covered with a layer of metal and/or of metal oxide having enhanced barrier properties at high temperature and under wet conditions.
  • Another essential aim of the present invention is to provide a method for producing a multilayer film which is easy to implement.
  • primer dispersion comprising core-shell polymeric particles for making the bonding primer layer allows for enhanced barrier properties and adhesion properties of the multilayer film.
  • the core-shell polymeric particles have a core comprising one type of polymer and a shell comprising a different type of polymer.
  • a core comprising one type of polymer
  • a shell comprising a different type of polymer.
  • the combination of different types of polymer takes place at the molecular level in the core-shell particles, there is no risk of phase separation of the different polymers. Therefore, there is also less risk of a defect on the bonding primer layer and the bonding primer layer is more homogeneous than with a simple combination of different polymers.
  • the barrier properties of the multilayer film prepared with the core-shell polymeric particles are enhanced.
  • the use of core-shell polymeric particles also allows for a high concentration of functional groups at the surface of the bonding primer layer which gives a good adhesion of the metal layer, without compromising the barrier properties of the multilayer film.
  • the core-shell polymeric particles used can be easily synthesized using cheap monomers and the process as described above is easy to implement.
  • the invention also relates to the use of a primer dispersion comprising core-shell polymeric particles to obtain a bonding primer layer that makes it possible to control the barrier properties and/or the adhesion properties of a multilayer film comprising a polymer support, a bonding primer layer and a coating.
  • Figure 1 shows Transmission Electron Microscopy (TEM) pictures of the core-shell polymeric particles.
  • Figure 1 a) shows a TEM picture of the core-shell particles CSEO synthesized according to example 1.
  • Figure 1 b) shows a TEM picture of the core-shell particles CSEl synthesized according to example 1.
  • Figure 1 c) shows a TEM picture of the core-shell particles CSE2 synthesized according to example 1.
  • Figure 2 shows cryo-TEM pictures of the core-shell polymeric particles and of the core alone.
  • Figure 2 a) shows a cryo-TEM picture of the core alone particle CI synthesized according to example 1.
  • Figure 2 b) shows a cryo-TEM picture of the core-shell particles CSEO synthesized according to example 1.
  • Figure 2 c) shows a cryo-TEM picture of the core-shell particles CSEl synthesized according to example 1.
  • Figure 2 d) shows a cryo-TEM picture of the core-shell particles CSE2 synthesized according to example 1.
  • Figure 3 shows a diagram of the water permeability of the multilayer film according to the protocol described in example 2.
  • Figure 4 shows a diagram of the oxygen permeability of the multilayer film according to the protocol described in example 2.
  • Figure 5 shows a diagram of the adhesion of the metal coating on the multilayer film under dry conditions according to the protocol described in example 2.
  • Figure 6 shows a diagram of the adhesion of the metal coating on the multilayer film under wet conditions (90% relative humidity) according to the protocol described in example 2.
  • Figure 7 shows an example of a multilayer film according to the present invention. Detailed description
  • the invention first relates to a method for producing a multilayer film using a primer dispersion comprising core-shell polymeric particles.
  • a primer dispersion comprising core-shell polymeric particles.
  • FIG 7. An example of a multilayer film obtained according to this method is shown in figure 7.
  • the core-shell polymeric particles of the primer dispersion are a key element of the present invention.
  • Core-shell polymeric particles is intended to mean particles comprising a core (inner material) and a shell (outer material), the core and the shell being in different materials.
  • the polymer comprised in the core is chemically different from the polymer comprised in the shell.
  • the shell of the core-shell polymeric particles is more hydrophilic than the core. In other words, the shell has a higher ability to form hydrogen bonds than the core.
  • the core-shell polymeric particles comprise acrylic and/or methacrylic polymers.
  • the acrylic and/or methacrylic polymers may represent at least 80%, 85%, 90%> or 95% by weight of the total weight of the polymers.
  • the shell of the core-shell polymeric particles comprises at least a polymer made from at least a hydrophilic monomer, preferably selected from the group consisting of alkyl acrylates and alkyl methacrylates, in which the alkyl moiety has 1 or 2 carbon atoms.
  • the preferred monomers are methyl acrylate, methyl methacrylate, ethyl acrylate, and mixtures thereof, methyl methacrylate and ethyl acrylate being the most preferred.
  • These hydrophilic monomers have a high affinity with the final coating, especially if it is a layer of metal or metal oxide.
  • hydrophilic monomers being on the shell of the particles, and therefore on the surface of the bonding primer layer, allows for a good adhesion of the metal coating on the polymer support.
  • the hydrophilic monomers may represent at least 50%, 70% or 80% by weight of the total weight of the monomers of the shell.
  • the shell of the core-shell polymeric particles comprises less than or equal to 20%> by weight of a cross-linking agent, relative to the total weight of monomers in the shell, preferably less than or equal to 10% by weight.
  • the shell comprises between 0.01 and 10% of a cross-linking agent.
  • the cross-linking agent can be selected from the group consisting of bifunctional ethylenically unsaturated monomers.
  • the bifunctional ethylenically unsaturated monomers that may be used in the present invention include diacrylate compounds, like glycol dimethacrylate, and divinylbenzenes.
  • the shell does not comprise a cross-linking agent.
  • the shell of the core-shell polymeric particles comprises at least a polymer made from at least a monomer selected from the group consisting of acrylic acid and methacrylic acid, and mixture thereof.
  • the shell can comprises less than or equal to 5% by weight of this monomer, relative to the total weight of monomers in the shell. Typically, the shell comprises around 2% of this monomer.
  • the shell of the core-shell polymeric particles comprises at least a polymer made from:
  • hydrophilic monomer selected from the group consisting of alkyl acrylates and alkyl methacrylates, in which the alkyl moiety has 1 or 2 carbon atoms, and
  • the core of the core-shell polymeric particles comprises:
  • At least a cross-linked polymer made from at least a hydrophilic monomer, preferably selected from the group consisting of alkyl acrylates and alkyl methacrylate, in which the alkyl moiety has 1 or 2 carbon atoms, or
  • At least a polymer made from at least a hydrophobic monomer preferably selected from the group consisting of alkyl acrylates and alkyl methacrylates, in which the alkyl moiety is linear or branched and contains at least 4 carbon atoms.
  • the preferred hydrophilic monomers are methyl acrylate, methyl methacrylate, ethyl acrylate, and mixtures thereof, methyl methacrylate and ethyl acrylate being the most preferred.
  • the polymer is cross-linked with at least a cross-linking agent and the core comprises less than or equal to 5 % by weight of a cross-linking agent, relative to the total weight of monomers in the core, preferably less than or equal to 1 % by weight.
  • the core comprises between 0.5 and 1 % by weight of a cross-linking agent.
  • the cross-linking agent can be selected from the group consisting of bifunctional ethylenically unsaturated monomers.
  • the bifunctional ethylenically unsaturated monomers that may be used in the present invention include diacrylate compounds, like glycol dimethacrylate, and divinylbenzenes.
  • the hydrophobic monomers that may be used for the present invention include alkyl acrylates and alkyl methacrylates where the alkyl moiety is linear or branched and contains at least 4 carbon atoms.
  • the alkyl moiety may be selected from the group constituted of n-butyl, isobutyl, t-butyl, n-pentyl, n-hexyl, ethyl-2-hexyl, decyl, dodecyl, and octadecyl.
  • the preferred hydrophobic monomers are butyl acrylate, butyl methacrylate and mixtures thereof.
  • the core of the core-shell polymeric particles comprises a co-polymer made from:
  • At least a hydrophobic monomer selected from the group consisting of alkyl acrylates and alkyl methacrylates, where the alkyl moiety is linear or branched and contains at least 4 carbon atoms;
  • hydrophobic monomer selected from the group consisting of ethylenically unsaturated aromatic compounds, like styrenic, butadiene, ethylene, vinylidene difluoride, and mixtures thereof.
  • the ratio of the hydrophobic monomer selected from the group consisting of alkyl acrylates and alkyl methacrylates, where the alkyl moiety is linear or branched and contains at least 4 carbon atoms to the hydrophobic monomer selected from the group consisting of ethylenically unsaturated aromatic compounds can, for example, be comprised between 5/95 and 95/5, between 10/90 and 80/20 or between 15/85 and 50/50.
  • the core/shell ratio of the core-shell polymeric particles can be comprised between 50/50 and 10/90 relative to the total weight of monomers. For example, the core/shell ratio is comprised between 40/60 and 20/80, or is around 30/70.
  • the core-shell polymeric particles are typically spherical particles.
  • the diameter of the core-shell polymeric particles can be comprised between 30 and 800 nm, or between 50 and 500, or between 75 and 200 nm.
  • the diameter can be determined, for example, by Dynamic-Light- Scattering (DLS), TEM or cryo-TEM.
  • the core-shell polymeric particles can easily be synthesized using free-radical emulsion polymerisation.
  • the core-shell polymeric particles comprise a shell comprising at least a polymer made from at least a hydrophilic monomer, preferably selected from the group consisting of alkyl acrylates and alkyl methacrylates, in which the alkyl moiety has 1 or 2 carbon atoms, and a core comprising
  • At least a cross-linked polymer made from a hydrophilic monomer preferably selected from the group consisting of alkyl acrylates and alkyl methacrylate, in which the alkyl moiety has 1 or 2 carbon atoms, or
  • At least a polymer made from at least a hydrophobic monomer preferably selected from the group consisting of alkyl acrylates and alkyl methacrylates, in which the alkyl moiety is linear or branched and contains at least 4 carbon atoms.
  • the method comprises the following steps:
  • the support implemented in the present method is a solid polymer support. Quite particularly, a polyester film and/or a polyolefm film is used.
  • the polymer support implemented for the present invention is preferably a film, more preferably a film with a thickness A such that:
  • the polymer support according to the invention may advantageously partly comprise recycled product originating from the support itself and/or from the coated support.
  • the support may contain up to 80% by weight of this recycled product relative to the total weight of the final support. This makes it possible to reduce the costs of production of the film and avoid economic losses due to the non-use of scraps of support and/or of coated support.
  • the polymer support implemented in the present invention is a film that may be oriented or not. Preferably, it is oriented.
  • the film used is bi-axially oriented.
  • the stretching sequences for obtaining an oriented film may be different depending on the machines used, without affecting the properties obtained by means of the invention.
  • so-called inverse-sequence machines or multistep machines, machines with alternating sequences or machines with simultaneous stretching, etc. may usefully be used.
  • the stretching temperature is for example comprised between the glass transition temperature Tg and a temperature at most equal to Tg + 60°C in the longitudinal direction as well as in the transverse direction.
  • thermosetting is carried out between 180°C and 250°C (for example at 240°C) for 1 to 60 seconds for example and then at a lower temperature in order to stabilize the film.
  • film-forming linear polyesters, crystallizable by orientation are used, and obtained in standard fashion starting from one or more aromatic dicarboxylic acids or derivatives thereof (esters of lower aliphatic alcohols or halides for example) and from one or more aliphatic diols (glycols).
  • the polyester constituting the polymer support may be selected from the polyesters that are usually used for obtaining bi-oriented semi crystalline films.
  • aromatic acids mention may be made of the phthalic, terephthalic, isophthalic, naphthalene-2,5-dicarboxylic, and naphthalene-2,6-dicarboxylic acids. These acids may be combined with a minor quantity of one or more aliphatic or cycloaliphatic dicarboxylic acids, such as the adipic, azelaic, tetra- or hexahydroterephthalic acids.
  • aliphatic diols mention may be made of ethylene glycol, propane- 1,3-diol and butane- 1,4-diol.
  • the crystallizable film- forming polyesters are polyterephthalates or alkylenediol polynaphthalenedicarboxylates and, in particular, polyethylene terephthalate of ethylene glycol (PET) or of butane- 1,4-diol or copolyesters comprising at least 80 mole percent of ethylene glycol terephthalate units.
  • the polyester is a poly(ethylene terephthalate) glycol the intrinsic viscosity of which measured at 25°C in ortho-chlorophenol is between 0.6 dl/g and 0.75 dl/g.
  • the bi-oriented polyester films are for example:
  • aromatic polyesters are in particular polyethylene terephthalate (PET), polyethylene isophthalate, polybutylene terephthalate, poly(dimethyl-l,4- cyclohexyleneterephthalate) and polyethylene-2,6-naphthalenedicarboxylate.
  • the aromatic polyester may be a copolymer of these polymers or a mixture of these polymers with a small quantity of other resins, a non- limitative example being polybutylene terephthalate (PBT).
  • PBT polybutylene terephthalate
  • PET polyethylene terephthalate
  • PEN polyethylene-2,6-naphthalenedicarboxylate
  • the content of terephthalic acid is at least 80.
  • the support is a film of polyethylene terephthalate PET (for example bi- axially oriented) or polyethylene naphthalate (PEN) or polybutylene terephthalate (PBT).
  • the polymer support according to the invention may be monolayer, bi-layer or tri-layer.
  • Each of the layers is composed of polyesters as defined above, preferably of PET, PBT or PEN, and/or of the copolyesters described above and/or of mixtures of polyesters/copolyesters.
  • the layer or layers may be of a structure M, MN, MNM or MNO, where M is different from N and O, N is different from O.
  • the main layer may be sandwiched between one or two layers, identical or not in terms of thickness and/or of composition.
  • the support may be symmetric or asymmetric. One of these layers of the support may increase the adhesion of the future coating described below.
  • the polymer support can also be a polyolefm film, like a biaxially oriented polypropylene film.
  • At least a portion of the surface of the film according to the invention is subjected to a physical treatment by electric discharge of the corona type and/or to a treatment of the plasma type. This treatment is carried out before the coating of step c).
  • Said treatment of the corona type is a corona discharge under ambient air at atmospheric pressure or under gases at high partial pressures, preferably between 100 mbar and 3000 mbar, even more preferably at atmospheric pressure.
  • the primer dispersion comprising core-shell polymeric particles is preferably in the form of an aqueous dispersion.
  • Coating of the polymer support with the primer dispersion may be carried out by the various techniques known to a person skilled in the art.
  • the dispersion may be deposited by gravity from a slot-orifice coater, or by passing the film through the dispersion, by means of transfer rollers, by in-line coating with a reverse gravure process.
  • coating of the polymer support, according to the present invention is carried out in-line, which not only allows simplification of industrial implementation but also a considerable saving of time and money.
  • the thickness of the coating depends in particular on the dry extract of the dispersion used and the conditions of drying of the coating. Of course, the thickness also depends on the quantity of coating deposited.
  • Coating of the support is carried out on at least one face of the polymer support. It may of course be carried out on both faces of the polymer support.
  • the drying of the coating can be done at room temperature or by heating.
  • infrared radiation can be used to dry the primer dispersion.
  • This coating step is done by coating the bonding primer layer with at least one coating of
  • At least one layer of adhesive at least one layer of adhesive.
  • the coating may be made on the bonding primer layer that is present on one or both faces of the support.
  • the multilayer film coated with a layer of metal and/or metal oxide and/or silicon oxide offers very good barrier properties, especially to oxygen and steam, under conditions of high temperature and humidity.
  • the conditions for hot filling or packaging, for example of food products such as tomato sauce, are conditions under high temperature and wet conditions.
  • the metallization can be carried out under vacuum. It consists of vaporizing under vacuum (4x10 ⁇ 4 mbar) a thin metallic layer (typically aluminium) on the film. Evaporation is carried out in ceramic crucibles heated by the Joule effect (1400°C to 1500°C). The metal is then sprayed onto the surface of the film which is in contact with a cooled roller called a coating roller. It then condenses immediately, thus forming a thin layer from 20 nm to 100 nm. During metallizing, the thickness of the layer of metal is monitored by measuring the optical density (OD, measurement of the transparency of the film).
  • OD optical density
  • the metal is selected from the group consisting of aluminium, copper, chromium, nickel, silver, gold, alloys thereof, and mixtures thereof.
  • the metal oxide is selected from the oxides of aluminium, silicon, copper, nickel, silver and mixtures thereof. Coating the support with zinc sulphide may also be envisaged.
  • the method comprises the following steps:
  • a shell comprising at least a polymer made from at least a hydrophilic monomer, preferably selected from the group consisting of alkyl acrylates and alkyl methacrylates, in which the alkyl moiety has 1 or 2 carbon atoms, and
  • At least a cross-linked polymer made from a hydrophilic monomer preferably selected from the group consisting of alkyl acrylates and alkyl methacrylate, in which the alkyl moiety has 1 or 2 carbon atoms, or (ii) at least a polymer made from at least a hydrophobic monomer, preferably selected from the group consisting of alkyl acrylates and alkyl methacrylates, in which the alkyl moiety is linear or branched and contains at least 4 carbon atoms;
  • the bonding primer layer with at least one coating of at least one metal and/or at least one metal oxide and/or silicon oxide.
  • the applications of the multilayer film according to the present invention are in particular food packaging, medical packaging and the so-called industrial applications (e.g. electrical insulation, electronic components and protective films, optical films, films filtering a part of the light spectrum, films for agriculture or building), printable films or else the decoration or protection of supports.
  • industrial applications e.g. electrical insulation, electronic components and protective films, optical films, films filtering a part of the light spectrum, films for agriculture or building
  • printable films e.g. electrical insulation, electronic components and protective films, optical films, films filtering a part of the light spectrum, films for agriculture or building
  • decoration or protection of supports e.g. electrical insulation, electronic components and protective films, optical films, films filtering a part of the light spectrum, films for agriculture or building
  • packaging it may be packaging of food products from their manufacture/production site to their arrival with the final consumer. These films have been developed quite especially for providing a barrier either to gases (oxygen, nitrogen, helium, water vapour, etc.) or to aromas. This may also be a packaging film for cooking foodstuffs in a microwave oven.
  • these films are used for creating surfaces of the simulated wood type, for example.
  • films or sheets for graphic art they may be printable supports, covered with inks or not.
  • the applications of the multilayer film obtained by the above described method are in particular food packaging. Examples
  • TEM and cryo- ⁇ images were recorded at an accelerating voltage of 80 and 120 kV respectively, with a Philips CM 120 transmission electron microscope at the Centre Technonova des Microstructures ( ⁇ ), platform at the Universite Claude Bernard Lyon 1 , Villeurbanne, France
  • the first step is the synthesis of a poly(styrene-co-butyl acrylate) P(S-co-BA) core (CI), the composition of which was set to obtain a copolymer with a T g of approximately 80°C, via batch emulsion polymerization in a 1 L double jacketed reactor.
  • the emulsifier and the buffer were separately solubilized in 150 and 100 mL (respectively) of distilled deionized (DDI) water and added to the reactor with the monomers (styrene (Sty) and butyl acrylate (BA)) and water.
  • the system was heated by means of a thermostatic bath under nitrogen flow.
  • the initiator was solubilized in 50 mL of DDI water and kept under nitrogen flow during 30 min. When the temperature of the reactor reached 72°C the initiator solubilized in the water was added into the reactor. The temperature of the reactor was set to 75°C and stirring speed was kept constant at 250 rpm. The reactor vessel was kept under nitrogen flow until the polymerization was complete.
  • the second step is the synthesis of the shell of acrylates around the core.
  • Monomers, buffer and emulsifier were then added to the reactor containing the poly(styrene-co- butyl acrylate) copolymer core (CI) using two tanks.
  • the reaction media, feeding tanks one and two were purged for 30min with nitrogen prior the start of the reaction and they were kept under N 2 flow until the end of the process.
  • SDS sodium dodecyl sulfate
  • APS ammonium persulfate
  • the initiator When the temperature inside of the reactor reached 72°C the initiator was added by using a syringe. The monomer started to be fed into the reactor right after the initiator shot and the buffer/surfactant/initiator solution started to be fed 10 minutes after. The reaction was considered started when the first drop of monomer touched the reaction medium. Samples were periodically withdrawn and polymerization was quenched by immersing sample flasks into an ice bath.
  • Hydrodynamic diameters were determined using a Malvern Zeta-Sizer Nano-ZS instrument. Samples were diluted in DDI water prior the analysis. For each sample, 3 measurements of 12 runs each were performed at 25°C to obtain the average 3 ⁇ 4 and polydispersity index (PDI). The angle from the scattering of the light when it finds an object of determined size is measured and 3 ⁇ 4 is then calculated using the Rayleigh equation (Berne, B. J.; Pecora, R., Dynamic light scattering: with applications to chemistry, biology, and physics. Courier Corporation, 1976). The PDI is a value provided by the instrument and is used to describe the width of the particle size distribution around a central value (Xu, R., Electrophoretic light scattering.
  • 3 ⁇ 4 is heavily weighted towards big particles and it reflects the effects of swelling and shrinking from polar groups present in the particles.
  • Poly is the measurement of the dispersion from the 3 ⁇ 4 data obtained from this analysis.
  • D w and D n were determined by measuring the diameter of 400 particles and finding the average values in terms of volume and number respectively.
  • I p is the polydispersity index given by D D n .
  • Example 2 Multilayer film synthesis using the core-shell particles
  • a bonding primer dispersion comprising core-shell polymeric particles or simple acrylic polymers according to example 1 is implemented.
  • This dispersion is coated on the support by an in-line heliographic coating process (pilot machine Toray Film Europe).
  • the rotating helio roller leads to dispersion coating on the PET film.
  • the coating is dried using infrared radiation at a wavelength of the order of 2 ⁇ .
  • the PET film coated with a bonding primer layer is coated with a layer of aluminium obtained by evaporation under vacuum (4x10 "4 mbar) in a conventional industrial metallizing process (TopMet machine from Applied Materials).
  • the thickness of the layer of metal is monitored by a measurement of film transparency expressed in terms of optical density OD.
  • the OD selected for the present example is between 2.4 and 3.0, which corresponds to a thickness of the metal layer from 30 to 60 nm.
  • the measurements of permeability to water vapour are carried out according to standard ASTM F-1249 "Standard Test Method for Water Vapour Transmission Rate through Plastic Film and Sheeting using a Modulated Infrared Sensor"; the results are expressed in g/m 2 /day.
  • the measurements of permeability to water vapour of the films are carried out on the Permatran-W®3/31 with the Mocon - Water Vapor Permeation Analysis System software.
  • the adhesion test AT is measured according to the AIMCAL TP- 105-92 recommendations (Metallizing Technical Reference published by the Association of Industrial Metallizers, Coaters and Laminators). It is described for metal but it is suitable for the other types of covering intended to be applied on the coated support according to the invention.
  • the AT test allows the adhesive strength between metal and PET to be measured, using a dynamometer. This test is carried out under dry and wet conditions. The metallized PET film is sealed with a treated polyethylene film. A test specimen with a width of 38 mm is then cut out of the sample and will be used for the measurement. The test specimen is tested under tension using an INSTRON dynamometer in order to determine the force to be applied to detach the layer of aluminium from the coated film. The PET film is fixed in the lower jaws and the treated polyethylene film film is fixed in the upper jaws.

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Abstract

L'invention concerne un procédé de production d'un film multicouche. En particulier, l'invention concerne un procédé de production d'un film multicouche comprenant au moins un support polymère, au moins une couche d'amorce de liaison et au moins un revêtement, ledit procédé comprenant les étapes suivantes : a) création d'un support polymère ; b) optionnellement, réalisation d'un prétraitement de surface sur au moins une face dudit support ; c) revêtement d'au moins une face dudit support avec une dispersion d'amorce comprenant des particules polymères cœur-écorce ; d) séchage de la dispersion afin de produire une couche d'amorce de liaison ; e) revêtement de la couche d'amorce de liaison avec au moins un revêtement d'au moins un métal et/ou d'au moins un oxyde de métal et/ou d'oxyde de silicium, ou d'au moins une couche d'encre, ou d'au moins une couche d'adhésif. L'invention concerne également l'utilisation d'une dispersion d'amorce comprenant des particules polymères cœur-écorce pour obtenir une couche d'amorce de liaison qui permet de contrôler les propriétés de barrière et/ou les propriétés d'adhérence d'un film multicouche comprenant un support polymère, une couche d'amorce de liaison et un revêtement.
EP17761314.8A 2017-06-23 2017-06-23 Procédé de production d'un film multicouche à l'aide de particules polymères coeur-écorce Pending EP3642270A1 (fr)

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FR2602777B1 (fr) 1986-08-12 1988-11-10 Rhone Poulenc Films Procede de revetement de films en polyester et nouveaux films comportant un revetement de surface
US5863595A (en) * 1996-10-04 1999-01-26 Dow Corning Corporation Thick ceramic coatings for electronic devices
FR2790263A1 (fr) * 1999-02-26 2000-09-01 Atochem Elf Sa Materiaux composites contenant une couche d'un film antichoc
US6926957B2 (en) * 2001-06-29 2005-08-09 3M Innovative Properties Company Water-based ink-receptive coating
EP2602357A1 (fr) * 2011-12-05 2013-06-12 Atotech Deutschland GmbH Nouveaux agents de promotion d'adhésion pour la métallisation des surfaces de substrats
FR3000415B1 (fr) 2012-12-27 2015-10-16 Toray Films Europ Procede d'enduction d'un support avec une dispersion a base de polymere acrylique et de reticulant, procede de revetement d'un tel support enduit et utilisations dudit support enduit et revetu

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