EP1725612A1 - Thermoplastic compositions based on olefinic or styrenic polymers and alkyl (meth)acrylate copolymers and the thus obtained layers or films - Google Patents

Thermoplastic compositions based on olefinic or styrenic polymers and alkyl (meth)acrylate copolymers and the thus obtained layers or films

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Publication number
EP1725612A1
EP1725612A1 EP05734333A EP05734333A EP1725612A1 EP 1725612 A1 EP1725612 A1 EP 1725612A1 EP 05734333 A EP05734333 A EP 05734333A EP 05734333 A EP05734333 A EP 05734333A EP 1725612 A1 EP1725612 A1 EP 1725612A1
Authority
EP
European Patent Office
Prior art keywords
acrylate
alkyl
meth
ethylene
styrene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP05734333A
Other languages
German (de)
French (fr)
Inventor
Laurent Quillet
Richard Chaigneau
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 EP1725612A1 publication Critical patent/EP1725612A1/en
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • C08L23/142—Copolymers of propene at least partially crystalline copolymers of propene with other olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/06—Polystyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0869—Acids or derivatives thereof

Definitions

  • the present invention relates to thermoplastic polymer compositions comprising a blend of an olefin polymer or sty? Ene, __ particular polyethylene or polystyrene, and at least one copolymer of (meth) acrylate al yl , and films or layers obtained from them, having a soft touch. It has long been sought to improve the soft touch ("soft touch" in English) of films produced from different thermoplastic resins and in particular polyolefins.
  • EP 1 104 782 describes a film comprising a mixture comprising: - from 70 to 98% by weight of a polymer (Z) chosen from (a) a polyethylene (C) obtained by metallocene catalysis, (b) a copolymer (A) of ethylene and of a monomer chosen from vinyl acetate and an alkyl (meth) acrylate, and (c) a mixture of said polyethylene (C) and said copolymer (A), and - -from 30 to 2% by weight of high density polyethylene (HDPE).
  • a polymer (Z) chosen from (a) a polyethylene (C) obtained by metallocene catalysis, (b) a copolymer (A) of ethylene and of a monomer chosen from vinyl acetate and an alkyl (meth) acrylate, and (c) a mixture of said polyethylene (C) and said copolymer (A), and - -from 30 to 2% by weight of high density polyethylene (HD
  • anti-blocking agents such as primary fatty acid amides and talc in the form of a masterbatch based on HDPE, creates micro-roughness on the surface of the film which improves the tactile aspect of the film and gives it a silky appearance.
  • This advantage is used for the manufacture of gloves from this film.
  • Application EP 0 688 826 describes a waterproof-breathable film consisting of a mixture comprising at least one thermoplastic elastomer having polyether blocks, and at least one copolymer of ethylene and of at least one alkyl (meth) acrylate. . This film has a silky appearance. The .
  • thermoplastic composition based on olefinic polymer or of polymer based on aromatic vinyl resin, chosen in particular from polystyrene and impact polystyrene, of a copolymer of ethylene and (meth) alkyl acrylate, surprisingly brought to the film or layer obtained from this composition a surface appearance and a softer feel.
  • the invention relates to a thermoplastic composition for obtaining a film or at least one layer of a multi-layer complex, having a soft feel, comprising a mixture of an olefinic or styrene polymer, in particular of the polyethylene type.
  • polystyrene characterized in that it comprises, in mixture with said polymer, a copolymer of ethylene and of alkyl (meth) acrylate, in an amount between 1 and 50% by weight of this composition.
  • this composition comprises a content of the copolymer of ethylene and of alkyl (meth) ⁇ cryl ⁇ te, which is between 5 and 30% by weight of the composition.
  • the styrene polymer based on an aromatic vinyl resin is impact polystyrene or crystal A, or a mixture of these.
  • the olefinic polymer is high density polyethylene, or polypropylene.
  • the composition according to the invention is characterized in that the comonomer of alkyl (meth) acrylate of said ethylene copolymer comprises 0 alkyl groups having up to 24 carbon atoms, and represents up to 40% in weight of said copolymer and preferably from 3 to 35%.
  • the comonomer of alkyl (meth) acrylate is chosen from methyl acrylate and butyl acrylate.
  • compositions find a particularly advantageous application in the production of the outer layer (or film) of a multilayer complex or composite material, obtained in particular by mono or co-extrusion, and calendering; this multilayer complex is used in particular for the manufacture by thermoforming of objects or of packaging, in particular of food products, in particular dairy products, such as jars of cottage cheese, or of yogurts.
  • thermoforming of objects or of packaging in particular of food products, in particular dairy products, such as jars of cottage cheese, or of yogurts.
  • dairy products such as jars of cottage cheese, or of yogurts.
  • the soft feel given to the surface layers of the objects thus obtained is closely linked to the surface roughness of these layers, which increases compared to that of layers produced with styrenic resins.
  • Another advantage of the layers obtained with the compositions according to the invention lies in the possibility of recycling them, for example after grinding, as an intermediate layer in a composite material comprising other layers based on olefinic or styrenic resins, due to their good compatibility with the latter and the adhesion thus obtained between them.
  • vinyl aromatic monomer is understood to mean an aromatic ethylenically unsaturated monomer such as styrene, vinyltoluene, alphamethylsfyrene, methyl-4- styrene, methyl-3-styrene, methoxy-4-styrene, hydroxymethyl-2-styrene, ethyl-4-styrene, ethoxy-4-styrene, dimetfvyl-3,4-styrene, chloro-2-styrene, chloro-3-styrene, chloro-4-methyl-3-styrene, tert.-butyl-3-styrene, 5 dichloro-2,4-styrene, dichloro-2,6 -styrene and vinyl-1-naphthalene.
  • the polymer obtained is advantageously a styrene polymer.
  • a styrene polymer mention may be made of polystyrene, modified polystyrene "p ⁇ r'-el ⁇ stomers, copolymers of styrene and of acrylonitrile
  • SAN SAN
  • SAN modified by elastomers in particular ABS which is obtained - for example by grafting (graft-polymerization) "of styrene and acrylonitrile on a trunk ⁇ of polybutadiene or of butadiene-acrylonitrile copolymer " , mixtures of SAN and ABS.
  • the elastomers mentioned above may for example be EPR (abbreviation of ethylene-propylene-rubber or ethylene-propylene elastomer), EPDM (abbreviation of ethylene-propylene-diene rubber or ethylene-propylene-diene elastomer), polybutadiene, acrylonitrile-butadiene copolymer, polyisoprene, isoprene-acrylonitrile copolymer.
  • EPR abbreviation of ethylene-propylene-rubber or ethylene-propylene elastomer
  • EPDM abbreviation of ethylene-propylene-diene rubber or ethylene-propylene-diene elastomer
  • polybutadiene acrylonitrile-butadiene copolymer
  • polyisoprene polyisoprene
  • isoprene-acrylonitrile copolymer abbreviation of ethylene-propylene-rubber or ethylene-propy
  • Impact polystyrene can be obtained (i) either by mixing polystyrene with elastomers such as polybutadiene, copolymers of butadiene and acrylonitrile, polyisoprene or copolymers of isoprene and acrylonitrile (ii) or more usually by grafting of styrene (graft-polymerization) on a trunk of polybutadiene or of butadiene-acrylonitrile copolymer.
  • elastomers such as polybutadiene, copolymers of butadiene and acrylonitrile, polyisoprene or copolymers of isoprene and acrylonitrile (ii) or more usually by grafting of styrene (graft-polymerization) on a trunk of polybutadiene or of butadiene-acrylonitrile copolymer.
  • part of the styrene can be replaced by unsaturated monomers copolymerizable with styrene, by way of example, we may mention alpha-methylstyrene and (meth) acrylic esters.
  • styrene copolymers mention may also be made of chloropolystyrene, poly-alpha-methylstyrene, styrene-chlorostyrene copolymers, styrene-propylene copolymers, styrene-butadiene copolymers, styrene-isoprene copolymers, styrene-chloride copolymers vinyl, styrene-vinyl acetate copolymers, styrene-alkyl acrylate copolymers (methyl, ethyl, butyl, octyl, phenyl acrylate), styrene - alkyl methacrylate copolymers (methacrylate methyl, ethyl, butyl, phenyl), styrene-methyl chloroacrylate copolymers and styrene -
  • the comonomer content generally ranges up to 20% by weight.
  • the present invention also relates to metallocene polystyrenes with a high melting point.
  • the aromatic vinyl resin is chosen from polystyrene and impact polystyrene.
  • Polystyrene can also contain impact modifiers such as block copolymers S SB (styrene / butadiene / styrene), which are described in "Ullmann's Encyclopedia of Industrial Chemistry", Vol A 26,. pages 655 - 659.
  • the olefin polymer it is defined as a homopolymer of an olefin or a copolymer of at least one alpha-olefin and at least one other copolymerizable monomer; the alpha-olefin advantageously having from 3 to 30 carbon atoms, is for example propylene, 1 -butene, 1-pentene, 3-methyl-1 -butene, 1- hexene, 4-methyl-1-pentene, 3-methyrApentene, 1-octene, 1-dececene, 1-dodecene, 1- tetra-decene, 1-hex ⁇ -decenel-oct ⁇ decene, 1-eicocene, 1-dococene, 1-tetracocene, 1- hex ⁇ cocene, 1-oct ⁇ cocene, and -1 -tri ⁇ contene.
  • These ⁇ lph ⁇ -olefins can be used
  • LDPE low density polyethylene
  • HDPE high density polyethylene
  • LLDPE linear low density polyethylene
  • VLDPE very low density polyethylene
  • APAO essentially amorphous or attactic polyalphaolefins
  • ethylene / alpha-olefin copolymers such as ethylene / propylene, EPR (ethylene - propylene - rubber), and EPDM (ethylene - propylene - diene) elastomers, and mixtures of polyethylene with an EPR or EPDM,
  • SEBS styrene / ethylene-butene / styrene block copolymers
  • SBS styrene / butadiene / styrene
  • SIS styrene / isoprene / styrene
  • SEPS styrene / ethylene-propylene / styrene
  • unsaturated carboxylic acids such as, for example, alkyl (meth) acrylates (alkyl may have up to 24 carbon atoms)
  • terpolymers obtained by copolymerization of the preceding copolymers with unsaturated carboxylic acids, their salts or their anhydrides are in particular maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride.
  • the amount of maleic anhydride of the terpolymer can be up to 10% and preferably 0.2 to 6% by weight.
  • Terpolymers can also be formed by copolymerization of the above ethylene copolymers with unsaturated epoxides, in particular aliphatic glycidyl esters and ethers such as glycidyl acrylate and methacrylate.
  • unsaturated epoxides in particular aliphatic glycidyl esters and ethers such as glycidyl acrylate and methacrylate.
  • these are preferably chosen from alkyl (meth) acrylates, the alkyl of which may have up to 24 carbon atoms.
  • alkyl acrylate or methacrylate examples are in particular methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, ethyl-2-hexyl acrylate , cyclohexyl acrylate, n-octyl acrylate. methyl methacrylate, ethyl methocrylate, and buty methacrylate.
  • the ethylene-alkyl (meth) acrylate copolymers can be obtained by radical route under high pressure and can contain up to 60% by weight of (meth) acrylate and preferably 2 to 40%.
  • the amount of copolymer of ethylene and of alkyl (meth) acrylate introduced into the olefinic polymer or the aromatic vinyl polymer chosen in particular from crystal polystyrene and impact polystyrene, or mixtures thereof, is between 1 and 50% by weight of said composition, and preferably between 5 and 30%, and more favorably between 10 and 20%.
  • the copolymer of ethylene and of alkyl (meth) acrylate is chosen from ethylene / methyl acrylate and ethylene / butyl acrylate copolymers.
  • the composition of the invention can also comprise additives, in particular in particular, slip agents such as N, N ′ -ethylene bis amide or metal salts of fatty acids such as zinc stearates, antiblocking agents such as primary fatty acid amides, silica, talc, and the mixture of at least two of the aforementioned compounds, antioxidants, anti UV and in particular mineral fillers. Examples of realization.
  • Composition of the main layer 40/60 mixture by weight of Lacqrene® polystyrenes from ATOFINA, of grade-PS 7240 (shock) and PS 1540 (crystal).
  • Composition of the surface layer in% by weight - for test 1: 667a of the previous composition, 30% of Lotryl® 18MA02 (A) from ARKEMA, and 4% of a brown masterbatch (on PS basis), for tests 2 and 3: 81%; from the previous composition, - 15%.
  • Lotryl® 18MA02 ethylene / methyl acrylate copolymer containing 17 to 20% by weight of acrylate and MFI of between 2 and 3 (g / lOmn, measured at 190 ° C under a pressure of 2.16 kg).
  • Lotryl® 20MA08 ethylene / methyl acrylate copolymer containing from 19 to 22% by weight of acrylate and of MFI of between 7 and 9 (g / 10 min, measured at 190 ° C. under a pressure of 2.16 kg).
  • Table 1 Table 1
  • the assessment “correct appearance” for the film means that there is homogeneity of the PS / Lotryl mixture in the surface layer.
  • the scratch sensitivity indicates that the surface layer has a soft feel.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Laminated Bodies (AREA)
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Abstract

The invention relates to thermoplastic compositions for producing a film or at least one layer of a multi-layer complex which exhibits a soft-touch impression comprising a mixture of an olefinic or styrenic polymer, in particular polyethylene or polystyrene and characterised in that said compositions comprise the mixture of an ethylene and alkyl (meth)acrylate copolymer with said polymer in a quantity ranging from 1 to 50 % by weight of said compositions. Said invention is advantageously used for producing Extrusion-formed multi-layer materials comprising, in particular an external layer made of said compositions. Said multi-layer materials are used for producing thermoshaped package articles or containers, in particular for milk products, exhibiting improved soft-touch characteristics.

Description

COMPOSITIONS THERMOPLASTIQUES À BASE DE POLYMÈRES OLEFINIQUES OU STYRENIQUES ET DE COPOLYMÈRES DE (METH)ACRYLATE D'ALKYLE ET COUCHES OU FILMS AINSI OBTENUSTHERMOPLASTIC COMPOSITIONS BASED ON OLEFINIC OR STYRENIC POLYMERS AND ALKYL (METH) ACRYLATE COPOLYMERS AND LAYERS OR FILMS THUS OBTAINED
La présente invention se rapporte à des compositions de polymères thermoplastiques, comprenant' un mélange d'un polymère oléfinique ou sty?èniqùe,__ notamment du type polyethylene ou polystyrène, et d'au moins un copolymère de (méth)acrylate d'al yle, et aux films ou couches obtenus à partir de celles-ci, ayant un toucher doux. On a recherché depuis longtemps à améliorer la douceur au toucher ("soft touch" en anglais) de films réalisés à partir de différentes résines thermoplastiques et notamment des polyoléfines. Il est décrit dans la demande EP 1 104 782 un film comprenant un mélange comportant : - de70 à 98% en poids d'un polymère (Z) choisi parmi (a) un polyethylene (C) obtenu par catalyse métallocène, (b) un copolymère (A) de l'éthylène et d'un monomère choisi parmi l'acétate de vinyle et un (méth)acrylate d'alkyle, et (c) un mélange dudit polyethylene (C) et dudit copolymère (A), et - -de 30 à 2% en poids de polyethylene haute densité (HDPE). L'ajout d'agents antiblôquants tels que des amides primaires d'acide gras et du talc sous forme d'un mélange maître à base de HDPE, crée à la surface du film des micro-rugosités qui améliorent l'aspect tactile du film et lui confère un aspect soyeux. Cet avantage est utilisé pour la fabrication de gants à partir de ce film. La demande EP 0 688 826 décrit un film imper-respirant constitué d'un mélange comprenant au moins un élastomère thermoplastique ayant des blocs polyéther, et au moins un copolymère de l'éthylène et d'au moins un (méth)acrylate d'alkyle. Ce film présente un aspect soyeux. La . demanderesse a trouvé que l'introduction dans une composition thermoplastique à base de polymère oléfinique ou de polymère à base de résine vinyle aromatique, choisi en particulier parmi le polystyrène et le polystyrène choc, d'un copolymère de l'éthylène et de (méth)acrylate d'alkyle, apportait de façon surprenante au film ou à la couche obtenus à partir de cette composition un aspect de surface et un toucher plus doux. L'invention concerne une composition thermoplastique pour l'obtention d'un film ou d'au moins une couche d'un complexe multi-couches, présentant un toucher doux, comprenant un mélange d'un polymère oléfinique ou styrènique, notamment du type polyethylene ou polystyrène, caractérisée en ce qu'elle comprend en mélange avec ledit polymère un copolymère d'éthylène et de (méth)acrylate d'alkyle, en quantité comprise entre 1 et 50 % en poids de cette composition. De préférence,* cette composition comporte une teneur du copolymère d'éthylène et de (méth)αcrylαte d'alkyle, qui est comprise entre 5 et 30% en poids de la composition. En particulier, le polymère styrènique à base de résine vinyle aromatique est du A polystyrène choc ou cristal, ou un mélange de ceux-ci. En outre, le polymère oléfinique est du polyethylene haute densité, ou du polypropylène. En particulier, la composition selon l'invention est caractérisée en ce que le comonomère de (méth)acrylate d'alkyle dudit copolymère d'éthylène comprend des0 groupes alkyle ayant jusqu'à 24 atomes de carbone, et représente jusqu'à 40% en poids dudit copolymère et de préférence de 3 à 35%. De préférence, dans cette composition le comonomère de (méth)acrylate d'alkyle est choisi parmi l'acrylate de méthyle et l'acrylate de butyle. Ces compositions trouvent une application particulièrement avantageuse dans5 la réalisation de la couche (ou film) externe d'un complexe multicouches ou matériau composite, obtenu notamment par mono ou co-extrusion, et calandrage ; ce complexe multicouches est utilisé en particulier pour la fabrication par thermoformage d'objets ou d'emballages, en particulier de produits alimentaires, notamment laitiers, tels que les pots de fromage blanc, ou de yaourts. On peut utiliser aussi un procédé de fabrication de ces0 objets par moulage par injection. Le toucher doux conféré aux couches de surface des objets ainsi obtenus est étroitement lié à la rugosité de surface de ces couches, qui augmente par rapport à celle de couches réalisées avec des résines styréniques. Un autre avantage des couches obtenues avec les compositions selon5 l'invention réside dans la possibilité de leur recyclage, par exemple après broyage, comme couche intermédiaire dans un matériau composite comprenant d'autres couches à base de résines oléfiniques ou styréniques, du fait de leur bonne compatibilité avec ces dernières et de l'adhésion ainsi obtenue entre elles . S'agissanl du polymère styrènique obtenu à base de résine vinyle aromatique,0 au sens de la présente invention, on entend par monomère vinylaromatiqυe un monomère aromatique à insaturation éthylénique tel que le styrène, le vinyltoluène, l'alphaméthylsfyrène, le méthyl-4-styrène, le méthyl-3-styrène, le méthoxy-4-styrène, l'hydroxyméthyl-2-styrène, l'éthyl-4-styrène, l'éthoxy-4-styrène, le dimétfvyl-3,4-styrène, le chloro-2-styrène, le chloro-3-styrène, le chloro-4-méthyl-3-styrène, le tert.-butyl-3-styrène,5 le dichloro-2,4-styrène, le dichloro-2,6-styrène et le vinyl-1-naphtalène. Le polymère obtenu est avantageusement un polymère styrènique. A' titre- d'exemple de polymère styrènique on peut citer le polystyrène, le polystyrène modifié" pαr'-des élαstomères, les copolymères du styrène et de l'αcrylonitrileThe present invention relates to thermoplastic polymer compositions comprising a blend of an olefin polymer or sty? Ene, __ particular polyethylene or polystyrene, and at least one copolymer of (meth) acrylate al yl , and films or layers obtained from them, having a soft touch. It has long been sought to improve the soft touch ("soft touch" in English) of films produced from different thermoplastic resins and in particular polyolefins. EP 1 104 782 describes a film comprising a mixture comprising: - from 70 to 98% by weight of a polymer (Z) chosen from (a) a polyethylene (C) obtained by metallocene catalysis, (b) a copolymer (A) of ethylene and of a monomer chosen from vinyl acetate and an alkyl (meth) acrylate, and (c) a mixture of said polyethylene (C) and said copolymer (A), and - -from 30 to 2% by weight of high density polyethylene (HDPE). The addition of anti-blocking agents such as primary fatty acid amides and talc in the form of a masterbatch based on HDPE, creates micro-roughness on the surface of the film which improves the tactile aspect of the film and gives it a silky appearance. This advantage is used for the manufacture of gloves from this film. Application EP 0 688 826 describes a waterproof-breathable film consisting of a mixture comprising at least one thermoplastic elastomer having polyether blocks, and at least one copolymer of ethylene and of at least one alkyl (meth) acrylate. . This film has a silky appearance. The . Applicant has found that the introduction into a thermoplastic composition based on olefinic polymer or of polymer based on aromatic vinyl resin, chosen in particular from polystyrene and impact polystyrene, of a copolymer of ethylene and (meth) alkyl acrylate, surprisingly brought to the film or layer obtained from this composition a surface appearance and a softer feel. The invention relates to a thermoplastic composition for obtaining a film or at least one layer of a multi-layer complex, having a soft feel, comprising a mixture of an olefinic or styrene polymer, in particular of the polyethylene type. or polystyrene, characterized in that it comprises, in mixture with said polymer, a copolymer of ethylene and of alkyl (meth) acrylate, in an amount between 1 and 50% by weight of this composition. Preferably, * this composition comprises a content of the copolymer of ethylene and of alkyl (meth) αcrylαte, which is between 5 and 30% by weight of the composition. In particular, the styrene polymer based on an aromatic vinyl resin is impact polystyrene or crystal A, or a mixture of these. In addition, the olefinic polymer is high density polyethylene, or polypropylene. In particular, the composition according to the invention is characterized in that the comonomer of alkyl (meth) acrylate of said ethylene copolymer comprises 0 alkyl groups having up to 24 carbon atoms, and represents up to 40% in weight of said copolymer and preferably from 3 to 35%. Preferably, in this composition the comonomer of alkyl (meth) acrylate is chosen from methyl acrylate and butyl acrylate. These compositions find a particularly advantageous application in the production of the outer layer (or film) of a multilayer complex or composite material, obtained in particular by mono or co-extrusion, and calendering; this multilayer complex is used in particular for the manufacture by thermoforming of objects or of packaging, in particular of food products, in particular dairy products, such as jars of cottage cheese, or of yogurts. One can also use a method of manufacturing these objects by injection molding. The soft feel given to the surface layers of the objects thus obtained is closely linked to the surface roughness of these layers, which increases compared to that of layers produced with styrenic resins. Another advantage of the layers obtained with the compositions according to the invention lies in the possibility of recycling them, for example after grinding, as an intermediate layer in a composite material comprising other layers based on olefinic or styrenic resins, due to their good compatibility with the latter and the adhesion thus obtained between them. As regards the styrene polymer obtained based on aromatic vinyl resin, 0 within the meaning of the present invention, the term vinyl aromatic monomer is understood to mean an aromatic ethylenically unsaturated monomer such as styrene, vinyltoluene, alphamethylsfyrene, methyl-4- styrene, methyl-3-styrene, methoxy-4-styrene, hydroxymethyl-2-styrene, ethyl-4-styrene, ethoxy-4-styrene, dimetfvyl-3,4-styrene, chloro-2-styrene, chloro-3-styrene, chloro-4-methyl-3-styrene, tert.-butyl-3-styrene, 5 dichloro-2,4-styrene, dichloro-2,6 -styrene and vinyl-1-naphthalene. The polymer obtained is advantageously a styrene polymer. As an example of a styrene polymer, mention may be made of polystyrene, modified polystyrene "pαr'-elαstomers, copolymers of styrene and of acrylonitrile
(SAN), le SAN modifié par des élastomères en particulier l'ABS qu'on obtient- par exemple par greffage (graft-polymérisation) "de styrène et d'acrylonitrile sur un tronc ~de polybutadiène ou de copolymère butadiène-acrylonitrile", les mélanges de SAN et d'ABS.(SAN), the SAN modified by elastomers in particular ABS which is obtained - for example by grafting (graft-polymerization) "of styrene and acrylonitrile on a trunk ~ of polybutadiene or of butadiene-acrylonitrile copolymer " , mixtures of SAN and ABS.
Les élastomères mentionnés ci dessus peuvent être par exemple l'EPR (abréviation d'éthylène-propylène-rubber ou élastomère éthylène-propylene), l'EPDM (abréviation d'éthylène-propylene-diène rubber ou élastomère éthylène-propylene-diène), le polybutadiène, le copolymère acrylonitrile-butadiène, le polyisoprène, le copolymère isoprène-acrylonitrile. Le polystyrène choc peut être obtenu (i) soit par mélange de polystyrène avec des élastomères tels que le polybutadiène, des copolymères du butadiène et de l'acrylonitrile, du polyisoprène ou des copolymères de l'isoprène et de l'acrylonitrile (ii) soit plus habituellement par greffage de styrène (graft-polymérisation) sur un tronc de polybutadiène ou de copolymère butadiène-acrylonitrile. Dans les polymères styréniques qu'on vient de citer une partie du styrène peut être remplacée par des monomères insaturés copolymèrisables avec le styrène, à titre d'exemple on peut citer l'alpha-méthylstyrène et les esters (méth)acryliques. Comme exemples des copolymères du styrène, on peut encore citer le chloropolystyrène, le poly- alpha-méthylstyrène, les copolymères styrène-chlorostyrène, les copolymères styrène- propylène, les copolymères styrène-butadiène, les copolymères styrène-isoprène, les copolymères styrène-chlorure de vinyle, les copolymères styrène-acétate de vinyle, les copolymères styrène-acrylate d'alkyle (acrylate de méthyle, d'éthyle, de butyie, d'octyle, de phényle), les copolymères styrène - méthacrylate d'alkyle (méthacrylate de méthyle, d'éthyle, de butyie, de phényle), les copolymères styrène -chloroacrylate de méthyle et les copolymères styrène - acrylonitrile - acrylate d'alkyle. Dans ces copolymères, la teneur en comonomères va généralement jusqu'à 20% en poids. La présente invention concerne aussi des polystyrènes metallocènes à haut point de fusion. Avantageusement la résine vinyle aromatique est choisie parmi le polystyrène et le polystyrène choc. Le polystyrène peut aussi contenir des modifiants choc tels que des copolymères-blocs S- B-S, (styrène/ butadiène/styrène) qui sont décrits dans « Ullmann's Encyclopedia of Industrial Chemistry », Vol A 26,. pages 655 - 659. S'agissant du polymère oléfinique, on le définit comme un homopolymère d'une oléfine ou un copolymère d'au moins une alpha-oléfine et d'au moins un autre monomère copolymérisable; l'alpha-oléfine ayant avantageusement de 3 à 30 atomes de carbone, est par exemple le propylène, 1 -butène, 1-pentène, 3-méthyl-l -butène, 1- hexène, 4-méthyl-l-pentène, 3-méthyrApentène, 1-octène, 1 -décène, 1-dodécène, 1- tétrαdécène, 1-hexαdécènerl-octαdécène, 1-eicocène, 1-dococène, 1-tétrαcocène, 1- hexαcocène, 1-octαcocène, et -1 -triαcontène. Ces αlphα-oléfines peuvent être utilisées seules ou en mélange de deux ou de-plus de deux. A titre d'exemples, on peut citer :The elastomers mentioned above may for example be EPR (abbreviation of ethylene-propylene-rubber or ethylene-propylene elastomer), EPDM (abbreviation of ethylene-propylene-diene rubber or ethylene-propylene-diene elastomer), polybutadiene, acrylonitrile-butadiene copolymer, polyisoprene, isoprene-acrylonitrile copolymer. Impact polystyrene can be obtained (i) either by mixing polystyrene with elastomers such as polybutadiene, copolymers of butadiene and acrylonitrile, polyisoprene or copolymers of isoprene and acrylonitrile (ii) or more usually by grafting of styrene (graft-polymerization) on a trunk of polybutadiene or of butadiene-acrylonitrile copolymer. In the styrenic polymers which have just been mentioned, part of the styrene can be replaced by unsaturated monomers copolymerizable with styrene, by way of example, we may mention alpha-methylstyrene and (meth) acrylic esters. As examples of the styrene copolymers, mention may also be made of chloropolystyrene, poly-alpha-methylstyrene, styrene-chlorostyrene copolymers, styrene-propylene copolymers, styrene-butadiene copolymers, styrene-isoprene copolymers, styrene-chloride copolymers vinyl, styrene-vinyl acetate copolymers, styrene-alkyl acrylate copolymers (methyl, ethyl, butyl, octyl, phenyl acrylate), styrene - alkyl methacrylate copolymers (methacrylate methyl, ethyl, butyl, phenyl), styrene-methyl chloroacrylate copolymers and styrene - acrylonitrile - alkyl acrylate copolymers. In these copolymers, the comonomer content generally ranges up to 20% by weight. The present invention also relates to metallocene polystyrenes with a high melting point. Advantageously, the aromatic vinyl resin is chosen from polystyrene and impact polystyrene. Polystyrene can also contain impact modifiers such as block copolymers S SB (styrene / butadiene / styrene), which are described in "Ullmann's Encyclopedia of Industrial Chemistry", Vol A 26,. pages 655 - 659. As regards the olefin polymer, it is defined as a homopolymer of an olefin or a copolymer of at least one alpha-olefin and at least one other copolymerizable monomer; the alpha-olefin advantageously having from 3 to 30 carbon atoms, is for example propylene, 1 -butene, 1-pentene, 3-methyl-1 -butene, 1- hexene, 4-methyl-1-pentene, 3-methyrApentene, 1-octene, 1-dececene, 1-dodecene, 1- tetra-decene, 1-hexα-decenel-octαdecene, 1-eicocene, 1-dococene, 1-tetracocene, 1- hexαcocene, 1-octαcocene, and -1 -triαcontene. These αlphα-olefins can be used alone or as a mixture of two or more than two. As examples, we can cite:
- les homopolymères et copolymères de l'éthylène, en particulier : le polyethylene basse densité (LDPE), le polyethylene haute densité (HDPE), le polyethylene linéaire basse densité (LLDPE), le polyethylene très basse densité (VLDPE), le polyethylene obtenu par catalyse métallocène.- homopolymers and copolymers of ethylene, in particular: low density polyethylene (LDPE), high density polyethylene (HDPE), linear low density polyethylene (LLDPE), very low density polyethylene (VLDPE), the polyethylene obtained by metallocene catalysis.
- les homopolymères et copolymères du propylène,- propylene homopolymers and copolymers,
- les polyalphaoléfines essentiellement amorphes ou attactiques (APAO),- essentially amorphous or attactic polyalphaolefins (APAO),
- les copolymères éthylène/alpha-oléfine tels qu'éthylène/propylène, les élastomères EPR (éthylène - propylène - rubber), et EPDM (éthylène - propylène - diène), et les mélanges de polyethylene avec un EPR ou un EPDM,- ethylene / alpha-olefin copolymers such as ethylene / propylene, EPR (ethylene - propylene - rubber), and EPDM (ethylene - propylene - diene) elastomers, and mixtures of polyethylene with an EPR or EPDM,
- les copolymères blocs styrène/éthylène- butène/styrène (SEBS), styrène/ butadiène/styrène (SBS), styrène/ isoprène/styrène (SIS), et styrène/éthylène- propylène/styrène (SEPS), - les copolymères de l'éthylène avec au moins un produit choisi parmi les sels ou les esters d'acides carboxyliques insaturés tels que par exemple les (méth)acrylates d'alkyle, (l'alkyle pouvant avoir jusqu'à 24 atomes de carbone), les esters vinyliques d'acides carboxyliques saturés tels que par exemple l'acétate ou le propionate de vinyle, et les diènes tels que par exemple le 1 ,4-hexadiène. On peut aussi utiliser avantageusement des terpolymères obtenus par copolymérisation des copolymères précédents avec des acides carboxyliques insaturés, leurs sels, ou leurs anhydrides. Des exemples d'anhydrides d'acide dicarboxylique insaturé sont notamment l'anhydride maléique, l'anhydride itaconique, l'anhydride citraconique, l'anhydride tétrahydrophtalique. La quantité d'anhydride maléique du terpolymère peut aller jusqu'à 10% et de préférence 0,2 à 6% en poids. On peut également former des terpolymères par copolymérisation des copolymères d'éthylène précédents avec des époxydes insaturés, notamment des esters et éthers de glycidyle aliphatiques tels que l'acrylate et le méthacrylate de gîycidyle. S'agissant du copolymère de l'éthylène et d'esters d'acides carboxyliques insaturés (ou leurs sels), ceux-ci sont choisis de préférence parmi les (méth)acrylates d'alkyle, dont l'alkyle peut avoir jusqu'à 24 atomes de carbone. Des exemples d'αcrylαte ou méthacrylate d'alkyle sont notamment l'acrylate de méthyle, l'acrylate d'éthyle, il'acrylate de n-butyle, l'acrylate d'isobutyle, l'acrylate d'éthyl-2-hexyle, l'acrylate de cyclohexyle, l'acrylate de n-octyle. le méthacrylate de- méthyle, le méthocrylate d'éthyle, et le méthacrylate de butyie. Les copolymères éthylène-(méth)acrylate d'alkyle peuvent être obtenus par voie radicalaire sous haute pression et peuvent contenir jusqu'à 60% en poids de (méth) acrylate et de préférence 2 à 40%. Leur MFI (Melt Flow Index ou Indice de fluidité) est avantageusement compris entre 1 et 2000 g/ 10 mn, et de préférence entre 60 et 1000 (mesuré à 1 0°C sous une pression de 2,16 kg selon la norme ASTM D 1238). Dans la composition selon l'invention, la quantité de copolymère d'éthylène et de (méth)acrylate d'alkyle introduite dans le polymère oléfinique ou le polymère vinyle aromatique choisi en particulier parmi le polystyrène cristal et le polystyrène choc, ou leurs mélanges, est comprise entre 1 et 50 % en poids de ladite composition, et de préférence entre 5 et 30%, et plus favorablement entre 10 et 20%. De préférence, le copolymère d'éthylène et de (méth)acrylate d'alkyle, est choisi parmi les copolymères éthylène/acrylate de méthyle et éthylène/acrylate de butyie En outre, la composition de l'invention peut aussi comprendre des additifs, en particulier, des agents glissants tels que des N,N '-éthylène bis amide ou des sels métalliques d'acides gras tels que les stéarates de zinc, des agents antibloquants tels que des amides primaires d'acide gras, la silice, le talc, et le mélange d'au moins deux des composés précité, des antioxydants, des anti U.V. et des charges notamment minérales. Exemples de réalisation. Des essais d' extrusion de films bi-couches ont été réalisés sur une ligne d' extrusion AMUT dont la filière plate de largeur 650 mm est alimentée par deux extrudeuses, ayant des profils de température de 200 à 220°C, l'une fournissant du polystyrène (PS) pour la couche principale (d'épaisseur comprise entre 600 et 650μm) et l'autre un mélange de polystyrène et de Lotryl pour former la couche de surface (d'épaisseur de 150μm). En sortie de filière les couches passent dans une calandre dont les cylindres sont à une température de 40°C, la vitesse de ligne étant de 4.1 m/mn. Des bobines sont obtenues ayant une laize de 470 mm.- styrene / ethylene-butene / styrene block copolymers (SEBS), styrene / butadiene / styrene (SBS), styrene / isoprene / styrene (SIS), and styrene / ethylene-propylene / styrene (SEPS), - copolymers of l ethylene with at least one product chosen from the salts or esters of unsaturated carboxylic acids such as, for example, alkyl (meth) acrylates (alkyl may have up to 24 carbon atoms), vinyl esters saturated carboxylic acids such as, for example, vinyl acetate or propionate, and dienes such as, for example, 1,4-hexadiene. It is also advantageous to use terpolymers obtained by copolymerization of the preceding copolymers with unsaturated carboxylic acids, their salts or their anhydrides. Examples of unsaturated dicarboxylic acid anhydrides are in particular maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride. The amount of maleic anhydride of the terpolymer can be up to 10% and preferably 0.2 to 6% by weight. Terpolymers can also be formed by copolymerization of the above ethylene copolymers with unsaturated epoxides, in particular aliphatic glycidyl esters and ethers such as glycidyl acrylate and methacrylate. As regards the copolymer of ethylene and of esters of unsaturated carboxylic acids (or their salts), these are preferably chosen from alkyl (meth) acrylates, the alkyl of which may have up to 24 carbon atoms. Examples of alkyl acrylate or methacrylate are in particular methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, ethyl-2-hexyl acrylate , cyclohexyl acrylate, n-octyl acrylate. methyl methacrylate, ethyl methocrylate, and buty methacrylate. The ethylene-alkyl (meth) acrylate copolymers can be obtained by radical route under high pressure and can contain up to 60% by weight of (meth) acrylate and preferably 2 to 40%. Their MFI (Melt Flow Index) is advantageously between 1 and 2000 g / 10 min, and preferably between 60 and 1000 (measured at 10 ° C. under a pressure of 2.16 kg according to ASTM D standard 1238). In the composition according to the invention, the amount of copolymer of ethylene and of alkyl (meth) acrylate introduced into the olefinic polymer or the aromatic vinyl polymer chosen in particular from crystal polystyrene and impact polystyrene, or mixtures thereof, is between 1 and 50% by weight of said composition, and preferably between 5 and 30%, and more favorably between 10 and 20%. Preferably, the copolymer of ethylene and of alkyl (meth) acrylate, is chosen from ethylene / methyl acrylate and ethylene / butyl acrylate copolymers. In addition, the composition of the invention can also comprise additives, in particular in particular, slip agents such as N, N ′ -ethylene bis amide or metal salts of fatty acids such as zinc stearates, antiblocking agents such as primary fatty acid amides, silica, talc, and the mixture of at least two of the aforementioned compounds, antioxidants, anti UV and in particular mineral fillers. Examples of realization. Extrusion tests of two-layer films were carried out on an AMUT extrusion line, the flat die of width 650 mm being fed by two extruders, having temperature profiles from 200 to 220 ° C, one providing polystyrene (PS) for the main layer (thickness between 600 and 650 μm) and the other a mixture of polystyrene and Lotryl to form the surface layer (thickness of 150 μm). At the outlet of the die, the layers pass through a calender, the cylinders of which are at a temperature of 40 ° C., the line speed being 4.1 m / min. Coils are obtained having a width of 470 mm.
Composition de la couche principale : mélange 40/60 en poids de polystyrènes Lacqrene ® de ATOFINA, de grade-PS 7240 (choc) et PS 1540 (cristal). Composition de la couche de surface en %poids: - pour l'essai 1 : 667a de la composition précédente, 30% de Lotryl® 18MA02 (A) de ARKEMA, et 4% d'un mélange maître marron (sur base PS), pour les -essais 2 -et 3 : 81%; de la composition précédente,- 15%. de Lotryl®' 8MA02 (A) de ARKEMA; et .4% du même mélange maître, pour l'essai-4 ; 81% de la composition précédente-,: 15% de Lotryl® 20MA08 (B) de ARKEMA, et 4% du même mélange maître.Composition of the main layer: 40/60 mixture by weight of Lacqrene® polystyrenes from ATOFINA, of grade-PS 7240 (shock) and PS 1540 (crystal). Composition of the surface layer in% by weight: - for test 1: 667a of the previous composition, 30% of Lotryl® 18MA02 (A) from ARKEMA, and 4% of a brown masterbatch (on PS basis), for tests 2 and 3: 81%; from the previous composition, - 15%. Lotryl® '8MA02 (A) from ARKEMA; and .4% of the same masterbatch, for test-4; 81% of the previous composition, 15% Lotryl® 20MA08 (B) from ARKEMA, and 4% of the same masterbatch.
Lotryl® 18MA02 copolymère éthylène/acrylate de méthyle contenant de 17 à 20% en poids d'acrylate et de MFI compris entre 2 et 3 (g/lOmn, mesuré à 190°C sous une pression de 2.16kg). Lotryl® 20MA08 : copolymère éthylène/acrylate de méthyle contenant de 19 à 22% en poids d'acrylate et de MFI compris entre 7 et 9 (g/lOmn, mesuré à 190°C sous une pression de 2.16kg). Les caractéristiques des couches obtenues sont indiquées dans le tableau 1 ci-après : Tableau 1Lotryl® 18MA02 ethylene / methyl acrylate copolymer containing 17 to 20% by weight of acrylate and MFI of between 2 and 3 (g / lOmn, measured at 190 ° C under a pressure of 2.16 kg). Lotryl® 20MA08: ethylene / methyl acrylate copolymer containing from 19 to 22% by weight of acrylate and of MFI of between 7 and 9 (g / 10 min, measured at 190 ° C. under a pressure of 2.16 kg). The characteristics of the layers obtained are shown in Table 1 below: Table 1
L'appréciation « aspect correct » pour le film signifie qu'il y a homogénéité du mélange PS/Lotryl dans la couche de surface. La sensibilité à la rayure indique que la couche de surface présente un toucher doux. The assessment “correct appearance” for the film means that there is homogeneity of the PS / Lotryl mixture in the surface layer. The scratch sensitivity indicates that the surface layer has a soft feel.

Claims

REVENDICATIONS
1. Composition thermoplαstique-pour l'obtention d'un film ou d'au moins une couche d'un complexe multi-couches, présentant un toucher doux, comprenant un mélange d'un polymère oléfinique ou styrènique, notamment du type polyethylene ou polystyrène, caractérisée en ce qu'elle comprend en mélange avec ledit polymère un copolymère d'éthylène et de (méth)acrylate d'alkyle, en quantité comprise entre 1 et 50 % en poids de cette composition.1. Thermoplastic composition - for obtaining a film or at least one layer of a multi-layer complex, having a soft feel, comprising a mixture of an olefinic or styrene polymer, in particular of the polyethylene or polystyrene type , characterized in that it comprises, in mixture with said polymer, a copolymer of ethylene and of alkyl (meth) acrylate, in an amount between 1 and 50% by weight of this composition.
2. Composition selon la revendication 1 , caractérisée en ce que la teneur du copolymère d'éthylène et de (méth)acrylate d'alkyle, est comprise entre 5 et 30% en poids de la composition.2. Composition according to Claim 1, characterized in that the content of the copolymer of ethylene and of alkyl (meth) acrylate is between 5 and 30% by weight of the composition.
3. Composition selon les revendications 1 et 2, caractérisée en ce que le polymère styrènique à base de résine vinyle aromatique est du polystyrène choc ou cristal, ou un mélange de ceux-ci.3. Composition according to claims 1 and 2, characterized in that the styrene polymer based on aromatic vinyl resin is impact polystyrene or crystal, or a mixture thereof.
4. Composition selon les revendications 1 et 2, caractérisée en ce que le polymère oléfinique est du polyethylene haute densité, ou du polypropylène.4. Composition according to claims 1 and 2, characterized in that the olefinic polymer is high density polyethylene, or polypropylene.
Composition selon l'une des revendications 1 à 4, caractérisée en ce que le comonomère de (méth)acrylate d'alkyle dudit copolymère d'éthylène comprend des groupes alkyle ayant jusqu'à 24 atomes de carbone, et représente jusqu'à 40% en poids dudit copolymère et de préférence de 3 à 35%.Composition according to one of Claims 1 to 4, characterized in that the alkyl (meth) acrylate comonomer of the said ethylene copolymer comprises alkyl groups having up to 24 carbon atoms, and represents up to 40% by weight of said copolymer and preferably from 3 to 35%.
Composition selon la revendication 5, caractérisée en ce que le comonomère de (méth)acrylate d'alkyle est choisi parmi l'acrylate de méthyle et l'acrylate de butyie.Composition according to Claim 5, characterized in that the comonomer of alkyl (meth) acrylate is chosen from methyl acrylate and buty acrylate.
7. Utilisation de la composition selon l'une quelconque des revendications précédentes, pour la fabrication de la couche externe ou de surface d'un complexe multicouches obtenu par mono ou co-extrusion.7. Use of the composition according to any one of the preceding claims, for the manufacture of the external or surface layer of a multilayer complex obtained by mono or co-extrusion.
8. Utilisation du._complexe. multicouches dont la couche externe est obtenue selon la revendication 7, pour la fabrication par thermoformage d'objets ou d'emballages de produits alimentaires, en particulier laitiers, tels que les pots de fromage blanc. Utilisation du complexe multicouches dont la couche externe est obtenue selon la revendication 7, pour la fabrication par moulage par injection d'objets ou d'emballages de produits alimentaires, en particulier laitiers, tels que les pots de fromage blanc. 8. Use of the complex. multilayers, the outer layer of which is obtained according to claim 7, for the manufacture by thermoforming of objects or packages of food products, in particular dairy products, such as jars of cottage cheese. Use of the multilayer complex, the outer layer of which is obtained according to claim 7, for the manufacture by injection molding of objects or packaging of food products, in particular dairy products, such as jars of fromage blanc.
EP05734333A 2004-03-05 2005-03-03 Thermoplastic compositions based on olefinic or styrenic polymers and alkyl (meth)acrylate copolymers and the thus obtained layers or films Pending EP1725612A1 (en)

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PCT/FR2005/000513 WO2005087861A1 (en) 2004-03-05 2005-03-03 Thermoplastic compositions based on olefinic or styrenic polymers and alkyl (meth)acrylate copolymers and the thus obtained layers or films

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