EP1957266A2 - (ligno)cellulose material board coated with a pmma and pvdf-based film - Google Patents

(ligno)cellulose material board coated with a pmma and pvdf-based film

Info

Publication number
EP1957266A2
EP1957266A2 EP06842102A EP06842102A EP1957266A2 EP 1957266 A2 EP1957266 A2 EP 1957266A2 EP 06842102 A EP06842102 A EP 06842102A EP 06842102 A EP06842102 A EP 06842102A EP 1957266 A2 EP1957266 A2 EP 1957266A2
Authority
EP
European Patent Office
Prior art keywords
parts
pmma
layer
pvdf
ligno
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Withdrawn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
EP06842102A
Other languages
German (de)
French (fr)
Inventor
Anthony Bonnet
Johann Laffargue
Nadine Rivas
Karine Triballier
Sandrine Duc
Cyrille Mathieu
Frédéric Godefroy
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.)
Arkema France SA
Original Assignee
Arkema France SA
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 Arkema France SA filed Critical Arkema France SA
Publication of EP1957266A2 publication Critical patent/EP1957266A2/en
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B21/00—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board
    • B32B21/04—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B21/08—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/10—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2274/00—Thermoplastic elastomer material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/71—Resistive to light or to UV
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/712—Weather resistant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2419/00—Buildings or parts thereof
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers

Definitions

  • the invention relates to the use of a multilayer film based on PMMA and PVDF to protect a (ligno) cellulosic material or a panel made of (ligno) cellulosic material.
  • the invention also relates to this panel.
  • This type of panel is widely used in everyday life, especially in the exterior cladding of facades. It is generally a sandwich panel.
  • the panels in cellulose (ligno) material, sandwich panel type, are panels used in the coating of exterior or interior facades or else in the production of floors. To ensure color and appearance stability, it is necessary to protect these panels against UV rays, chemicals, scratches, atmospheric agents (humidity, salt spray, ...), fungi and mold or graffiti. It is known to use a plastic film covering and protecting one of the faces of the panel.
  • EP 1405872 A1 describes a multilayer film based on PVDF and PMMA for covering objects made of thermoset material.
  • the adhesive layer of the film in contact with the object to be covered comprises a functional PMMA.
  • EP 1382640 A1 and EP 1566408 A1 describe a multilayer film for which the adhesive composition in contact with the object to be covered comprises a mixture of PVDF and PMMA.
  • PMMA can be functional.
  • European application EP 1199157 A1 describes a laminated panel coated with a multilayer transparent / translucent acrylic film on at least one of its faces. There is no mention of the film of the invention nor even less of functional PMMA.
  • European application EP 1388414 A1 describes a laminated panel coated with a PMMA / PVDF bilayer film or monolayer based on a PMMA / PVDF mixture. There is no mention of the film of the invention nor even less of functional PMMA.
  • the multilayer film comprises in order a layer of PMMA, a decorative layer and a layer of PVDF. There is no mention of a functional PMMA layer.
  • the invention relates to the use of a coextruded multilayer film to protect a cellulosic (ligno) material, the multilayer film comprising in order arranged one against the other:
  • a surface layer (I) comprising as main constituents a PVDF and possibly a PMMA;
  • An intermediate layer (II) comprising as main constituents from 0 to 60 parts of a PVDF, from 40 to 100 parts of a PMMA, from 0 to 25 parts of an acrylic elastomer and from 0 to 10 parts of a UV absorber, the total making 100 parts;
  • An adhesive layer (III) comprising as main constituent a functional PMMA
  • the adhesive layer (III) being disposed on the side of the cellulosic (ligno) material.
  • the invention also relates to the use of the multilayer film to protect a panel comprising at least one layer of a (ligno) cellulosic material, the film being applied to at least one of the two external faces of the panel consisting of 'A (ligno) cellulosic material, the adhesive layer (III) being arranged on the side of at least one of said external faces of the panel.
  • a panel comprising at least one layer of a (ligno) cellulosic material
  • the film being applied to at least one of the two external faces of the panel consisting of 'A (ligno) cellulosic material, the adhesive layer (III) being arranged on the side of at least one of said external faces of the panel.
  • the invention also relates to a multilayer structure comprising at least one layer of a cellulosic (ligno) material and the multilayer film disposed against this layer, the adhesive layer (III) being disposed on the side of the cellulosic (ligno) material.
  • the invention also relates to a panel comprising at least one layer of a cellulosic (ligno) material of which at least one of the two external faces of the panel made of a cellulosic (ligno) material is protected by the multilayer film, the adhesive layer (III) being disposed on the side of at least one of said faces of the panel.
  • (Meth) acrylate denotes both an acrylate and a methacrylate.
  • (Meth) acrylic acid means both acrylic acid and methacrylic acid.
  • (Ligno) cellulosique designates both cellulosic and lignocellulosic.
  • the PVDF comprises by weight at least 75%, preferably at least 85% of VDF.
  • the comonomer is fluorinated, it can be chosen for example from vinyl fluoride; trifluoroethylene (VF3); chlorotrifluoroethylene (CTFE); 1,2-difluoroethylene; tetrafluoroethylene (TFE); 1 hexafluoropropylene (HFP); perfluoro (alkyl vinyl) ethers such as perfluoro (methyl vinyl) ether (PMVE), perfluoro (ethyl vinyl) ether (PEVE) and perfluoro (propyl vinyl) ether (PPVE); perfluoro (1, 3 -dioxole); perfluoro (2,2-dimethyl-1,3-dioxole) (PDD).
  • VF3 trifluoroethylene
  • CTFE chlorotrifluoroethylene
  • TFE tetrafluoroethylene
  • HFP 1 hexafluoropropylene
  • perfluoro (alkyl vinyl) ethers such as perfluoro (
  • the optional comonomer is chosen from chlorotrifluoroethylene (CTFE), hexafluoropropylene (HFP), trifluoroethylene (VF3) and tetrafluoroethylene (TFE). Most preferably, it is HFP.
  • the PVDF has a viscosity ranging from 100 Pa. S to 2000 Pa. S, the viscosity being measured at 230 ° C., at a shear gradient of 100 s "1 using a capillary rheometer.
  • these PVDFs are well suited for extrusion and injection.
  • the PVDF has a viscosity ranging from 300 Pa. s to 1200 Pa. s, the viscosity being measured at 230 ° C., at a shear gradient 100 s "1 using a capillary rheometer.
  • PMMA denotes a homopolymer of methyl methacrylate (MMA) or a copolymer comprising by weight at least 50% by weight of MMA and at least one comonomer copolymerizable with MMA.
  • the PMMA comprises by weight at least 70% of MMA.
  • alkyl (meth) acrylates By way of example of a comonomer, mention may, for example, be made of alkyl (meth) acrylates, more particularly those in which the alkyl group contains from 2 to 4 carbon atoms, acrylonitrile, vinyl aromatic monomers such as styrene .
  • alkyl (meth) acrylates are described in Kirk-Othmer, Encyclopedia of Chemical Technology, 4th edition in Vol. 1, pages 292-293 and in Vol. 16 pages 475-478.
  • the PMMA can contain 0 to 30% by weight and preferably 5 to 30% of a C2-C4 alkyl (meth) acrylate, preferably methyl acrylate and / or ethyl acrylate .
  • the term functional PMMA denotes a PMMA which comprises acid, acid salt, acid chloride, epoxide, alcohol or anhydride. These functions can be introduced by grafting or by copolymerization of at least one monomer carrying at least one acid, acid salt, acid chloride, epoxide, alcohol or anhydride function.
  • the functional PMMA can comprise by weight from 0.5 to 15%, advantageously from 1 to 10%, preferably from 2 to 10% of at least one monomer carrying at least one acid function, acid salt, chloride acid, epoxide, alcohol or anhydride.
  • the copolymerization can be carried out according to a bulk process, in solution in a solvent, in emulsion or else in suspension.
  • the grafting is carried out in solution in a solvent or else in the molten state in a suitable mixing tool, such as for example an extruder.
  • a monomer carrying an epoxy function By way of example of a monomer carrying an epoxy function, mention may be made of allyl glycidyl ether, vinyl glycidyl ether, glycidyl maleate and itaconate, acrylate and glycidyl methacrylate. Glycidyl methacrylate is a preferred monomer because it efficiently copolymerizes with MMA.
  • a monomer carrying an acid function By way of example of a monomer carrying an acid function, mention may be made of 2-acrylamido-2-methylpropane sulfonic acid, vinyl sulfonic acid, styrene sulfonic acid, 1-allyloxy-2- acid hydroxypropane sulfonic, alkyl allyl sulfosuccinic acid, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid. Preferably, it is acrylic acid or methacrylic acid because these two monomers copolymerize very well with MMA.
  • Methacrylic acid is very particularly preferred when the copolymerization is carried out in an aqueous dispersed medium, since acrylic acid tends to remain largely dissolved in water which is not the case with methacrylic acid.
  • a monomer carrying an anhydride function mention may be made of maleic anhydride, itaconic anhydride, citraconic anhydride.
  • the anhydride function can also be introduced by reaction of two neighboring acid functions.
  • a PMMA is reacted with a secondary amine.
  • the reaction is carried out at a temperature above 150 ° C., preferably between 200 and 280 ° C., optionally in the presence of a reduced pressure of less than 1 bar and optionally in the presence of an acid or basic catalyst.
  • This reaction can be carried out in an extruder provided with a degassing well or else in a devolatilizer.
  • a functional PMMA obtained by copolymerizing MMA, of (meth) acrylic acid and optionally a 3rd monomer copolymerizable with MMA.
  • the 3 rd comonomer is chosen from the list of PMMA comonomers defined above.
  • Two neighboring (meth) acrylic acid functions can dehydrate to form an anhydride function. Dehydration can for example take place in the devolatilization and / or extrusion stages which follow the copolymerization stage.
  • This functional PMMA includes by weight:
  • the MVI (melt volume index or melt flow rate by volume in the molten state) of the PMMA may be between 2 and 15 cm 3/10 min measured at 23O 0 C under a load of 3.8 kg.
  • ALTUGLAS ® HT121 grade marketed by ALTUGLAS INTERNATIONAL.
  • This product contains about 4.5% by weight of methacrylic acid or anhydride from methacrylic acid. It has a melt-index of 2 g / 10 min (230 ° C., 3.8 kg).
  • acrylic elastomer denotes an elastomer based on at least one monomer chosen from acrylonitrile, alkyl (meth) acrylates and multilayer particles of the core-shell (core-shell) type.
  • particles of the core-shell type are in the form of fine multilayer particles having at least one elastomeric layer (i.e.
  • Soft and at least one thermoplastic layer (that is to say “hard”), the particle size is generally less than ⁇ m and advantageously between 50 and 300 nm.
  • elastomeric layer mention may be made of isoprene or butadiene homopolymers, isoprene copolymers with at most 30 mol% of a vinyl monomer and butadiene copolymers with at most 30% in moles of a vinyl monomer.
  • the vinyl monomer can be styrene, an alkylstyrene, acrylonitrile or an alkyl (meth) acrylate.
  • Another family of elastomeric layer consists of homopolymers of an alkyl (meth) acrylate and copolymers of an alkyl (meth) acrylate with at most 30 mol% of a monomer chosen from another ( meth) alkyl acrylate and a vinyl monomer.
  • the alkyl (meth) acrylate is advantageously butyl acrylate.
  • the vinyl monomer can be styrene, an alkylstyrene, acrylonitrile, butadiene or isoprene.
  • the thermoplastic layer may be a homopolymer of styrene, an alkylstyrene or methyl methacrylate or a copolymer comprising at least 70 mol% of one of these preceding monomers and at least one comonomer chosen from the other preceding monomers, a other alkyl (meth) acrylate, vinyl acetate and acrylonitrile.
  • Each of the layers can be crosslinked in whole or in part. It suffices to add at least one at least difunctional monomer during the preparation of the layer, this monomer being able to be chosen from poly (meth) acrylic esters of polyols such as butylene di (meth) acrylate and trimethylol propane trimethacrylate. Other difunctional monomers are for example divinylbenzene, trivinylbenzene, vinyl acrylate and vinyl methacrylate. It is also possible to crosslink by introducing an unsaturated functional monomer such as an unsaturated carboxylic acid anhydride, an unsaturated carboxylic acid or an unsaturated epoxide. We can cite as an example maleic anhydride, (meth) acrylic acid and glycidyl methacrylate.
  • multilayer particles of core-shell type mention may be made of those called soft / hard having an inner layer (core) of elastomer and an outer layer (shell) of thermoplastic. There are also particles with two thermoplastic layers, one made of polystyrene and the other outside of PMMA.
  • the core represents, by weight, 70 to 90% of the particle and the shell 30 to 10%.
  • soft / hard particles By way of example of soft / hard particles, mention may be made of these: (i) from 75 to 80 parts of a core comprising in moles at least 93% of butadiene, 5% of styrene and 0.5 to 1% of divinylbenzene and (ii) 25 to 20 parts of two barks of essentially the same weight, one inside made of polystyrene and the other outside made of PMMA.
  • soft / hard particles mention may be made of those having a core of poly (butyl acrylate) or of a copolymer of butyl acrylate and butadiene and a shell of PMMA.
  • European application EP 1061100 A1 describes such particles.
  • hard / soft / hard having in order a thermoplastic core, an elastomeric intermediate layer and a hard shell.
  • Application US 2004/0030046 A1 describes examples of such particles. Mention may be made, for example, of those constituted in order: (i) of a hard core made of a copolymer of methyl methacrylate and of ethyl acrylate, (ii) of a intermediate layer of copolymer of butyl acrylate and styrene, (iii) of a hard shell made of a copolymer of methyl methacrylate and ethyl acrylate. Mention may also be made of those constituted in order: (i) of a hard core (23% by weight) obtained by polymerizing 92.7 parts of MMA,
  • hard / soft / semi hard There are still other types of core shell type particles called hard / soft / semi hard. Compared to the previous ones, the difference comes from the outer bark "semi hard" which consists of two barks: one intermediate and the other outside.
  • the intermediate shell is a copolymer of methyl methacrylate, styrene and at least one monomer chosen from alkyl acrylates, butadiene and isoprene.
  • the outer shell is a homopolymer or copolymer PMMA.
  • impact quality which contain acrylic impact modifiers, most often of the core-bark type.
  • shock modifiers acrylics can be present in PMMA because they were introduced during its polymerization or prepared simultaneously during its polymerization. Examples of particles and their preparation process are described in the following patents: US 4180494, US 3808180, US 4096202, US 4260693, US 3287443, US 3657391, US 4299928, US 3985704 and US 5773520.
  • Core-type particles Shell usable are for example 1 IRH 70 from the company MITSUBISHI (soft / hard bilayer with a soft core of butadiene-butyl acrylate copolymer and a hard shell of PMMA) or KM-355 from the company ROHM and HAAS.
  • MITSUBISHI soft / hard bilayer with a soft core of butadiene-butyl acrylate copolymer and a hard shell of PMMA
  • KM-355 from the company ROHM and HAAS.
  • this is a coextruded multilayer film comprising in order arranged one against the other:
  • a surface layer (I) comprising as main constituents a PVDF and possibly a PMMA;
  • an intermediate layer (II) comprising as main constituents from 0 to 60 parts of a PVDF
  • the main function of the surface layer (I) is to protect the substrate.
  • the main function of the intermediate layer (II) is to provide flexibility to the film (eg during its manufacture and handling) and also when the layer contains a UV absorber to enhance UV protection.
  • the main function of the adhesive layer (III) is to ensure adhesion to the substrate and to prevent delamination of the film.
  • the multilayer film can be prepared by coextrusion. The coextrusion technique is based on the use of as many extruders as there are layers to be extruded, the layers of molten material coming from each of the extruders then being combined to form the multilayer film (for more details , we can refer to the book Principles of Polymer Processing by Z. Tadmor, Wiley edition, 1979).
  • the mixtures of the ingredients forming each of the layers are obtained in each of the coextrusion extruders or else beforehand in separate extruders.
  • the blown-film technique can be used.
  • the thickness of the surface layer (I) is advantageously between 1 and 100 ⁇ m, preferably between 2 and 40 ⁇ m.
  • the thickness of the intermediate layer (II) is advantageously between 1 and 100 ⁇ m, preferably between 10 and 60 ⁇ m.
  • the thickness of the adhesive layer (III) is advantageously between 1 and 100 ⁇ m, preferably between 2 and 40 ⁇ m.
  • the film with the advantageous thicknesses described has sufficient mechanical properties to allow its handling, processing and use.
  • the surface layer (I) comprises as main constituents a PVDF and possibly a PMMA.
  • the surface layer (I) comprises as main constituents from 50 to 100 parts of PVDF for respectively from 50 to 0 parts of PMMA, the total making 100 parts.
  • the surface layer (I) comprises as main constituents from 70 to 100 parts of PVDF for respectively from 30 to 0 parts of PMMA and preferably of 75 to 85 parts of PVDF for respectively 25 to 15 parts of PMMA, the total making 100 parts.
  • the surface layer (I) is in the form of two superposed layers:
  • a layer (Ia) comprising as main constituents 75 to 100 parts of PVDF for respectively 25 to 0 parts of PMMA;
  • a layer (Ib) comprising as main constituents 50 to 90 parts of PVDF for respectively 50 to 10 parts of PMMA.
  • the layer (Ib) is the layer in contact with the intermediate layer (II) and the layer (Ia) is the “outer” layer, that is to say that the multilayer film comprises in order the layers (Ia) / (Ib) / (II) / (III).
  • this comprises as main constituents from 0 to 60 parts of PVDF, from 40 to 100 parts of PMMA, from 0 to 25 parts of acrylic elastomer and from 0 to 10 parts of UV absorber, the total making 100 parts.
  • it comprises from 20 to 60 parts of PVDF, from 40 to 60 parts of PMMA, from 0 to 25 parts of acrylic elastomer, from 0 to 10 parts of UV absorber, the total making 100 parts.
  • it comprises from 30 to 50 parts of PVDF, from 40 to 60 parts of PMMA, from 0 to 20 parts of an acrylic elastomer, from 0 to 5 parts of a UV absorber, the total making 100 parts.
  • the intermediate layer does not contain any acrylic elastomer. It comprises from 20 to 50 parts of PVDF, from 50 to 80 parts of a PMMA comprising by weight from 90 to 50% of MMA for respectively from 10 to 50% of a alkyl (meth) acrylate, the alkyl having from 2 to 4 carbon atoms, from 0 to 5 parts of a UV absorber, the total making 100 parts.
  • the PMMA comprises by weight from 85 to 70% of MMA for respectively from 15 to 30% of an alkyl (meth) acrylate, the alkyl having from 2 to 4 carbon atoms.
  • the PMMA comprises by weight from 80 to 70% of MMA for respectively from 20 to 30% of an alkyl (meth) acrylate, the alkyl having from 2 to 4 carbon atoms.
  • alkyl (meth) acrylate methyl, ethyl or butyl acrylate.
  • the adhesive layer (III) comprises as main constituent a functional PMMA.
  • it is the PMMA block obtained by the copolymerization of MMA, of (meth) acrylic acid and optionally a 3rd monomer copolymerizable with MMA.
  • the adhesive layer (III) comprises by weight more than 60%, advantageously more than 80%, preferably more than 90%, even more preferably more than 95% of functional PMMA.
  • the adhesive layer (III) does not comprise a fluoropolymer to promote adhesion.
  • Functional PMMA provides good adhesion on many substrates.
  • the adhesion is reinforced as soon as the functional PMMA has a content by weight of carrier monomer with a function greater than 0.5%, advantageously greater than 1%, preferably greater than 2%.
  • UV absorber As regards the UV absorber, this is known in itself. A list of UV absorbers can be found in the document US
  • Benzotriazoles and benzophenones are advantageously used.
  • the panel comprises at least one layer of a (ligno) cellulosic material, which may for example be:
  • paper preferably Kraft paper
  • the panel can have a rectangular shape.
  • the invention is not limited only to panels of rectangular shape but can be applied to other shapes, for example a wedge shape.
  • the panel finds applications for example in the coating of external or internal facades or the realization of floors.
  • a chipboard panel is made of wood particles
  • thermosetting resin in different forms: sawdust, shavings, fibers, ...) treated with at least one thermosetting resin and subjected to high pressure and temperature.
  • It may also be a panel comprising several identical or different layers of cellulosic material (s). We often speak in this case of sandwich panel.
  • the panel can also comprise at least one layer of an elastomeric material or of a foam whose function is to improve the sound insulation of the panel. It can also include at least one counterbalancing layer whose function is to mechanically stabilize the panel to avoid buckling or deformation of the panel.
  • an intermediate layer of an adhesive is provided between them, generally of thin thickness.
  • the glue is often a thermosetting glue, for example of the phenolic or melamine type. examples of panels
  • a decorative layer composed of a tinted cellulose film and a cellulose film impregnated with melamine and having a silica filler.
  • a sandwich panel comprises in order a layer of paper, a layer of wood and possibly a decorative layer or else a layer of paper and a decorative layer.
  • Another example of a sandwich panel optionally includes, in order, a decorative layer, a layer of wood, a layer of paper, a layer of wood and possibly a decorative layer.
  • Another example of a sandwich panel comprises, in order, a decorative layer, a layer of wood and a decorative layer.
  • the multilayer film is applied to the wood layer or to the decorative layer.
  • the paper layer can also be replaced by a stack of several layers of paper.
  • the paper used is kraft paper.
  • the decorative layer can be a single color or have a printed pattern. It can be one or more cellulose film (s) or printed paper. It can also be a layer of thermosetting adhesive loaded with pigments. Adhesion between the layers is ensured by a layer of glue.
  • the adhesive is a thermosetting adhesive of the phenolic or melamine type.
  • the BAQ + ® panel from PRODEMA is described on the website of this company as being a high density panel consisting of a core of cellulose fibers impregnated with thermosetting phenolic resins and a layer of natural wood.
  • the MAD ® panel from PRODEMA is described as being a panel composed of a plywood core impregnated with thermosetting phenolic resins and a layer of natural wood.
  • the PARKLEX ® 1000 panel from the company GUREA is described on the website of this company as being a high density wooden laminated panel formed inside by wood or paper fibers treated with thermoset phenolic resins and very strongly pressed at high temperatures and a layer of natural wood. The multilayer film is applied against the layer of wood.
  • the multilayer film of the invention is used to protect a (ligno) cellulosic material such as wood, cardboard or paper.
  • the adhesive layer (III) is arranged on the side of the cellulosic (ligno) material.
  • the adhesion of the film is reinforced if it comes into contact with a thermosetting adhesive placed on the surface or in the mass of the (ligno) cellulosic material.
  • a thermosetting adhesive is placed between the (ligno) cellulosic material and the film.
  • the glue is placed on the surface of the material in the form of a layer or else in the form of spots of glue in several places of the material.
  • the (ligno) cellulosic material is therefore covered in whole or part of its surface by thermosetting glue.
  • the adhesive may for example be a phenolic adhesive, for example phenol-formaldehyde, or melamine or urea-formaldehyde.
  • the glue can also be present in the mass of the (ligno) cellulosic material, as for example in the case of an agglomerated panel.
  • the invention also relates to a multilayer structure comprising at least one layer of a cellulosic (ligno) material and the film of the invention disposed against this layer, the adhesive layer (III) being disposed on the side of the material (ligno) cellulosic. More particularly, the film can be applied to a panel of which at least one of the two external faces consists of a (ligno) cellulosic material. The adhesive layer (III) is arranged on the side of at least one of the two external faces of (ligno) cellulosic material. The invention also relates to such a panel. advantages of the multilayer film
  • the cellulosic (ligno) material is protected by the multilayer film of the invention. This provides protection against UV rays, chemicals, scratches, atmospheric agents (humidity, salt spray, ...), fungi and molds or even graffiti.
  • the film ensures color and appearance stability over time.
  • the film can be applied by hot compression. The compression is carried out under a pressure generally between 2 and 30 MPa and hot at a temperature generally between 100 and 16O 0 C.
  • ALTUGLAS ® BS8 PMMA society INTERNATIONAL ALTUGLAS MVI of 4.5 cm 3/10 min (23O 0 C, 3.8 kg) in bead form containing as comonomer, methyl acrylate, up to 6% by weight. This PMMA does not contain a shock modifier.
  • ALTUGLAS ® PRD 510 A PMMA PRD 510 A is a copolymer of methyl methacrylate and ethyl acrylate (25% by weight). Its MFI is 5 g / 10 minutes at 230 ° C. under 3.8 kg.
  • ALTUGLAS ® V825T PMMA homopolymer from the company ALTUGLAS INTERNATIONAL of melt-flow 5.5 g / 10 min (230 ° C., 3.8 kg) in the form of granules. This PMMA is not a functional PMMA.
  • ALTUGLAS ® HT121 marketed by ALTUGLAS INTERNATIONAL. This product contains about 4.5% by weight of methacrylic acid or anhydride from methacrylic acid. It has a melt-index of 2 g / 10 min (230 ° C., 3.8 kg).
  • TINUVIN ® 234 UV absorber of hydroxyphenyl benzotriazole type from the company CIBA SPECIALTY CHEMICALS.
  • KYNAR ® 740 Homopolymer PVDF from the company ARKEMA from MFI 13 g / 10 minutes at 12.5 kg at 230 ° C.
  • Example 1 (according to the invention)
  • a three-layer film is prepared with the following layers from the inside to the outside of the bubble:
  • the film obtained is very transparent and has excellent resistance to external aging as well as excellent chemical resistance.
  • This film is placed at the bottom of a mold.
  • the three-layer film has excellent adhesion just after curing, it is not possible to peel this film from the surface of the crosslinked phenolic resin.
  • This plate is cut on its four edges in order to have perfectly straight plate sides and dimensions of 5 cm x 5 cm. This plate is then introduced into a boiling water bath for 2 hours. After this treatment, there is no bleaching or detachment.
  • Example 2 comparative
  • the film obtained is very transparent and has excellent resistance to external aging as well as excellent chemical resistance. This film is placed at the bottom of a mold.
  • On the film on the side of PMMA ALTUGLAS ® V825 T 2 layers of Kraft paper coated with phenolic resin of the TPS type color from COVERIGHT are deposited, these layers are laid on a 200 ⁇ m thick wooden strip previously coated.
  • the three-layer film has good adhesion just after curing, it is not possible to peel this film from the surface of the crosslinked phenolic resin.
  • This plate is cut on its four edges in order to have perfectly straight plate sides and dimensions of 5 cm x 5 cm. This plate is then introduced into a boiling water bath for 2 hours, after this treatment the appearance of the plate is inspected. There is a bleaching as well as a separation of the edges of the film.

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  • Wood Science & Technology (AREA)
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Abstract

The invention relates to the use of a coextruded multilayer film for protecting a (ligno)cellulose material, wherein said multilayer film consists of the following arranged to each other layers: a surface layer (I) comprising PVDF and possibly PMMA in the form of the main components, an intermediate layer (II) comprising in the form of main components 0-60 PVDF parts, 40-100 PMMA parts, 0-25 acrylic elastomer parts and 0-10 UV absorber parts, the totality thereof being equal to 100 parts, and an adhesive layer (III), which comprises a functional PMMA in the form of the main component and is arranged on the side of the (ligno)cellulose material.

Description

Panneau en matériau (ligno) cellulosique recouvert d'un film multicouche à base de PMMA et de PVDF  Panel made of (ligno) cellulosic material covered with a multilayer film based on PMMA and PVDF
L'invention est relative à l'utilisation d'un film multicouche à base de PMMA et de PVDF pour protéger un matériau (ligno) cellulosique ou un panneau en matériau (ligno) cellulosique . L'invention est aussi relative à ce panneau. Ce type de panneau est largement utilisé dans la vie courante, notamment dans le revêtement extérieur des façades. II s'agit généralement d'un panneau sandwich. The invention relates to the use of a multilayer film based on PMMA and PVDF to protect a (ligno) cellulosic material or a panel made of (ligno) cellulosic material. The invention also relates to this panel. This type of panel is widely used in everyday life, especially in the exterior cladding of facades. It is generally a sandwich panel.
[Le problème technique] [The technical problem]
Les panneaux en matériau (ligno) cellulosique type panneau sandwich, sont des panneaux utilisés dans le revêtement de façades extérieures ou intérieures ou bien dans la réalisation de planchers. Afin d'assurer une stabilité de couleur et d'aspect, il est nécessaire de protéger ces panneaux contre les rayons UV, les produits chimiques, les rayures, les agents atmosphériques (humidité, brouillard salin,...), les champignons et moisissures ou encore les graffitis. Il est connu d'utiliser un film plastique venant recouvrir et protéger l'une des faces du panneau.  The panels in cellulose (ligno) material, sandwich panel type, are panels used in the coating of exterior or interior facades or else in the production of floors. To ensure color and appearance stability, it is necessary to protect these panels against UV rays, chemicals, scratches, atmospheric agents (humidity, salt spray, ...), fungi and mold or graffiti. It is known to use a plastic film covering and protecting one of the faces of the panel.
Afin d'assurer une protection optimale, il est nécessaire que le film adhère parfaitement sur le panneau et que l'adhérence se maintienne dans le temps. De plus, dans le cas où le panneau est au contact d'une atmosphère humide (pluie, brouillard salin, ...) , il est nécessaire que le contact avec l'humidité n'entraîne pas de blanchiment du film. Il ne doit pas y avoir non plus de décollement dans les conditions du test qui consiste à plonger une plaque recouverte du film dans de l'eau bouillante pendant 2 heures. La demanderesse a mis au point un film multicouche qui adhère parfaitement sur le panneau sans blanchir au contact de l'humidité et qui assure une telle protection. [L'art antérieur] In order to ensure optimal protection, it is necessary that the film adheres perfectly to the panel and that the adhesion is maintained over time. In addition, in the case where the panel is in contact with a humid atmosphere (rain, salt spray, etc.), it is necessary that contact with humidity does not lead to bleaching of the film. There should also be no delamination under the conditions of the test which consists in immersing a plate covered with the film in boiling water for 2 hours. The Applicant has developed a multilayer film which adheres perfectly to the panel without bleaching on contact with moisture and which provides such protection. [The prior art]
La demande européenne EP 1405872 Al décrit un film multicouche à base de PVDF et de PMMA pour recouvrir des objets en matériau thermodur . La couche adhésive du film en contact avec l'objet à recouvrir comprend un PMMA fonctionnel.  European application EP 1405872 A1 describes a multilayer film based on PVDF and PMMA for covering objects made of thermoset material. The adhesive layer of the film in contact with the object to be covered comprises a functional PMMA.
Les demandes EP 1382640 Al et EP 1566408 Al décrivent un film multicouche pour lequel la composition adhésive en contact avec l'objet à recouvrir comprend un mélange de PVDF et de PMMA. Le PMMA peut être fonctionnel. Applications EP 1382640 A1 and EP 1566408 A1 describe a multilayer film for which the adhesive composition in contact with the object to be covered comprises a mixture of PVDF and PMMA. PMMA can be functional.
La demande européenne EP 1199157 Al décrit un panneau stratifié revêtu d'un film de nature acrylique transparent/translucide multicouche sur au moins l'une de ses faces. Il n'est pas fait mention du film de l'invention ni encore moins de PMMA fonctionnel. European application EP 1199157 A1 describes a laminated panel coated with a multilayer transparent / translucent acrylic film on at least one of its faces. There is no mention of the film of the invention nor even less of functional PMMA.
La demande européenne EP 1388414 Al décrit un panneau stratifié revêtu d'un film bicouche PMMA/PVDF ou monocouche à base d'un mélange PMMA/PVDF. Il n'est pas fait mention du film de l'invention ni encore moins de PMMA fonctionnel. European application EP 1388414 A1 describes a laminated panel coated with a PMMA / PVDF bilayer film or monolayer based on a PMMA / PVDF mixture. There is no mention of the film of the invention nor even less of functional PMMA.
Le brevet américain US 5232164 décrit un film multicouche comprenant une couche de surface et une couche venant en contact avec le substrat à base d'un PMMA qui peut être fontionnel. American patent US 5232164 describes a multilayer film comprising a surface layer and a layer coming into contact with the substrate based on a PMMA which can be functional.
La demande US 2003/0180564 Al décrit un film multicouche qui peut servir à protéger un plastique, un métal ou le bois. Le film multicouche comprend dans l'ordre une couche de PMMA, une couche décorative et une couche de PVDF. Il n'est pas fait mention d'une couche de PMMA fonctionnel. Application US 2003/0180564 A1 describes a multilayer film which can be used to protect plastic, metal or wood. The multilayer film comprises in order a layer of PMMA, a decorative layer and a layer of PVDF. There is no mention of a functional PMMA layer.
[Brève description de l'invention] [Brief description of the invention]
L'invention est relative à l'utilisation d'un film multicouche coextrudé pour protéger un matériau (ligno) cellulosique, le film multicouche comprenant dans l'ordre disposées l'une contre l'autre : The invention relates to the use of a coextruded multilayer film to protect a cellulosic (ligno) material, the multilayer film comprising in order arranged one against the other:
• une couche de surface (I) comprenant comme constituants principaux un PVDF et éventuellement un PMMA ;  • a surface layer (I) comprising as main constituents a PVDF and possibly a PMMA;
• une couche intermédiaire (II) comprenant comme constituants principaux de 0 à 60 parties d'un PVDF, de 40 à 100 parties d'un PMMA, de 0 à 25 parties d'un élastomère acrylique et de 0 à 10 parts d'un absorbeur UV, le total faisant 100 parties ;  An intermediate layer (II) comprising as main constituents from 0 to 60 parts of a PVDF, from 40 to 100 parts of a PMMA, from 0 to 25 parts of an acrylic elastomer and from 0 to 10 parts of a UV absorber, the total making 100 parts;
• une couche adhésive (III) comprenant comme constituant principal un PMMA fonctionnel,  An adhesive layer (III) comprising as main constituent a functional PMMA,
la couche adhésive (III) étant disposée du côté du matériau (ligno) cellulosique . the adhesive layer (III) being disposed on the side of the cellulosic (ligno) material.
L'invention est aussi relative à l'utilisation du film multicouche pour protéger un panneau comprenant au moins une couche d'un matériau ( ligno) cellulosique, le film s 'appliquant sur au moins l'une des deux faces externes du panneau constituée d'un matériau (ligno) cellulosique, la couche adhésive (III) étant disposée du côté d'au moins une desdites faces externes du panneau. The invention also relates to the use of the multilayer film to protect a panel comprising at least one layer of a (ligno) cellulosic material, the film being applied to at least one of the two external faces of the panel consisting of 'A (ligno) cellulosic material, the adhesive layer (III) being arranged on the side of at least one of said external faces of the panel.
L'invention est aussi relative à une structure multicouche comprenant au moins une couche d'un matériau (ligno) cellulosique et le film multicouche disposé contre cette couche, la couche adhésive (III) étant disposée du côté du matériau (ligno) cellulosique . L'invention est relative aussi à un panneau comprenant au moins une couche d'un matériau (ligno) cellulosique dont au moins l'une des deux faces externes du panneau constituée d'un matériau (ligno) cellulosique est protégée par le film multicouche, la couche adhésive (III) étant disposée du côté d'au moins une desdites faces externes du panneau. The invention also relates to a multilayer structure comprising at least one layer of a cellulosic (ligno) material and the multilayer film disposed against this layer, the adhesive layer (III) being disposed on the side of the cellulosic (ligno) material. The invention also relates to a panel comprising at least one layer of a cellulosic (ligno) material of which at least one of the two external faces of the panel made of a cellulosic (ligno) material is protected by the multilayer film, the adhesive layer (III) being disposed on the side of at least one of said faces of the panel.
La demande française antérieure FR 05.12336 dont la priorité est revendiquée est incorporée ici toute entière par référence . The prior French application FR 05.12336 whose priority is claimed is incorporated here entirely by reference.
[Description détaillée de l'invention] [Detailed description of the invention]
Définitions préliminaires  Preliminary definitions
(Méth) acrylate désigne à la fois un acrylate et un méthacrylate . Acide (méth) acrylique désigne à la fois l'acide acrylique et l'acide méthacrylique . (Ligno) cellulosique désigne à la fois cellulosique et lignocellulosique .  (Meth) acrylate denotes both an acrylate and a methacrylate. (Meth) acrylic acid means both acrylic acid and methacrylic acid. (Ligno) cellulosique designates both cellulosic and lignocellulosic.
On désigne par PVDF un homopolymère du VDF (fluorure de vinylidène, CH2=CF2) ou un copolymère du VDF comprenant de préférence au moins 50% en poids de VDF et d'au moins un autre monomère copolymérisable avec le VDF. De préférence, le PVDF comprend en poids au moins 75%, de préférence au moins 85% de VDF. Avantageusement, le comonomère est fluoré, il peut être choisi par exemple parmi le fluorure de vinyle; le trifluoroéthylène (VF3); le chlorotrifluoroéthylène (CTFE); le 1,2- difluoroéthylène; le tétrafluoroéthylène (TFE) ; 1 'hexafluoropropylène (HFP); les perfluoro (alkyl vinyl) éthers tels que le perfluoro (méthyl vinyl) éther (PMVE), le perfluoro (éthyl vinyl) éther (PEVE) et le perfluoro (propyl vinyl) éther (PPVE); le perfluoro ( 1, 3 -dioxole) ; le perfluoro (2, 2-diméthyl-l, 3-dioxole) (PDD) . De préférence le comonomère éventuel est choisi parmi le chlorotrifluoroéthylène (CTFE), 1 'hexafluoropropylène (HFP), le trifluoroéthylène (VF3) et le tétrafluoroéthylène (TFE) . De façon toute préférée, il s'agit de 1 'HFP . PVDF denotes a VDF homopolymer (vinylidene fluoride, CH2 = CF2) or a VDF copolymer preferably comprising at least 50% by weight of VDF and at least one other monomer copolymerizable with VDF. Preferably, the PVDF comprises by weight at least 75%, preferably at least 85% of VDF. Advantageously, the comonomer is fluorinated, it can be chosen for example from vinyl fluoride; trifluoroethylene (VF3); chlorotrifluoroethylene (CTFE); 1,2-difluoroethylene; tetrafluoroethylene (TFE); 1 hexafluoropropylene (HFP); perfluoro (alkyl vinyl) ethers such as perfluoro (methyl vinyl) ether (PMVE), perfluoro (ethyl vinyl) ether (PEVE) and perfluoro (propyl vinyl) ether (PPVE); perfluoro (1, 3 -dioxole); perfluoro (2,2-dimethyl-1,3-dioxole) (PDD). Preferably the optional comonomer is chosen from chlorotrifluoroethylene (CTFE), hexafluoropropylene (HFP), trifluoroethylene (VF3) and tetrafluoroethylene (TFE). Most preferably, it is HFP.
Avantageusement, le PVDF a une viscosité allant de 100 Pa. s à 2000 Pa. s, la viscosité étant mesurée à 23O0C, à un gradient de cisaillement de 100 s"1 à l'aide d'un rhéomètre capillaire. En effet, ces PVDF sont bien adaptés à l'extrusion et a l'injection. De préférence, le PVDF a une viscosité allant de 300 Pa. s à 1200 Pa. s, la viscosité étant mesurée à 23O0C, à un gradient de cisaillement de 100 s"1 à l'aide d'un rhéomètre capillaire . On désigne par PMMA un homopolymère du méthacrylate de méthyle (MMA) ou un copolymère comprenant en poids au moins 50% en poids de MMA et au moins un comonomère copolymérisable avec le MMA. De préférence, le PMMA comprend en poids au moins 70% de MMA. Advantageously, the PVDF has a viscosity ranging from 100 Pa. S to 2000 Pa. S, the viscosity being measured at 230 ° C., at a shear gradient of 100 s "1 using a capillary rheometer. , these PVDFs are well suited for extrusion and injection. Preferably, the PVDF has a viscosity ranging from 300 Pa. s to 1200 Pa. s, the viscosity being measured at 230 ° C., at a shear gradient 100 s "1 using a capillary rheometer. PMMA denotes a homopolymer of methyl methacrylate (MMA) or a copolymer comprising by weight at least 50% by weight of MMA and at least one comonomer copolymerizable with MMA. Preferably, the PMMA comprises by weight at least 70% of MMA.
A titre d'exemple de comonomère, on peut citer par exemple les (méth) acrylates d'alkyle, plus particulièrement ceux dont le groupe alkyle contient de 2 à 4 atomes de carbone, 1 ' acrylonitrile, le monomères vinyl aromatiques tels que le styrène. Des exemples de (méth) acrylates d'alkyle sont décrits dans KIRK-OTHMER, Encyclopedia of chemical technology, 4eme édition dans le Vol. 1, pages 292-293 et dans le Vol. 16 pages 475-478. Avantageusement, le PMMA peut contenir 0 à 30% en poids et de préférence 5 à 30% d'un (méth) acrylate d'alkyle en C2-C4, de préférence l 'acrylate de méthyle et/ou l 'acrylate d'éthyle . By way of example of a comonomer, mention may, for example, be made of alkyl (meth) acrylates, more particularly those in which the alkyl group contains from 2 to 4 carbon atoms, acrylonitrile, vinyl aromatic monomers such as styrene . Examples of (meth) alkyl acrylates are described in Kirk-Othmer, Encyclopedia of Chemical Technology, 4th edition in Vol. 1, pages 292-293 and in Vol. 16 pages 475-478. Advantageously, the PMMA can contain 0 to 30% by weight and preferably 5 to 30% of a C2-C4 alkyl (meth) acrylate, preferably methyl acrylate and / or ethyl acrylate .
On désigne par PMMA fonctionnel, un PMMA qui comprend des fonctions acide, sel d'acide, chlorure d'acide, époxyde, alcool ou anhydride. Ces fonctions peuvent être introduites par greffage ou par copolymérisation d'au moins un monomère porteur d'au moins une fonction acide, sel d'acide, chlorure d'acide, époxyde, alcool ou anhydride. The term functional PMMA denotes a PMMA which comprises acid, acid salt, acid chloride, epoxide, alcohol or anhydride. These functions can be introduced by grafting or by copolymerization of at least one monomer carrying at least one acid, acid salt, acid chloride, epoxide, alcohol or anhydride function.
Le PMMA fonctionnel peut comprendre en poids de 0,5 à 15%, avantageusement de 1 à 10%, de préférence de 2 à 10% d'au moins un monomère porteur d'au moins une fonction acide, sel d'acide, chlorure d'acide, époxyde, alcool ou anhydride. La copolymérisation peut être conduite selon un procédé masse, en solution dans un solvant, en émulsion ou bien en suspension. Le greffage est conduit en solution dans un solvant ou bien à l'état fondu dans un outil de mélange adapté, comme par exemple une extrudeuse. The functional PMMA can comprise by weight from 0.5 to 15%, advantageously from 1 to 10%, preferably from 2 to 10% of at least one monomer carrying at least one acid function, acid salt, chloride acid, epoxide, alcohol or anhydride. The copolymerization can be carried out according to a bulk process, in solution in a solvent, in emulsion or else in suspension. The grafting is carried out in solution in a solvent or else in the molten state in a suitable mixing tool, such as for example an extruder.
A titre d'exemple de monomère porteur d'une fonction époxyde, on peut citer 1 'allylglycidyléther, le vinylglycidyléther, le maléate et l'itaconate de glycidyle, l'acrylate et le méthacrylate de glycidyle. Le méthacrylate de glycidyle est un monomère préféré car il copolymérise efficacement avec le MMA. By way of example of a monomer carrying an epoxy function, mention may be made of allyl glycidyl ether, vinyl glycidyl ether, glycidyl maleate and itaconate, acrylate and glycidyl methacrylate. Glycidyl methacrylate is a preferred monomer because it efficiently copolymerizes with MMA.
A titre d'exemple de monomère porteur d'une fonction acide, on peut citer l'acide 2-acrylamido-2-méthylpropane sulfonique, l'acide vinyl sulfonique, l'acide styrène sulfonique, l'acide l-allyloxy-2-hydroxypropane sulfonique, l'acide alkyl allyl suifosuccinique, l'acide acrylique, l'acide méthacrylique, l'acide crotonique, l'acide itaconique, l'acide fumarique, l'acide maléique. De préférence, il s'agit de l'acide acrylique ou de l'acide méthacrylique car ces deux monomères copolymérisent très bien avec le MMA. L'acide méthacrylique est tout particulièrement préféré lorsque la copolymérisation est conduite en milieu dispersé aqueux, car l'acide acrylique a tendance à rester en grande partie solubilisé dans l'eau ce qui n'est pas le cas avec l'acide méthacrylique. A titre d'exemple de monomère porteur d'une fonction anhydride, on peut citer l'anhydride maléique, l'anhydride itaconique, l'anhydride citraconique . La fonction anhydride peut être aussi introduite par réaction de deux fonctions acide voisines. By way of example of a monomer carrying an acid function, mention may be made of 2-acrylamido-2-methylpropane sulfonic acid, vinyl sulfonic acid, styrene sulfonic acid, 1-allyloxy-2- acid hydroxypropane sulfonic, alkyl allyl sulfosuccinic acid, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid. Preferably, it is acrylic acid or methacrylic acid because these two monomers copolymerize very well with MMA. Methacrylic acid is very particularly preferred when the copolymerization is carried out in an aqueous dispersed medium, since acrylic acid tends to remain largely dissolved in water which is not the case with methacrylic acid. By way of example of a monomer carrying an anhydride function, mention may be made of maleic anhydride, itaconic anhydride, citraconic anhydride. The anhydride function can also be introduced by reaction of two neighboring acid functions.
Pour l'obtention d'un PMMA fonctionnel porteur de groupements anhydride glutarique, on peut utiliser l'une des méthodes décrites dans les documents EP 0318197 Bl, Japanese Kokai 60/231756, Japanese Kokai 61/254608 ou Japanese Kokai 61/43604, GB 1437176, US 4789709. Selon la méthode décrite dans EP 0318197, on fait réagir un PMMA avec une aminé secondaire. La réaction est conduite à une température supérieure à 15O0C, de préférence entre 200 et 28O0C, éventuellement en présence d'une pression réduite inférieure à 1 bar et éventuellement en présence d'un catalyseur acide ou basique. Cette réaction peut être réalisée dans une extrudeuse munie d'un puits de dégazage ou bien dans un dévolatiliseur . One of the methods described in documents EP 0318197 Bl, Japanese Kokai 60/231756, Japanese Kokai 61/254608 or Japanese Kokai 61/43604, GB can be used to obtain a functional PMMA carrying glutaric anhydride groups. 1437176, US 4789709. According to the method described in EP 0318197, a PMMA is reacted with a secondary amine. The reaction is carried out at a temperature above 150 ° C., preferably between 200 and 280 ° C., optionally in the presence of a reduced pressure of less than 1 bar and optionally in the presence of an acid or basic catalyst. This reaction can be carried out in an extruder provided with a degassing well or else in a devolatilizer.
On utilise de préférence un PMMA fonctionnel obtenu par la copolymérisation du MMA, de l'acide (méth) acrylique et éventuellement d'un 3eme monomère copolymérisable avec le MMA. Le 3eme comonomère est choisi dans la liste des comonomères du PMMA définis plus haut. Deux fonctions acide (méth) acrylique voisines peuvent se déshydrater pour former une fonction anhydride. La déshydratation peut par exemple s'opérer dans les étapes de dévolatilisation et/ou d'extrusion qui suivent l'étape de copolymérisation. Ce PMMA fonctionnel comprend en poids : Is preferably used a functional PMMA obtained by copolymerizing MMA, of (meth) acrylic acid and optionally a 3rd monomer copolymerizable with MMA. The 3 rd comonomer is chosen from the list of PMMA comonomers defined above. Two neighboring (meth) acrylic acid functions can dehydrate to form an anhydride function. Dehydration can for example take place in the devolatilization and / or extrusion stages which follow the copolymerization stage. This functional PMMA includes by weight:
• de 65 à 99,5% de MMA,  • from 65 to 99.5% of MMA,
• de 0 , 5 à 15% d'acide (méth) acrylique et/ou de l'anhydride issu de l'acide (méth) acrylique,  From 0.5 to 15% of (meth) acrylic acid and / or of the anhydride derived from (meth) acrylic acid,
• de 0 à 20% du 3eme monomère copolymérisable avec le MMA. Avantageusement, il comprend en poids : • 0 to 20% of the 3 rd monomer copolymerizable with MMA. Advantageously, it comprises by weight:
• de 70 à 99% de MMA,  • from 70 to 99% of MMA,
• de 1 à 10% d'acide (méth) acrylique et/ou de l'anhydride issu de l'acide (méth) acrylique,  From 1 to 10% of (meth) acrylic acid and / or of the anhydride derived from (meth) acrylic acid,
• de 0 à 20% du 3eme monomère copolymérisable avec le MMA. • 0 to 20% of the 3 rd monomer copolymerizable with MMA.
De préférence, il comprend en poids : Preferably, it comprises by weight:
• de 70 à 98% de MMA,  • from 70 to 98% of MMA,
• de 2 à 10% d'acide (méth) acrylique et/ou de l'anhydride issu de l'acide (méth) acrylique,  From 2 to 10% of (meth) acrylic acid and / or of the anhydride derived from (meth) acrylic acid,
• de 0 à 20% du 3eme monomère copolymérisable avec le MMA. • 0 to 20% of the 3 rd monomer copolymerizable with MMA.
Le MVI (melt volume index ou indice de fluidité en volume à l'état fondu) du PMMA peut être compris entre 2 et 15 cm3/10 min mesuré à 23O0C sous une charge de 3,8 kg. The MVI (melt volume index or melt flow rate by volume in the molten state) of the PMMA may be between 2 and 15 cm 3/10 min measured at 23O 0 C under a load of 3.8 kg.
Un exemple de PMMA fonctionnel est le grade ALTUGLAS® HT121 commercialisé par ALTUGLAS INTERNATIONAL. Ce produit renferme environ 4,5% en poids d'acide méthacrylique ou d'anhydride issu de l'acide méthacrylique. Il présente un melt-index de 2 g/10 min (23O0C, 3,8 kg). An example of a functional PMMA is the ALTUGLAS ® HT121 grade marketed by ALTUGLAS INTERNATIONAL. This product contains about 4.5% by weight of methacrylic acid or anhydride from methacrylic acid. It has a melt-index of 2 g / 10 min (230 ° C., 3.8 kg).
On désigne par élastomère acrylique, un élastomère à base d'au moins un monomère choisi parmi 1 ' acrylonitrile, les (méth) acrylates d'alkyle et les particules multicouches de type core-shell (noyau-écorce) . The term “acrylic elastomer” denotes an elastomer based on at least one monomer chosen from acrylonitrile, alkyl (meth) acrylates and multilayer particles of the core-shell (core-shell) type.
S 'agissant des particules de type core-shell, celles-ci se présentent sous la forme de fines particules multicouches ayant au moins une couche élastomérique (c'est-à-direWith regard to particles of the core-shell type, these are in the form of fine multilayer particles having at least one elastomeric layer (i.e.
« molle ») et au moins une couche thermoplastique (c'est-à- dire « dure ») , la taille des particules est en général inférieure au μm et avantageusement comprise entre 50 et 300 nm. A titre d'exemple de couche élastomérique, on peut citer les homopolymères de l'isoprène ou du butadiène, les copolymères de l'isoprène avec au plus 30% en moles d'un monomère vinylique et les copolymères du butadiène avec au plus 30% en moles d'un monomère vinylique. Le monomère vinylique peut être le styrène, un alkylstyrène, 1 ' acrylonitrile ou un (méth) acrylate d'alkyle. Une autre famille de couche élastomérique est constituée par les homopolymères d'un (méth) acrylate d'alkyle et les copolymères d'un (méth) acrylate d'alkyle avec au plus 30% en moles d'un monomère choisi parmi un autre (méth) acrylate d'alkyle et un monomère vinylique. Le (méth) acrylate d'alkyle est avantageusement l' acrylate de butyle. Le monomère vinylique peut être le styrène, un alkylstyrène, 1 ' acrylonitrile, le butadiène ou l'isoprène. "Soft") and at least one thermoplastic layer (that is to say "hard"), the particle size is generally less than μm and advantageously between 50 and 300 nm. By way of example of an elastomeric layer, mention may be made of isoprene or butadiene homopolymers, isoprene copolymers with at most 30 mol% of a vinyl monomer and butadiene copolymers with at most 30% in moles of a vinyl monomer. The vinyl monomer can be styrene, an alkylstyrene, acrylonitrile or an alkyl (meth) acrylate. Another family of elastomeric layer consists of homopolymers of an alkyl (meth) acrylate and copolymers of an alkyl (meth) acrylate with at most 30 mol% of a monomer chosen from another ( meth) alkyl acrylate and a vinyl monomer. The alkyl (meth) acrylate is advantageously butyl acrylate. The vinyl monomer can be styrene, an alkylstyrene, acrylonitrile, butadiene or isoprene.
La couche thermoplastique peut être un homopolymère du styrène, d'un alkylstyrène ou du méthacrylate de méthyle ou un copolymère comprenant au moins 70% en moles de l'un de ces monomères précédents et au moins un comonomère choisi parmi les autres monomères précédents, un autre (méth) acrylate d'alkyle, l'acétate de vinyle et 1 ' acrylonitrile . The thermoplastic layer may be a homopolymer of styrene, an alkylstyrene or methyl methacrylate or a copolymer comprising at least 70 mol% of one of these preceding monomers and at least one comonomer chosen from the other preceding monomers, a other alkyl (meth) acrylate, vinyl acetate and acrylonitrile.
Chacune des couches peut être réticulée en tout ou partie. Il suffit d'ajouter au moins un monomère au moins difonctionnel au cours de la préparation de la couche, ce monomère pouvant être choisi parmi les esters poly (méth) acryliques de polyols tels que le di (méth) acrylate de butylène et le triméthylol propane triméthacrylate . D'autres monomères difonctionnels sont par exemple le divinylbenzène, le trivinylbenzène, l' acrylate de vinyle et le méthacrylate de vinyle. On peut aussi réticuler en introduisant un monomère fonctionnel insaturé tel qu'un anhydride d'acide carboxylique insaturé, un acide carboxylique insaturé ou un époxyde insaturé. On peut citer à titre d'exemple l'anhydride maléique, l'acide (méth) acrylique et le méthacrylate de glycidyle. Each of the layers can be crosslinked in whole or in part. It suffices to add at least one at least difunctional monomer during the preparation of the layer, this monomer being able to be chosen from poly (meth) acrylic esters of polyols such as butylene di (meth) acrylate and trimethylol propane trimethacrylate. Other difunctional monomers are for example divinylbenzene, trivinylbenzene, vinyl acrylate and vinyl methacrylate. It is also possible to crosslink by introducing an unsaturated functional monomer such as an unsaturated carboxylic acid anhydride, an unsaturated carboxylic acid or an unsaturated epoxide. We can cite as an example maleic anhydride, (meth) acrylic acid and glycidyl methacrylate.
A titre d'exemple de particules multicouches de type core- shell, on peut citer celles appelées mou/dur ayant une couche intérieure (noyau) élastomérique et une couche extérieure (écorce) thermoplastique. Il existe aussi des particules ayant deux couches thermoplastiques, l'une en polystyrène et l'autre à l'extérieur en PMMA. Avantageusement le noyau représente, en poids, 70 à 90% de la particule et l'écorce 30 à 10%. A titre d'exemple de particules mou/dur, on peut citer cellles constituées : (i) de 75 à 80 parties d'un noyau comprenant en moles au moins 93% de butadiène, 5% de styrène et 0,5 à 1% de divinylbenzène et (ii) de 25 à 20 parties de deux écorces essentiellement de même poids l'une intérieure en polystyrène et l'autre extérieure en PMMA. A titre d'autre exemple de particules mou/dur, on peut citer celles ayant un noyau en poly (acrylate de butyle) ou en copolymère de l'acrylate de butyle et du butadiène et une écorce en PMMA. On peut citer aussi celles constituées dans l'ordre : (i) d'un noyau mou (40% en poids) obtenu en polymérisant 99 parts d'acrylate de butyle et 1 part de méthacrylate d'allyle, (ii) d'une écorce dure (60% en poids) obtenue en polymérisant 95 parts de MMA, 5 parts d'acrylate de butyle en présence de 0,002 parts de n-dodécyle mercaptan. La demande européenne EP 1061100 Al décrit de telles particules. By way of example of multilayer particles of core-shell type, mention may be made of those called soft / hard having an inner layer (core) of elastomer and an outer layer (shell) of thermoplastic. There are also particles with two thermoplastic layers, one made of polystyrene and the other outside of PMMA. Advantageously, the core represents, by weight, 70 to 90% of the particle and the shell 30 to 10%. By way of example of soft / hard particles, mention may be made of these: (i) from 75 to 80 parts of a core comprising in moles at least 93% of butadiene, 5% of styrene and 0.5 to 1% of divinylbenzene and (ii) 25 to 20 parts of two barks of essentially the same weight, one inside made of polystyrene and the other outside made of PMMA. As another example of soft / hard particles, mention may be made of those having a core of poly (butyl acrylate) or of a copolymer of butyl acrylate and butadiene and a shell of PMMA. Mention may also be made of those constituted in order: (i) of a soft core (40% by weight) obtained by polymerizing 99 parts of butyl acrylate and 1 part of allyl methacrylate, (ii) a hard bark (60% by weight) obtained by polymerizing 95 parts of MMA, 5 parts of butyl acrylate in the presence of 0.002 parts of n-dodecyl mercaptan. European application EP 1061100 A1 describes such particles.
Il existe aussi d'autres types de particules de type core- shell appelées dur/mou/dur ayant dans l'ordre un noyau thermoplastique, une couche intermédiaire élastomérique et une écorce dure. La demande US 2004/0030046 Al décrit des exemples de telles particules. On peut citer par exemple celles constituées dans l'ordre : (i) d'un noyau dur en copolymère du méthacrylate de méthyle et de l'acrylate d'éthyle, (ii) d'une couche intermédiaire en copolymère de l'acrylate de butyle et du styrène, (iii) d'une écorce dur en copolymère du méthacrylate de méthyle et de l'acrylate d'éthyle. On peut citer aussi celles constituées dans l'ordre : (i) d'un noyau dur (23% en poids) obtenu en polymérisant 92,7 parts de MMA,There are also other types of core-shell particles called hard / soft / hard having in order a thermoplastic core, an elastomeric intermediate layer and a hard shell. Application US 2004/0030046 A1 describes examples of such particles. Mention may be made, for example, of those constituted in order: (i) of a hard core made of a copolymer of methyl methacrylate and of ethyl acrylate, (ii) of a intermediate layer of copolymer of butyl acrylate and styrene, (iii) of a hard shell made of a copolymer of methyl methacrylate and ethyl acrylate. Mention may also be made of those constituted in order: (i) of a hard core (23% by weight) obtained by polymerizing 92.7 parts of MMA,
10 parts d'acrylate d'éthyle, 0,3 part de méthacrylate d'allyle, (ii) d'une couche intermédiaire molle (47% en poids) obtenue en polymérisant 81,7 parts d'acrylate de butyle, 17 parts de styrène et 1,3 parts de méthacrylate d'allyle, (iii) d'une écorce dure (30% en poids) obtenue en polymérisant 96 parts de MMA et 4 parts d'acrylate d'éthyle. 10 parts of ethyl acrylate, 0.3 part of allyl methacrylate, (ii) a soft intermediate layer (47% by weight) obtained by polymerizing 81.7 parts of butyl acrylate, 17 parts of styrene and 1.3 parts of allyl methacrylate, (iii) of a hard shell (30% by weight) obtained by polymerizing 96 parts of MMA and 4 parts of ethyl acrylate.
11 existe encore d'autres types de particules de type core- shell appelées dur/mou/mi dur. Par rapport aux précédentes, la différence vient de l' écorce extérieure "mi dur" qui est constituée de deux écorces : l'une intermédiaire et l'autre extérieure. L 'écorce intermédiaire est un copolymère du méthacrylate de méthyle, du styrène et d'au moins un monomère choisi parmi les acrylates d'alkyle, le butadiène et l'isoprène. L 'écorce extérieure est un PMMA homopolymère ou copolymère. On peut citer par exemple ceux constitués dans cet ordre : (i) d'un noyau en copolymère du méthacrylate de méthyle et de l'acrylate d'éthyle, (ii) d'une couche intermédiaire en copolymère de l'acrylate de butyle et du styrène, (iii) d'une lere écorce en copolymère du méthacrylate de méthyle, de l'acrylate de butyle et du styrène, (iv) d'une 2nde écorce en copolymère du méthacrylate de méthyle et de l'acrylate d'éthyle. En choisissant les proportions d'élastomère acrylique il faut tenir compte de celui qui peut être déjà contenu dans le PMMA. En effet il existe des qualités commerciales de PMMA dites "qualité choc" qui contiennent des modifiants choc acryliques le plus souvent de type cœur écorce. Ces modifiants choc acryliques peuvent être présents dans le PMMA parce qu'ils ont été introduits au cours de sa polymérisation ou préparés simultanément au cours de sa polymérisation. Des exemples de particules ainsi que leur procédé de préparation sont décrits dans les brevets suivants : US 4180494, US 3808180, US 4096202, US 4260693, US 3287443, US 3657391, US 4299928, US 3985704 et US 5773520. Les particules de type core-shell utilisables sont par exemple 1 ' IRH 70 de la société MITSUBISHI (bicouche mou/dur avec un cœur mou en copolymère butadiène-acrylate de butyle et une écorce dure en PMMA) ou le KM-355 de la société ROHM and HAAS. There are still other types of core shell type particles called hard / soft / semi hard. Compared to the previous ones, the difference comes from the outer bark "semi hard" which consists of two barks: one intermediate and the other outside. The intermediate shell is a copolymer of methyl methacrylate, styrene and at least one monomer chosen from alkyl acrylates, butadiene and isoprene. The outer shell is a homopolymer or copolymer PMMA. Mention may be made, for example, of those constituted in this order: (i) of a core made of a copolymer of methyl methacrylate and of ethyl acrylate, (ii) of an intermediate layer made of a copolymer of butyl acrylate and styrene, (iii) a l ere bark copolymer of methyl methacrylate, butyl acrylate and styrene, (iv) a 2 nd bark copolymer of methyl methacrylate and acrylate 'ethyl. When choosing the proportions of acrylic elastomer, account must be taken of that which may already be contained in the PMMA. Indeed, there are commercial qualities of PMMA known as "impact quality" which contain acrylic impact modifiers, most often of the core-bark type. These shock modifiers acrylics can be present in PMMA because they were introduced during its polymerization or prepared simultaneously during its polymerization. Examples of particles and their preparation process are described in the following patents: US 4180494, US 3808180, US 4096202, US 4260693, US 3287443, US 3657391, US 4299928, US 3985704 and US 5773520. Core-type particles Shell usable are for example 1 IRH 70 from the company MITSUBISHI (soft / hard bilayer with a soft core of butadiene-butyl acrylate copolymer and a hard shell of PMMA) or KM-355 from the company ROHM and HAAS.
S' agissant du film multicouche, celui-ci est un film multicouche coextrudé comprenant dans l'ordre disposées l'une contre l'autre : As regards the multilayer film, this is a coextruded multilayer film comprising in order arranged one against the other:
• une couche de surface (I) comprenant comme constituants principaux un PVDF et éventuellement un PMMA ;  • a surface layer (I) comprising as main constituents a PVDF and possibly a PMMA;
• une couche intermédiaire (II) comprenant comme constituants principaux de 0 à 60 parties d'un PVDF, de • an intermediate layer (II) comprising as main constituents from 0 to 60 parts of a PVDF,
40 à 100 parties d'un PMMA, de 0 à 25 parties d'un élastomère acrylique et de 0 à 10 parts d'un absorbeur UV, le total faisant 100 parties ; 40 to 100 parts of a PMMA, 0 to 25 parts of an acrylic elastomer and 0 to 10 parts of a UV absorber, the total making 100 parts;
• une couche adhésive (III) comprenant comme constituant principal un PMMA fonctionnel.  • an adhesive layer (III) comprising as main constituent a functional PMMA.
La fonction principale de la couche de surface (I) est de protéger le substrat. La fonction principale de la couche intermédiaire (II) est d'assurer une flexibilité au film (par ex. pendant sa fabrication et sa manipulation) et aussi lorsque la couche contient un absorbeur UV de renforcer la protection UV. La fonction principale de la couche adhésive (III) est d'assurer l'adhésion sur le substrat et d'éviter la délamination du film. Le film multicouche peut être préparé par coextrusion. La technique de coextrusion s'appuie sur l'utilisation d'autant d'extrudeuses qu'il y a de couches à extruder, les nappes de matières fondues issues de chacune des extrudeuses étant ensuite réunies pour former le film multicouche (pour plus de détails, on pourra se reporter à l'ouvrage Principles of Polymer Processing de Z.Tadmor, édition Wiley, 1979) . Les mélanges des ingrédients formant chacune des couches sont obtenus dans chacune des extrudeuses servant à la coextrusion ou bien préalablement dans des extrudeuses séparées. On peut utiliser comme dans les exemples la technique d'extrusion- soufflage (blown-film) . L'épaisseur de la couche de surface (I) est avantageusement comprise entre 1 et 100 μm, de préférence entre 2 et 40 μm. L'épaisseur de la couche intermédiaire (II) est avantageusement comprise entre 1 et 100 μm, de préférence entre 10 et 60 μm. L'épaisseur de la couche adhésive (III) est avantageusement comprise entre 1 et 100 μm, de préférence entre 2 et 40 μm. Le film avec les épaisseurs avantageuses décrites présente les propriétés mécaniques suffisantes pour permettre sa manipulation, sa mise en œuvre et son utilisation . The main function of the surface layer (I) is to protect the substrate. The main function of the intermediate layer (II) is to provide flexibility to the film (eg during its manufacture and handling) and also when the layer contains a UV absorber to enhance UV protection. The main function of the adhesive layer (III) is to ensure adhesion to the substrate and to prevent delamination of the film. The multilayer film can be prepared by coextrusion. The coextrusion technique is based on the use of as many extruders as there are layers to be extruded, the layers of molten material coming from each of the extruders then being combined to form the multilayer film (for more details , we can refer to the book Principles of Polymer Processing by Z. Tadmor, Wiley edition, 1979). The mixtures of the ingredients forming each of the layers are obtained in each of the coextrusion extruders or else beforehand in separate extruders. As in the examples, the blown-film technique can be used. The thickness of the surface layer (I) is advantageously between 1 and 100 μm, preferably between 2 and 40 μm. The thickness of the intermediate layer (II) is advantageously between 1 and 100 μm, preferably between 10 and 60 μm. The thickness of the adhesive layer (III) is advantageously between 1 and 100 μm, preferably between 2 and 40 μm. The film with the advantageous thicknesses described has sufficient mechanical properties to allow its handling, processing and use.
S' agissant de la couche de surface (I), celle-ci comprend comme constituants principaux un PVDF et éventuellement un PMMA. De préférence, la couche de surface (I) comprend comme constituants principaux de 50 à 100 parties de PVDF pour respectivement de 50 à 0 parties de PMMA, le total faisant 100 parties. Avantageusement, la couche de surface (I) comprend comme constituants principaux de 70 à 100 parties de PVDF pour respectivement de 30 à 0 parties de PMMA et de préférence de 75 à 85 parties de PVDF pour respectivement 25 à 15 parties de PMMA, le total faisant 100 parties. As regards the surface layer (I), this comprises as main constituents a PVDF and possibly a PMMA. Preferably, the surface layer (I) comprises as main constituents from 50 to 100 parts of PVDF for respectively from 50 to 0 parts of PMMA, the total making 100 parts. Advantageously, the surface layer (I) comprises as main constituents from 70 to 100 parts of PVDF for respectively from 30 to 0 parts of PMMA and preferably of 75 to 85 parts of PVDF for respectively 25 to 15 parts of PMMA, the total making 100 parts.
Selon une variante, la couche de surface (I) se présente sous forme de deux couches superposées : According to a variant, the surface layer (I) is in the form of two superposed layers:
• une couche (Ia) comprenant comme constituants principaux 75 à 100 parties de PVDF pour respectivement 25 à 0 parties de PMMA ;  • a layer (Ia) comprising as main constituents 75 to 100 parts of PVDF for respectively 25 to 0 parts of PMMA;
• une couche (Ib) comprenant comme constituants principaux 50 à 90 parties de PVDF pour respectivement 50 à 10 parties de PMMA.  • a layer (Ib) comprising as main constituents 50 to 90 parts of PVDF for respectively 50 to 10 parts of PMMA.
La couche (Ib) est la couche en contact avec la couche intermédiaire (II) et la couche (Ia) est la couche « extérieure » c'est-à-dire que le film multicouche comprend dans l'ordre les couches ( Ia) / ( Ib) / ( II ) / ( III ) . The layer (Ib) is the layer in contact with the intermediate layer (II) and the layer (Ia) is the “outer” layer, that is to say that the multilayer film comprises in order the layers (Ia) / (Ib) / (II) / (III).
S' agissant de la couche intermédiaire (II), celle-ci comprend comme constituants principaux de 0 à 60 parties de PVDF, de 40 à 100 parties de PMMA, de 0 à 25 parties d'élastomère acrylique et de 0 à 10 parts d'absorbeur UV, le total faisant 100 parties. Avantageusement, elle comprend de 20 à 60 parties de PVDF, de 40 à 60 parties de PMMA, de 0 à 25 parties d'élastomère acrylique, de 0 à 10 parts d'absorbeur UV, le total faisant 100 parties. Avantageusement, elle comprend de 30 à 50 parties de PVDF, de 40 à 60 parties de PMMA, de 0 à 20 parties d'un élastomère acrylique, de 0 à 5 parties d'un absorbeur UV, le total faisant 100 parties. Afin de garantir que le film ne blanchisse pas, même dans les conditions du test à l'eau bouillante, la couche intermédiaire ne contient aucun élastomère acrylique. Elle comprend de 20 à 50 parties de PVDF, de 50 à 80 parties d'un PMMA comprenant en poids de 90 à 50% de MMA pour respectivement de 10 à 50% d'un (méth) acrylate d'alkyle, l'alkyle ayant de 2 à 4 atomes de carbone, de 0 à 5 parties d'un absorbeur UV, le total faisant 100 parties. Encore plus préférentiellement , elle comprend en poids de 25 à 45 parties de PVDF, de 55 à 75 parties de PMMA comprenant en poids de 90 à 50% de MMA pour respectivement de 10 à 50% d'un (méth) acrylate d'alkyle, l'alkyle ayant de 2 à 4 atomes de carbone, de 0 à 5 parties d'un absorbeur UV, le total faisant 100 parties. De préférence, le PMMA comprend en poids de 85 à 70% de MMA pour respectivement de 15 à 30% d'un (méth) acrylate d'alkyle, l'alkyle ayant de 2 à 4 atomes de carbone. As regards the intermediate layer (II), this comprises as main constituents from 0 to 60 parts of PVDF, from 40 to 100 parts of PMMA, from 0 to 25 parts of acrylic elastomer and from 0 to 10 parts of UV absorber, the total making 100 parts. Advantageously, it comprises from 20 to 60 parts of PVDF, from 40 to 60 parts of PMMA, from 0 to 25 parts of acrylic elastomer, from 0 to 10 parts of UV absorber, the total making 100 parts. Advantageously, it comprises from 30 to 50 parts of PVDF, from 40 to 60 parts of PMMA, from 0 to 20 parts of an acrylic elastomer, from 0 to 5 parts of a UV absorber, the total making 100 parts. In order to ensure that the film does not bleach, even under the conditions of the boiling water test, the intermediate layer does not contain any acrylic elastomer. It comprises from 20 to 50 parts of PVDF, from 50 to 80 parts of a PMMA comprising by weight from 90 to 50% of MMA for respectively from 10 to 50% of a alkyl (meth) acrylate, the alkyl having from 2 to 4 carbon atoms, from 0 to 5 parts of a UV absorber, the total making 100 parts. Even more preferably, it comprises by weight from 25 to 45 parts of PVDF, from 55 to 75 parts of PMMA comprising by weight from 90 to 50% of MMA for respectively from 10 to 50% of an alkyl (meth) acrylate , the alkyl having from 2 to 4 carbon atoms, from 0 to 5 parts of a UV absorber, the total making 100 parts. Preferably, the PMMA comprises by weight from 85 to 70% of MMA for respectively from 15 to 30% of an alkyl (meth) acrylate, the alkyl having from 2 to 4 carbon atoms.
De préférence, le PMMA comprend en poids de 80 à 70% de MMA pour respectivement de 20 à 30% d'un (méth) acrylate d'alkyle, l'alkyle ayant de 2 à 4 atomes de carbone. On utilise avantageusement comme (méth) acrylate d'alkyle 1 'acrylate de méthyle, d'éthyle ou de butyle. S' agissant de la couche adhésive (III), celle-ci comprend comme constituant principal un PMMA fonctionnel. De préférence, il s'agit du PMMA fonctionnel obtenu par la copolymérisation du MMA, de l'acide (méth) acrylique et éventuellement d'un 3eme monomère copolymérisable avec le MMA. Preferably, the PMMA comprises by weight from 80 to 70% of MMA for respectively from 20 to 30% of an alkyl (meth) acrylate, the alkyl having from 2 to 4 carbon atoms. Advantageously used as alkyl (meth) acrylate, methyl, ethyl or butyl acrylate. As regards the adhesive layer (III), this comprises as main constituent a functional PMMA. Preferably, it is the PMMA block obtained by the copolymerization of MMA, of (meth) acrylic acid and optionally a 3rd monomer copolymerizable with MMA.
La couche adhésive (III) comprend en poids plus de 60%, avantageusement plus de 80%, de préférence plus de 90%, encore plus préférentiellement plus de 95% de PMMA fonctionnel. De préférence, la couche adhésive (III) ne comprend pas de polymère fluoré pour favoriser l'adhésion. The adhesive layer (III) comprises by weight more than 60%, advantageously more than 80%, preferably more than 90%, even more preferably more than 95% of functional PMMA. Preferably, the adhesive layer (III) does not comprise a fluoropolymer to promote adhesion.
Le PMMA fonctionnel permet d'obtenir une bonne adhésion sur de nombreux substrats. L'adhésion est renforcée dès que le PMMA fonctionnel présente une teneur en poids en monomère porteur de fonction supérieure à 0,5%, avantageusement supérieure à 1%, de préférence supérieure à 2%. Functional PMMA provides good adhesion on many substrates. The adhesion is reinforced as soon as the functional PMMA has a content by weight of carrier monomer with a function greater than 0.5%, advantageously greater than 1%, preferably greater than 2%.
S' agissant de l'absorbeur UV, celui-ci est connu en lui-même. On trouvera une liste d'absorbeurs UV dans le document USAs regards the UV absorber, this is known in itself. A list of UV absorbers can be found in the document US
5256472. On utilise avantageusement les benzotriazoles et les benzophénones . A titre d'exemple on peut utiliser le TINUVIN® 213 ou le TINUVIN® 109 et de façon préférable le TINUVIN® 234 de la société Ciba Speciality Chemicals. 5256472. Benzotriazoles and benzophenones are advantageously used. As an example we can use the ® TINUVIN 213 or TINUVIN ® 109 and preferably TINUVIN ® 234 from Ciba Specialty Chemicals.
S' agissant du panneau, celui-ci comprend au moins une couche d'un matériau ( ligno) cellulosique, qui peut être par exemple :As regards the panel, it comprises at least one layer of a (ligno) cellulosic material, which may for example be:
• le bois ; • wood ;
• le papier, de préférence le papier Kraft ;  • paper, preferably Kraft paper;
• le bois aggloméré.  • agglomerated wood.
Le panneau peut avoir une forme parallélipidique . Cependant l'invention n'est pas limitée uniquement aux panneaux de forme parallélipidique mais peut s'appliquer à d'autres formes, par exemple une forme en coin. Le panneau trouve des applications par exemple dans le revêtement de façades extérieures ou intérieures ou bien la réalisation de planchers. The panel can have a rectangular shape. However, the invention is not limited only to panels of rectangular shape but can be applied to other shapes, for example a wedge shape. The panel finds applications for example in the coating of external or internal facades or the realization of floors.
Il peut s'agir d'un panneau comprenant une seule couche comme un panneau de bois massif ou un panneau de bois aggloméré. Un panneau de bois aggloméré est constitué de particules de boisIt can be a single layer panel such as a solid wood panel or a chipboard panel. A chipboard panel is made of wood particles
(sous différentes formes : sciure, copeaux, fibres,...) traitées avec au moins une résine thermodurcissable et soumises à une pression et une température élevées. Il peut s'agir aussi d'un panneau comprenant plusieurs couches identiques ou différentes, de matériau(x) (ligno) cellulosique (s ). On parle souvent dans ce cas de panneau sandwich. Le panneau peut aussi comprendre au moins une couche en une matière élastomérique ou en une mousse dont la fonction est d'améliorer l'isolation phonique du panneau. Il peut comprendre aussi au moins une couche de contre-balancement dont la fonction est de stabiliser mécaniquement le panneau pour éviter le flambage ou la déformation du panneau. (in different forms: sawdust, shavings, fibers, ...) treated with at least one thermosetting resin and subjected to high pressure and temperature. It may also be a panel comprising several identical or different layers of cellulosic material (s). We often speak in this case of sandwich panel. The panel can also comprise at least one layer of an elastomeric material or of a foam whose function is to improve the sound insulation of the panel. It can also include at least one counterbalancing layer whose function is to mechanically stabilize the panel to avoid buckling or deformation of the panel.
Pour favoriser l'adhésion entre les couches, on dispose entre celles-ci une couche intermédiaire d'une colle, généralement de fine épaisseur. La colle est souvent une colle thermodurcissable, par exemple du type phénolique ou mélaminique . exemples de panneaux To promote adhesion between the layers, an intermediate layer of an adhesive is provided between them, generally of thin thickness. The glue is often a thermosetting glue, for example of the phenolic or melamine type. examples of panels
Des exemples de panneaux sandwich sont donnés dans les demandes EP 1388414 Al, EP 1199157 Al ou GB 2307882 A. Ainsi l'exemple 1 de la demande EP 1199157 Al décrit un panneau comprenant dans l'ordre : Examples of sandwich panels are given in applications EP 1388414 A1, EP 1199157 A1 or GB 2307882 A. Thus example 1 of application EP 1199157 A1 describes a panel comprising in order:
une couche en papier Kraft phénolique de grammage 180/290 g/m2 ; a layer of phenolic Kraft paper with a basis weight of 180/290 g / m 2 ;
une couche de colle ;  a layer of glue;
une couche de bois ;  a layer of wood;
une couche décorative composée d'un film de cellulose teinté et un film de cellulose imprégné de mélamine et ayant une charge de silice.  a decorative layer composed of a tinted cellulose film and a cellulose film impregnated with melamine and having a silica filler.
Un autre exemple de panneau sandwich comprend dans l'ordre une couche de papier, une couche de bois et éventuellement une couche décorative ou bien une couche de papier et une couche décorative. Un autre exemple de panneau sandwich comprend dans l'ordre éventuellement une couche décorative, une couche de bois, une couche de papier, une couche de bois et éventuellement une couche décorative. Un autre exemple de panneau sandwich comprend dans l'ordre une couche décorative, une couche de bois et une couche décorative. Le film multicouche est appliqué sur la couche de bois ou sur la couche décorative. La couche de papier peut être aussi remplacée par un empilement de plusieurs couches de papier. De préférence, le papier utilisé est le papier kraft. La couche décorative peut être unicolore ou avoir un motif imprimé. Il peut s'agir d'un ou plusieurs film(s) de cellulose ou de papier imprimé. Il peut s'agir aussi d'une couche de colle thermodurcissable chargée en pigments. L'adhésion entre les couches est assurée par une couche de colle. De préférence, la colle est une colle thermodurcissable du type phénolique ou mélaminique . Another example of a sandwich panel comprises in order a layer of paper, a layer of wood and possibly a decorative layer or else a layer of paper and a decorative layer. Another example of a sandwich panel optionally includes, in order, a decorative layer, a layer of wood, a layer of paper, a layer of wood and possibly a decorative layer. Another example of a sandwich panel comprises, in order, a decorative layer, a layer of wood and a decorative layer. The multilayer film is applied to the wood layer or to the decorative layer. The paper layer can also be replaced by a stack of several layers of paper. Preferably, the paper used is kraft paper. The decorative layer can be a single color or have a printed pattern. It can be one or more cellulose film (s) or printed paper. It can also be a layer of thermosetting adhesive loaded with pigments. Adhesion between the layers is ensured by a layer of glue. Preferably, the adhesive is a thermosetting adhesive of the phenolic or melamine type.
On pourra encore donner des exemples de panneaux sandwich qui sont commercialisés. Le panneau BAQ+® de la société PRODEMA est décrit sur le site internet de cette société comme étant un panneau de haute densité constitué d'une âme en fibres de cellulose imprégnées de résines phénoliques thermodurcissables et d'une couche de bois naturel. Le panneau MAD® de PRODEMA est décrit comme étant un panneau composé d'une âme en contreplaqué bois imprégné de résines phénoliques thermodurcissables et d'une couche de bois naturel. Le panneau PARKLEX® 1000 de la société GUREA est décrit sur le site internet de cette société comme étant un panneau stratifié en bois à haute densité constitué à l'intérieur par des fibres de bois ou de papier traitées avec des résines phénoliques thermodurcies et très fortement pressées à des températures levées et d'une couche de bois naturel. Le film multicouche est appliqué contre la couche de bois. We can also give examples of sandwich panels that are marketed. The BAQ + ® panel from PRODEMA is described on the website of this company as being a high density panel consisting of a core of cellulose fibers impregnated with thermosetting phenolic resins and a layer of natural wood. The MAD ® panel from PRODEMA is described as being a panel composed of a plywood core impregnated with thermosetting phenolic resins and a layer of natural wood. The PARKLEX ® 1000 panel from the company GUREA is described on the website of this company as being a high density wooden laminated panel formed inside by wood or paper fibers treated with thermoset phenolic resins and very strongly pressed at high temperatures and a layer of natural wood. The multilayer film is applied against the layer of wood.
Utilisation du film multicouche Use of multilayer film
Le film multicouche de l'invention est utilisé pour protéger un matériau ( ligno) cellulosique tel que le bois, le carton ou le papier. La couche adhésive (III) est disposée du côté du matériau ( ligno) cellulosique . L'adhésion du film est renforcée si celui-ci vient en contact d'une colle thermodurcissable disposée à la surface ou dans la masse du matériau (ligno) cellulosique . On dispose entre le matériau (ligno) cellulosique et le film une colle thermodurcissable. La colle est disposée à la surface du matériau sous forme d'une couche ou bien sous forme de points de colle en plusieurs endroits du matériau. Le matériau ( ligno) cellulosique est donc recouvert en tout ou partie de sa surface par la colle thermodurcissable. La colle peut être par exemple une colle phénolique, par exemple phénol-formol, ou mélaminique ou urée- formol. La colle peut aussi être présente dans la masse du matériau (ligno) cellulosique, comme par exemple dans le cas d'un panneau aggloméré. The multilayer film of the invention is used to protect a (ligno) cellulosic material such as wood, cardboard or paper. The adhesive layer (III) is arranged on the side of the cellulosic (ligno) material. The adhesion of the film is reinforced if it comes into contact with a thermosetting adhesive placed on the surface or in the mass of the (ligno) cellulosic material. A thermosetting adhesive is placed between the (ligno) cellulosic material and the film. The glue is placed on the surface of the material in the form of a layer or else in the form of spots of glue in several places of the material. The (ligno) cellulosic material is therefore covered in whole or part of its surface by thermosetting glue. The adhesive may for example be a phenolic adhesive, for example phenol-formaldehyde, or melamine or urea-formaldehyde. The glue can also be present in the mass of the (ligno) cellulosic material, as for example in the case of an agglomerated panel.
L'invention est aussi relative à une structure multicouche comprenant au moins une couche d'un matériau (ligno) cellulosique et le film de l'invention disposée contre cette couche, la couche adhésive (III) étant disposée du côté du matériau (ligno) cellulosique . De façon plus particulière, le film peut s'appliquer sur un panneau dont l'une au moins des deux faces externes est constituée d'un matériau (ligno) cellulosique . La couche adhésive (III) est disposée du côté d'au moins une des deux faces externes en matériau (ligno) cellulosique . L'invention est aussi relative à un tel panneau. avantages procurés par le film multicouche The invention also relates to a multilayer structure comprising at least one layer of a cellulosic (ligno) material and the film of the invention disposed against this layer, the adhesive layer (III) being disposed on the side of the material (ligno) cellulosic. More particularly, the film can be applied to a panel of which at least one of the two external faces consists of a (ligno) cellulosic material. The adhesive layer (III) is arranged on the side of at least one of the two external faces of (ligno) cellulosic material. The invention also relates to such a panel. advantages of the multilayer film
Le matériau (ligno) cellulosique est protégé par le film multicouche de l'invention. Celui-ci assure une protection contre les rayons UV, les produits chimiques, les rayures, les agents atmosphériques (humidité, brouillard salin,...), les champignons et moisissures ou encore les graffitis. Le film assure une stabilité de couleur et d'aspect dans le temps. Le film peut être appliqué par compression à chaud. Le compression se fait sous une pression comprise généralement entre 2 et 30 MPa et à chaud à une température comprise généralement entre 100 et 16O0C. The cellulosic (ligno) material is protected by the multilayer film of the invention. This provides protection against UV rays, chemicals, scratches, atmospheric agents (humidity, salt spray, ...), fungi and molds or even graffiti. The film ensures color and appearance stability over time. The film can be applied by hot compression. The compression is carried out under a pressure generally between 2 and 30 MPa and hot at a temperature generally between 100 and 16O 0 C.
[EXEMPLES] [EXAMPLES]
produits utilisés products used
ALTUGLAS® BS8 : PMMA de la société ALTUGLAS INTERNATIONAL de MVI 4,5 cm3/10 min (23O0C, 3,8 kg) sous forme de perles contenant comme comonomère, l'acrylate de méthyle, à hauteur de 6% en poids. Ce PMMA ne contient pas de modifiant choc. ALTUGLAS ® BS8: PMMA society INTERNATIONAL ALTUGLAS MVI of 4.5 cm 3/10 min (23O 0 C, 3.8 kg) in bead form containing as comonomer, methyl acrylate, up to 6% by weight. This PMMA does not contain a shock modifier.
ALTUGLAS® PRD 510 A : le PMMA PRD 510 A est un copolymère de méthacrylate de méthyle et d'acrylate d'éthyle (25% en poids). Son MFI est de 5 g/10 minutes à 23O0C sous 3,8 kg. ALTUGLAS ® PRD 510 A: PMMA PRD 510 A is a copolymer of methyl methacrylate and ethyl acrylate (25% by weight). Its MFI is 5 g / 10 minutes at 230 ° C. under 3.8 kg.
ALTUGLAS® V825T : PMMA homopolymère de la société ALTUGLAS INTERNATIONAL de melt-flow 5,5 g/10 min (23O0C, 3,8 kg) sous forme de granulés. Ce PMMA n'est pas un PMMA fonctionnel. ALTUGLAS ® V825T: PMMA homopolymer from the company ALTUGLAS INTERNATIONAL of melt-flow 5.5 g / 10 min (230 ° C., 3.8 kg) in the form of granules. This PMMA is not a functional PMMA.
ALTUGLAS® HT121 : commercialisé par ALTUGLAS INTERNATIONAL. Ce produit renferme environ 4,5% en poids d'acide méthacrylique ou d'anhydride issu de l'acide méthacrylique. Il présente un melt-index de 2 g/10 min (23O0C, 3,8 kg). ALTUGLAS ® HT121: marketed by ALTUGLAS INTERNATIONAL. This product contains about 4.5% by weight of methacrylic acid or anhydride from methacrylic acid. It has a melt-index of 2 g / 10 min (230 ° C., 3.8 kg).
TINUVIN® 234 : absorbeur UV de type hydroxyphényl benzotriazole de la société CIBA SPECIALITY CHEMICALS. TINUVIN ® 234: UV absorber of hydroxyphenyl benzotriazole type from the company CIBA SPECIALTY CHEMICALS.
KYNAR® 740 : PVDF homopolymère de la société ARKEMA de MFI 13 g/10 minutes sous 12,5 kg à 23O0C. Exemple 1 (selon l'invention) KYNAR ® 740: Homopolymer PVDF from the company ARKEMA from MFI 13 g / 10 minutes at 12.5 kg at 230 ° C. Example 1 (according to the invention)
Sur une extrudeuse Kieffel, on prépare un film à tricouche avec de l'intérieur vers l'extérieur de la bulle les couches suivantes :  On a Kieffel extruder, a three-layer film is prepared with the following layers from the inside to the outside of the bubble:
• une couche de PMMA ALTUGLAS® HT121 de 10 μm d'épaisseur,• a layer of ALTUGLAS ® HT121 PMMA 10 μm thick,
• une couche de 40 μm d'un mélange contenant en poids 40,2% de KYNAR® 740, 57% d'un PMMA ALTUGLAS® PRD 510 A et 2,8% de TINUVIN® 234 puis • a layer of 40 microns of a mixture containing 40.2% by weight of KYNAR ® 740, 57% of a PMMA Altuglas ® PRD 510 A and 2.8% of TINUVIN ® 234 and then
• une couche d'un mélange contenant en poids 80% de KYNAR® 740 et 20% de PMMA ALTUGLAS® BS8 de 10 μm d'épaisseur. • a layer of a mixture containing by weight 80% KYNAR ® 740 and 20% PMMA Altuglas ® BS8, 10 .mu.m thick.
Le film obtenu est très transparent et présente une excellente tenue au vieillissement extérieur ainsi qu'une excellente résistance chimique. Ce film est placé au fond d'un moule. Sur le film du côté du PMMA ALTUGLAS® HT121, on dépose 2 couches de papier Kraft enduites de résine phénolique de couleur du type TPS de la société COVERIGHT, ces couches sont posées sur une lame de bois de 200 μm d'épaisseur préalablement enduite de résine phénolique déposée au pinceau, elle-même déposée sur 30 feuilles de papiers Kraft. Après cuisson et réaction de la résine phénolique (30 minutes à 15O0C), l'objet formé se présente sous la forme d'une plaque épaisse d'environ 8 mm présentant un aspect de type bois. Le film tricouche présente une excellente adhésion juste après la cuisson, il n'est pas possible de peler ce film de la surface de la résine phénolique réticulée. Cette plaque est découpée sur ses quatre bords afin d'avoir des côtés de plaque parfaitement rectilignes et des dimensions de 5 cm x 5 cm. Cette plaque est ensuite introduite dans un bain d'eau bouillante pendant 2 heures. Après ce traitement, on ne constate aucun blanchiment ni aucun décollement. Exemple 2 (comparatif) The film obtained is very transparent and has excellent resistance to external aging as well as excellent chemical resistance. This film is placed at the bottom of a mold. On the film on the side of PMMA ALTUGLAS ® HT121, 2 layers of Kraft paper coated with color phenolic resin of the TPS type from COVERIGHT are deposited, these layers are placed on a 200 μm thick wooden strip previously coated with phenolic resin deposited with a brush, itself deposited on 30 sheets of Kraft paper. After cooking and reaction of the phenolic resin (30 minutes at 150 ° C.), the object formed is in the form of a thick plate of approximately 8 mm having a wood-like appearance. The three-layer film has excellent adhesion just after curing, it is not possible to peel this film from the surface of the crosslinked phenolic resin. This plate is cut on its four edges in order to have perfectly straight plate sides and dimensions of 5 cm x 5 cm. This plate is then introduced into a boiling water bath for 2 hours. After this treatment, there is no bleaching or detachment. Example 2 (comparative)
Sur extrudeuse Kieffel, une structure à tricouche est préparée avec de l'intérieur vers l'extérieur de la bulle les couches suivantes :  On a Kieffel extruder, a three-layer structure is prepared with the following layers from inside to outside of the bubble:
• une couche de PMMA ALTUGLAS® V825T de 10 μm d'épaisseur,• a layer of ALTUGLAS ® V825T PMMA 10 μm thick,
• une couche de 40 μm d'un mélange contenant 40,2% de KYNAR 740 de la société ARKEMA, 57% d'un PMMA ALTUGLAS® PRD 510 A et 2,8% de TINUVIN® 234 puis • a layer of 40 microns of a mixture containing 40.2% KYNAR 740 Arkema, 57% of PMMA Altuglas ® PRD 510 A and 2.8% of TINUVIN ® 234 and
• une couche d'un mélange de KYNAR® 740 (80%) et de PMMA ALTUGLAS® BS8 (20%) de 10 μm d'épaisseur. • a layer of a mixture of KYNAR ® 740 (80%) and PMMA ALTUGLAS ® BS8 (20%), 10 μm thick.
Le film obtenu est très transparent et présente une excellente tenue au vieillissement extérieur ainsi qu'une excellente résistance chimique. Ce film est placé au fond d'un moule. Sur le film du côté du PMMA ALTUGLAS® V825 T, on dépose 2 couches de papier Kraft enduites de résine phénolique de couleur du type TPS de la société COVERIGHT, ces couches sont posées sur une lame de bois de 200 μm d'épaisseur préalablement enduite de résine phénolique déposée au pinceau, elle-même déposée sur 30 feuilles de papier Kraft. Après cuisson et réaction de la résine phénolique (30 minutes à 15O0C) l'objet formé se présente sous la forme d'une plaque épaisse d'environ 8 mm présentant un aspect de type bois. Le film tricouche présente une bonne adhésion juste après cuisson, il n'est pas possible de peler ce film de la surface de la résine phénolique réticulée. Cette plaque est découpée sur ses quatre bords afin d'avoir des côtés de plaque parfaitement rectilignes et des dimensions de 5 cm x 5 cm. Cette plaque est ensuite introduite dans un bain d'eau bouillante pendant 2 heures, après ce traitement l'aspect de la plaque est inspecté. On constate un blanchiment ainsi qu'un décollement des bords du film. The film obtained is very transparent and has excellent resistance to external aging as well as excellent chemical resistance. This film is placed at the bottom of a mold. On the film on the side of PMMA ALTUGLAS ® V825 T, 2 layers of Kraft paper coated with phenolic resin of the TPS type color from COVERIGHT are deposited, these layers are laid on a 200 μm thick wooden strip previously coated. phenolic resin deposited with a brush, itself deposited on 30 sheets of Kraft paper. After cooking and reaction of the phenolic resin (30 minutes at 150 ° C.) the object formed is in the form of a thick plate of approximately 8 mm having a wood-like appearance. The three-layer film has good adhesion just after curing, it is not possible to peel this film from the surface of the crosslinked phenolic resin. This plate is cut on its four edges in order to have perfectly straight plate sides and dimensions of 5 cm x 5 cm. This plate is then introduced into a boiling water bath for 2 hours, after this treatment the appearance of the plate is inspected. There is a bleaching as well as a separation of the edges of the film.

Claims

REVENDICATIONS 1. Utilisation d'un film multicouche coextrudé pour protéger un matériau (ligno) cellulosique, le film multicouche comprenant dans l'ordre disposées l'une contre l'autre :  CLAIMS 1. Use of a coextruded multilayer film to protect a (ligno) cellulosic material, the multilayer film comprising in order arranged one against the other:
• une couche de surface (I) comprenant comme constituants principaux un PVDF et éventuellement un PMMA ;  • a surface layer (I) comprising as main constituents a PVDF and possibly a PMMA;
• une couche intermédiaire (II) comprenant comme constituants principaux de 0 à 60 parties d'un PVDF, de 40 à 100 parties d'un PMMA, de 0 à 25 parties d'un élastomère acrylique et de 0 à 10 parts d'un absorbeur UV, le total faisant 100 parties ;  An intermediate layer (II) comprising as main constituents from 0 to 60 parts of a PVDF, from 40 to 100 parts of a PMMA, from 0 to 25 parts of an acrylic elastomer and from 0 to 10 parts of a UV absorber, the total making 100 parts;
• une couche adhésive (III) comprenant comme constituant principal un PMMA fonctionnel,  An adhesive layer (III) comprising as main constituent a functional PMMA,
la couche adhésive (III) étant disposée du côté du matériau (ligno) cellulosique . the adhesive layer (III) being disposed on the side of the cellulosic (ligno) material.
2. Utilisation d'un film multicouche coextrudé pour protéger un panneau comprenant au moins une couche d'un matériau (ligno) cellulosique, le film multicouche comprenant dans l'ordre disposées l'une contre l'autre : 2. Use of a coextruded multilayer film to protect a panel comprising at least one layer of a (ligno) cellulosic material, the multilayer film comprising in order arranged one against the other:
• une couche de surface (I) comprenant comme constituants principaux un PVDF et éventuellement un PMMA ;  • a surface layer (I) comprising as main constituents a PVDF and possibly a PMMA;
• une couche intermédiaire (II) comprenant comme constituants principaux de 0 à 60 parties d'un PVDF, de 40 à 100 parties d'un PMMA, de 0 à 25 parties d'un élastomère acrylique et de 0 à 10 parts d'un absorbeur UV, le total faisant 100 parties ;  An intermediate layer (II) comprising as main constituents from 0 to 60 parts of a PVDF, from 40 to 100 parts of a PMMA, from 0 to 25 parts of an acrylic elastomer and from 0 to 10 parts of a UV absorber, the total making 100 parts;
• une couche adhésive (III) comprenant comme constituant principal un PMMA fonctionnel ; et s 'appliquant sur au moins l'une des deux faces externes du panneau constituée d'un matériau (ligno) cellulosique, la couche adhésive (III) étant disposée du côté d'au moins une desdites faces externes du panneau. • an adhesive layer (III) comprising as main constituent a functional PMMA; and applying to at least one of the two external faces of the panel made of a (ligno) cellulosic material, the adhesive layer (III) being arranged on the side of at least one of said external faces of the panel.
3. Utilisation selon la revendication 1 ou 2 caractérisée en ce que le film vient en contact d'une colle thermodurcissable disposée à la surface ou dans la masse du matériau (ligno) cellulosique . 3. Use according to claim 1 or 2 characterized in that the film comes into contact with a thermosetting adhesive disposed on the surface or in the mass of the (ligno) cellulosic material.
4. Utilisation selon l'une des revendications 1 à 3 caractérisée en ce que la couche de surface (I) comprend comme constituants principaux de 50 à 100 parties d'un PVDF pour respectivement de 50 à 0 parties de PMMA, le total faisant 100 parties. 4. Use according to one of claims 1 to 3 characterized in that the surface layer (I) comprises as main constituents from 50 to 100 parts of a PVDF for respectively from 50 to 0 parts of PMMA, the total making 100 parts.
5. Utilisation selon l'une des revendications 1 à 4 caractérisée en ce que la couche de surface (I) comprend comme constituants principaux de 70 à 100 parties de PVDF pour respectivement de 30 à 0 parties de PMMA et de préférence de 75 à 85 parties de PVDF pour respectivement 25 à 15 parties de PMMA, le total faisant 100 parties. 5. Use according to one of claims 1 to 4 characterized in that the surface layer (I) comprises as main constituents from 70 to 100 parts of PVDF for respectively from 30 to 0 parts of PMMA and preferably from 75 to 85 parts of PVDF for respectively 25 to 15 parts of PMMA, the total making 100 parts.
6. Utilisation selon la revendication 1 à 3 caractérisée en ce que la couche de surface (I) se présente sous forme de deux couches superposées : 6. Use according to claim 1 to 3 characterized in that the surface layer (I) is in the form of two superimposed layers:
• une couche (Ia) comprenant comme constituants principaux 75 à 100 parties de PVDF pour respectivement 25 à 0 parties de PMMA ;  • a layer (Ia) comprising as main constituents 75 to 100 parts of PVDF for respectively 25 to 0 parts of PMMA;
• une couche (Ib) en contact avec la couche intermédiaire (II) comprenant comme constituants principaux 50 à 90 parties de PVDF pour respectivement 50 à 10 parties de PMMA. • a layer (Ib) in contact with the intermediate layer (II) comprising as main constituents 50 to 90 parts of PVDF for respectively 50 to 10 parts of PMMA.
7. Utilisation selon l'une quelconque des revendications 1 à7. Use according to any one of claims 1 to
6 caractérisée en ce que la couche intermédiaire (II) comprend comme constituants principaux de 0 à 60 parties de PVDF, de 40 à 100 parties de PMMA, de 0 à 25 parties d'élastomère acrylique, de 0 à 10 parts d'absorbeur UV, le total faisant 100 parties. 6 characterized in that the intermediate layer (II) comprises as main constituents from 0 to 60 parts of PVDF, from 40 to 100 parts of PMMA, from 0 to 25 parts of acrylic elastomer, from 0 to 10 parts of UV absorber , the total making 100 parts.
8. Utilisation selon l'une quelconque des revendications 1 à8. Use according to any one of claims 1 to
7 caractérisée en ce que la couche intermédiaire (II) comprend comme constituants principaux de 20 à 60 parties de PVDF, de7 characterized in that the intermediate layer (II) comprises as main constituents from 20 to 60 parts of PVDF, of
40 à 60 parties de PMMA, de 0 à 25 parties d'élastomère acrylique, de 0 à 10 parts d'absorbeur UV, le total faisant 100 parties. 40 to 60 parts of PMMA, from 0 to 25 parts of acrylic elastomer, from 0 to 10 parts of UV absorber, the total making 100 parts.
9. Utilisation selon l'une quelconque des revendications 1 à9. Use according to any one of claims 1 to
8 caractérisée en ce que la couche intermédiaire (II) comprend comme constituants principaux de 30 à 50 parties de PVDF, de 40 à 60 parties de PMMA, de 0 à 20 parties d'élastomère acrylique, de 0 à 5 parties d'absorbeur UV, le total faisant 100 parties. 8 characterized in that the intermediate layer (II) comprises as main constituents from 30 to 50 parts of PVDF, from 40 to 60 parts of PMMA, from 0 to 20 parts of acrylic elastomer, from 0 to 5 parts of UV absorber , the total making 100 parts.
10. Utilisation selon l'une quelconque des revendications 1 à 7 caractérisée en ce que la couche intermédiaire (II) comprend de 20 à 50 parties de PVDF, de 50 à 80 parties d'un PMMA comprenant en poids de 90 à 50% de MMA pour respectivement de 10 à 50% d'un (méth) acrylate d'alkyle, l'alkyle ayant de 2 à 4 atomes de carbone, de 0 à 5 parties d'un absorbeur UV, le total faisant 100 parties. 10. Use according to any one of claims 1 to 7 characterized in that the intermediate layer (II) comprises from 20 to 50 parts of PVDF, from 50 to 80 parts of a PMMA comprising by weight from 90 to 50% of MMA for respectively from 10 to 50% of an alkyl (meth) acrylate, the alkyl having from 2 to 4 carbon atoms, from 0 to 5 parts of a UV absorber, the total making 100 parts.
11. Utilisation selon l'une quelconque des revendications 1 à 7 ou selon la revendication 10 caractérisée en ce que la couche intermédiaire (II) comprend de 25 à 45 parties de PVDF, de 55 à 75 parties de PMMA comprenant en poids de 90 à 50% de MMA pour respectivement de 10 à 50% d'un (méth) acrylate d'alkyle, l'alkyle ayant de 2 à 4 atomes de carbone, de 0 à 5 parties d'un absorbeur UV, le total faisant 100 parties. 11. Use according to any one of claims 1 to 7 or according to claim 10 characterized in that the intermediate layer (II) comprises from 25 to 45 parts of PVDF, from 55 to 75 parts of PMMA comprising by weight from 90 to 50% MMA for respectively 10 to 50% of a (meth) acrylate alkyl, the alkyl having from 2 to 4 carbon atoms, from 0 to 5 parts of a UV absorber, the total making 100 parts.
12. Utilisation selon la revendication 10 ou 11 caractérisée en ce que le PMMA comprend en poids de 85 à 70% de MMA pour respectivement de 15 à 30% d'un (méth) acrylate d'alkyle, l'alkyle ayant de 2 à 4 atomes de carbone. 12. Use according to claim 10 or 11 characterized in that the PMMA comprises by weight from 85 to 70% of MMA for respectively from 15 to 30% of an alkyl (meth) acrylate, the alkyl having from 2 to 4 carbon atoms.
13. Utilisation selon la revendication 10 ou 11 caractérisée en ce que le PMMA comprend en poids de 80 à 70% de MMA pour respectivement de 20 à 30% d'un (méth) acrylate d'alkyle, l'alkyle ayant de 2 à 4 atomes de carbone. 13. Use according to claim 10 or 11 characterized in that the PMMA comprises by weight from 80 to 70% of MMA for respectively from 20 to 30% of an alkyl (meth) acrylate, the alkyl having from 2 to 4 carbon atoms.
14. Utilisation selon l'une des revendications 10 à 13 caractérisée en ce que le (méth) acrylate d'alkyle est l 'acrylate de méthyle, d'éthyle ou de butyle. 14. Use according to one of claims 10 to 13 characterized in that the alkyl (meth) acrylate is methyl, ethyl or butyl acrylate.
15. Utilisation selon l'une quelconque des revendications 1 à 14 caractérisée en ce que la couche adhésive (III) comprend en poids plus de 60%, avantageusement plus de 80%, de préférence plus de 90%, encore plus préférentiellement plus de 95% d'un PMMA fonctionnel. 15. Use according to any one of claims 1 to 14 characterized in that the adhesive layer (III) comprises by weight more than 60%, advantageously more than 80%, preferably more than 90%, even more preferably more than 95 % of a functional PMMA.
16. Utilisation selon la revendication 15 caractérisée en ce que la couche adhésive (III) ne comprend pas de polymère fluoré . 16. Use according to claim 15 characterized in that the adhesive layer (III) does not comprise fluoropolymer.
17. Utilisation selon l'une quelconque des revendications 1 à 16 caractérisée en ce que le PMMA fonctionnel comprend en poids de 0,5 à 15%, avantageusement de 1 à 10%, de préférence de 2 à 10% d'au moins un monomère porteur d'au moins une fonction acide, sel d'acide, chlorure d'acide, époxyde, alcool ou anhydride. 17. Use according to any one of claims 1 to 16 characterized in that the functional PMMA comprises by weight from 0.5 to 15%, advantageously from 1 to 10%, preferably from 2 to 10% of at least one monomer carrying at least one acid function, acid salt, acid chloride, epoxide, alcohol or anhydride.
18. Utilisation selon l'une quelconque des revendications 1 à 16 caractérisée en ce que le PMMA fonctionnel comprend en poids : 18. Use according to any one of claims 1 to 16 characterized in that the functional PMMA comprises by weight:
• de 65 à 99,5% de MMA,  • from 65 to 99.5% of MMA,
• de 0 , 5 à 15% d'acide (méth) acrylique et/ou de l'anhydride issu de l'acide (méth) acrylique,  From 0.5 to 15% of (meth) acrylic acid and / or of the anhydride derived from (meth) acrylic acid,
• de 0 à 20% du 3eme monomère copolymérisable avec le MMA. • 0 to 20% of the 3 rd monomer copolymerizable with MMA.
19. Structure multicouche comprenant au moins une couche d'un matériau (ligno) cellulosique et le film tel que défini à l'une quelconque des revendications 1 à 18 disposé contre cette couche, la couche adhésive (III) étant disposée du côté du matériau (ligno) cellulosique . 19. Multilayer structure comprising at least one layer of a cellulosic (ligno) material and the film as defined in any one of claims 1 to 18 disposed against this layer, the adhesive layer (III) being disposed on the side of the material (ligno) cellulosic.
20. Panneau comprenant au moins une couche d'un matériau (ligno) cellulosique dont au moins l'une des deux faces externes du panneau constituée d'un matériau (ligno) cellulosique est protégée par le film multicouche tel que défini à l'une quelconque des revendications 1 à 18, la couche adhésive (III) étant disposée du côté d'au moins une desdites faces externes du panneau. 20. Panel comprising at least one layer of cellulosic (ligno) material of which at least one of the two external faces of the panel made of cellulosic (ligno) material is protected by the multilayer film as defined in one any one of claims 1 to 18, the adhesive layer (III) being disposed on the side of at least one of said external faces of the panel.
EP06842102A 2005-12-06 2006-12-06 (ligno)cellulose material board coated with a pmma and pvdf-based film Withdrawn EP1957266A2 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0512336A FR2894178A1 (en) 2005-12-06 2005-12-06 PROTECTIVE MULTILAYER FILM
PCT/FR2006/051291 WO2007066042A2 (en) 2005-12-06 2006-12-06 (ligno)cellulose material board coated with a pmma and pvdf-based film

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EP1957266A2 true EP1957266A2 (en) 2008-08-20

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EP06842102A Withdrawn EP1957266A2 (en) 2005-12-06 2006-12-06 (ligno)cellulose material board coated with a pmma and pvdf-based film

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US (1) US20080311406A1 (en)
EP (1) EP1957266A2 (en)
FR (1) FR2894178A1 (en)
WO (1) WO2007066042A2 (en)

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Also Published As

Publication number Publication date
FR2894178A1 (en) 2007-06-08
WO2007066042A3 (en) 2007-09-13
WO2007066042A2 (en) 2007-06-14
US20080311406A1 (en) 2008-12-18

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