FR2839976A1 - Polymer composition for injection molded article, e.g. bag, comprises cyclic olefin polymer, and syndiotactic polypropylene - Google Patents

Polymer composition for injection molded article, e.g. bag, comprises cyclic olefin polymer, and syndiotactic polypropylene Download PDF

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Publication number
FR2839976A1
FR2839976A1 FR0204644A FR0204644A FR2839976A1 FR 2839976 A1 FR2839976 A1 FR 2839976A1 FR 0204644 A FR0204644 A FR 0204644A FR 0204644 A FR0204644 A FR 0204644A FR 2839976 A1 FR2839976 A1 FR 2839976A1
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layer
copolymers
ethylene
sebs
seps
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FR2839976B1 (en
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Petrus J A Karsten
Vries Piet De
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Solvay SA
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Solvay SA
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Priority to FR0204644A priority Critical patent/FR2839976B1/en
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Priority to US10/515,061 priority patent/US20050238830A1/en
Priority to JP2004506407A priority patent/JP4209384B2/en
Priority to EP03752732A priority patent/EP1509569A1/en
Priority to AU2003232758A priority patent/AU2003232758A1/en
Priority to PCT/EP2003/004953 priority patent/WO2003097739A1/en
Priority to CNB038113856A priority patent/CN1303148C/en
Priority to KR1020047018695A priority patent/KR100933434B1/en
Priority to TW092113240A priority patent/TW200400212A/en
Publication of FR2839976A1 publication Critical patent/FR2839976A1/en
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    • 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
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • C08L23/0823—Copolymers of ethene with aliphatic cyclic olefins
    • 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
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/10—Peculiar tacticity
    • C08L2207/12—Syndiotactic polypropylene
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • 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
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1334—Nonself-supporting tubular film or bag [e.g., pouch, envelope, packet, etc.]

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Manufacturing & Machinery (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Laminated Bodies (AREA)
  • Wrappers (AREA)
  • Medical Preparation Storing Or Oral Administration Devices (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

A polymer composition comprises a cyclic olefin polymer; and syndiotactic polypropylene.

Description

1 5 raffinage.1 5 refining.

:ti Composition polymere comportant un copolymere olefinique cyclique La presente invention a trait a une composition polymere comportant un copolymere olefinique cyclique, a un film comportant une couche comprenant  The present invention relates to a polymer composition comprising a cyclic olefinic copolymer, to a film comprising a layer comprising

cette composition, et a des applications specifiques de celui-ci.  this composition, and to specific applications thereof.

Les articles destines a des applications medicales dolvent satisfaire non seulement des conditions classiques, telles qutune bonne resistance mecanique et un faible cout, mais egalement des conditions extremement skictes specifiques a ce champ d' application specifique, telles que par exemple, les conditions ayant trait aux proprietes de biocompatibilite desdits articles, leur capacite a etre soumis a un traitement de sterilisation, leur souplesse, leur transparence, leur soudabilite, leur resistance aux chocs (y compris en ce qu concerne les recipients remplis de liquide), la quantite de substances extractibles (par exemple, avec de  Articles intended for medical applications must satisfy not only conventional conditions, such as good mechanical resistance and low cost, but also extremely strict conditions specific to this specific field of application, such as, for example, the conditions relating to biocompatibility properties of said articles, their capacity to be subjected to a sterilization treatment, their flexibility, their transparency, their weldability, their impact resistance (including as regards containers filled with liquid), the quantity of extractable substances ( for example, with

l'hexane) et dans certains cas, leurs proprietes barriere.  hexane) and in some cases, their barrier properties.

Jusquta present, les articles disponibles dans le commerce destines un usage medical, par exemple les sacs de perfilsion ou de sang, et les sacs destines a conserver des fluides en rapport avec la medecine, ont ete bases sur des  Hitherto, commercially available articles for medical use, for example perfusion or blood bags, and bags for storing fluids related to medicine, have been based on

polymeres du chlorure de vinyle, par exemple sur le PVC.  vinyl chloride polymers, for example on PVC.

Bien que presentant plusieurs avantages, ce type de polymere presente toutefois ceriains inconvenients, tels gue le besoin d'incorporer de grandes quantites de stabilisants dans celui-ci, en vue d'ameliorer sa stabilite thermique, ou d'incorporer de grandes quantites de plastifiants dans celui-ci, dans le but d'obtenir une souplesse suffisante. En consequence, il existe une demande sur le marche pour des articles destines aux applications medicales, qui vent exempts  Although having several advantages, this type of polymer has certain drawbacks, however, such as the need to incorporate large amounts of stabilizers therein, in order to improve its thermal stability, or to incorporate large amounts of plasticizers in it, in order to obtain sufficient flexibility. Consequently, there is a demand in the market for articles intended for medical applications, which are exempt.

de polymeres chlores.of chlorinated polymers.

Pour obtenir de tels articles, il est connu de partir de films a base de polyolefines et de les souder entre eux (ou sur eux-memes) afin de fabriquer des sacs ou des poches. La demande de brevet WO 00/61062 au nom de SOLVY decrit de tels films qui peuvent comprendre un polymere olefinique cyclique (COP). Toutefois, le demandeur a trouve que lorsqu'on emplole un COP seul (a savoir, en tent que constituent pur d'un film ou d'une couche de celui-ci), le soudage est tres difficile et les soudures obtenues vent d'une qualite mediocre, en p arti culi er avec l es durees de s oudage courses employees couramment dans l es - 2 procedes industrials. En outre, la sterilisation par la chaleur, la transparence et la souplesse ne vent pas optimales lorsqu'on emploie du COP pur, meme en une senle couche d'une structure multicouches. Plus particulierement, les structures multicouches comportant une couche pure de COP ont tendance a s'exfolier apres une sterilisation par la chaleur. Le demandeur a trouve que, de facon etonnante, lorsqu'on ajoute un polypropylene syndiotactique (s-PP) a un COP, ce dernier devient tres facile a souder et permet de fabriquer des sacs ou des poches medicales que lton peut steriliser par la chaleur, qui vent et restent (apres sterilisation) transparents, couples, ont une resistance elevee aux chocs, et par ailleurs presentent d'excellentes proprietes barriere (a savoir, a la vapeur d'eau, aux acides et aux alcools) et ne presentent aucune exfoliation apres sterilisation par la chaleur dans le cas d'une structure multicouches. D'autre part, le s-PP est obtenu par l'intermediaire de catalyseurs metallocenes, de sorte qu'il presente une faible quantite de composes extractibles, et moins de residue catalytiques que d'autres  To obtain such articles, it is known to start from films based on polyolefins and to weld them together (or on themselves) in order to make bags or pockets. Patent application WO 00/61062 in the name of SOLVY describes such films which can comprise a cyclic olefin polymer (COP). However, the applicant has found that when a COP is used alone (that is to say, as a pure film or a layer thereof), the welding is very difficult and the welds obtained are a mediocre quality, in particular with the durations of seaming courses commonly used in es - 2 industrial processes. In addition, heat sterilization, transparency and flexibility are not optimal when using pure COP, even in a single layer of a multilayer structure. More particularly, multilayer structures comprising a pure layer of COP tend to exfoliate after sterilization by heat. The applicant has found that, surprisingly, when a syndiotactic polypropylene (s-PP) is added to a COP, the latter becomes very easy to weld and makes it possible to manufacture medical bags or pouches which can be sterilized by heat. , which wind and remain (after sterilization) transparent, couples, have a high resistance to shocks, and on the other hand have excellent barrier properties (namely, water vapor, acids and alcohols) and exhibit no exfoliation after sterilization by heat in the case of a multilayer structure. On the other hand, s-PP is obtained through metallocene catalysts, so that it presents a small quantity of extractable compounds, and less catalytic residue than others.

resines PP obtenues par l'intermediaire de catalyseurs non metallocenes.  PP resins obtained through non-metallocene catalysts.

En consequence, la presente invention a trait a une composition polymere  Accordingly, the present invention relates to a polymer composition

comprenant un COP et un s-PP.including a COP and an s-PP.

I1 est entendu que le terme "COP" designe un homo- ou un copolymere d'un monomere cyclique en C5 a C2, et/ou d'un monomere dicyclique (dimere), qui peut porter des chanes laterales de sorte a atteindre un total de 5 a 30 atomes de C. Generalement, les copolymeres comportent en plus du monomere cyclique, une oleLme en C2 a CIO, en une teneur respective de 2 a 95% (de preference de 10 a 80%) en poids, pour le monomere cyclique, et de 5 a 98% (de preference de 20 a 90%) en poids, pour l'olefne. Le motif monomere cyclique de base peut etre un cyclopentene, cyclohexene, norbornene, dicyclopentadiene, tetracyclododecene, ou methyltetracyclododecene. De preference, c'est le norbornene: - 1\ 3s hicyc10[..1)hept--ene portent eventuellement des chanes laterales qui peuvent etre lineaires: hicyo10.2. 1 hept-2-ene Rl, R2 (=CXH,+I avec x, y = 0, 1, 2,) ou cycliques, telles que dans le dicyclopentadiene (qui est en fait le norbornene avec une chane laterale cyclopentadiene): 4\\ L'olefne est avantageusement ['ethylene. Le COP est de preference un homo- ou copolymere du norbornene avec ou sans chane laterale; de maniere particulierement preferee, c'est un homopolymere du norbornene (avec ou sans chame laterale, mais de preference avec un groupe cyclopentadiene sous forme de chaine laterale, c.-a-d. qu'il s'agit de preference d'un homopolymere du dicyclopentadiene), ou un copolymere du norbornene (avec ou sans cha^ne laterale) et de ['ethylene. Dans ce dernier cas, la teneur en ethylene est avantageusement comprise entre 30 et 95% (de preference entre 40 et 80%) en - 4 poids, et la teneur en norbornene est comprise entre 5 et 70% (de preference entre  It is understood that the term "COP" denotes a homo- or a copolymer of a C5 to C2 cyclic monomer, and / or of a dicyclic (dimer) monomer, which can carry lateral chains so as to reach a total from 5 to 30 atoms of C. Generally, the copolymers contain, in addition to the cyclic monomer, a C2 to IOC olem, in a respective content of 2 to 95% (preferably 10 to 80%) by weight, for the monomer cyclic, and 5 to 98% (preferably 20 to 90%) by weight, for olefne. The basic cyclic monomer unit can be a cyclopentene, cyclohexene, norbornene, dicyclopentadiene, tetracyclododecene, or methyltetracyclododecene. Preferably, it is norbornene: - 1 \ 3s hicyc10 [.. 1) hept - ene possibly carry lateral chains which can be linear: hicyo10.2. 1 hept-2-ene Rl, R2 (= CXH, + I with x, y = 0, 1, 2,) or cyclic, such as in dicyclopentadiene (which is in fact norbornene with a cyclopentadiene side chain): 4 \\ The olefin is advantageously ['ethylene. The COP is preferably a homo- or copolymer of norbornene with or without a side chain; in a particularly preferred way, it is a homopolymer of norbornene (with or without side chain, but preferably with a cyclopentadiene group in the form of side chain, ie it is preferably a homopolymer of dicyclopentadiene), or a copolymer of norbornene (with or without side chain) and ethylene. In the latter case, the ethylene content is advantageously between 30 and 95% (preferably between 40 and 80%) in - 4 weight, and the norbornene content is between 5 and 70% (preferably between

et 60%).and 60%).

Le s-PP selon la presente invention peut etre un homopolymere ou copolymere du propylene avec jusqu'a 30% d'un comonomere en C2 a C, de preference [' ethylene. De preference, c' est une polyolefine a cristallinite controlee, telle que decrite dans WO 00/61062. Wile presente de preference un point de ramollissement (ou "point Vicat"), inferieur a 121 C (mesure selon la norme ASTM D1525), tout au moins apres avoir ete transformee dans des conditions appropriees (que l'on decrit dans WO 00/061062, incorpore dans la presente par reference), meme si le producteur de la resine annonce des valeurs plus elevees. Ainsi les s-PP selon la presente invention presentent de preference la caracteristique distinctive d'avoir une cristallinite qui peut etre facilement reduite pendant leur transformation. Ce contr61e aise de la cristallinite est avantageux dans le contexte de ['invention, dans la mesure ou il permet de conferer une cristallinite reduite a ces resines s-PP, a condition que lton emploie les conditions de transformation appropriees, augmentant ainsi la transparence et  The s-PP according to the present invention can be a homopolymer or copolymer of propylene with up to 30% of a C2 to C comonomer, preferably ethylene. Preferably, it is a polyolefin with controlled crystallinity, as described in WO 00/61062. Wile preferably has a softening point (or "Vicat point"), lower than 121 C (measurement according to standard ASTM D1525), at least after having been transformed under suitable conditions (which is described in WO 00 / 061062, incorporated in this reference), even if the producer of the resin announces higher values. Thus, the s-PPs according to the present invention preferably have the distinctive characteristic of having a crystallinity which can be easily reduced during their transformation. This easy crystallinity control is advantageous in the context of the invention, insofar as it makes it possible to confer reduced crystallinity on these s-PP resins, provided that the appropriate processing conditions are used, thereby increasing the transparency and

la souplesse de la structure entiere.  the flexibility of the entire structure.

La polydispersite du s-PP selon la presente invention est avantageusement inferieure a 8 et de preference inferieure a 4. Cette caracteristique reflete une faible dispersion des masses moleculaires, ce qui accroAlt la separation entre les plages de temperature de fusion et les plages de temperature de ramollissement et permet ainsi d'avoir une action plus efficace sur  The polydispersity of s-PP according to the present invention is advantageously less than 8 and preferably less than 4. This characteristic reflects a low dispersion of the molecular masses, which increases the separation between the melting temperature ranges and the temperature ranges of softening and thus allows to have a more effective action on

la cristallinite pendant la transformation.  crystallinity during transformation.

De plus, l'indice de fluidite a l'etat fondu du s-PP utilise est avantageusement inferieur a 10 g/10 min. de preference inferieur a 6 g/10 min (mesure selon la norme ASTM D1238, dans les conditions 190 C/2,16 kg pour les polymeres de ['ethylene et les copolymeres du butene et dans les conditions 230 C/2,16 kg pour les polymeres du propylene et les homopolymeres du butene). Dans la composition selon la presente invention, le s-PP est generalement - 5 present en une quantite de 1% ou plus, ou meme de 10% ou plus (en poids par rapport au poids total du melange), tandis que la teneur en COP du melange est generalement de 70% ou plus, ou meme de 80% ou plus. Generalement, le s-PP est present en une quantite de 30% ou moins, ou meme de 20% ou moins, tandis S que le COP est present en une quantite de 99% ou moins, ou meme de 90% ou moins. Outre la resine s-PP et le COP, la composition selon la presente invention peut comprendre d'autres polymeres thermoplastiques. On choisit avantageusement ces autres polymeres parmi les polyolefines ou les hydrocarbures peu cristallins ou amorphes des types suivants: - les copolymeres olefiniques se composant d'au moins deux alcenes comprenant au moins 60% en poids d'ethylene et/ou de propylene etlou de butene, mais ne comprenant pas plus de 90% en poids du meme comonomere, ou parmi - les copolymeres olefiniques comprenant de ['ethylene et/ou du propylene et/ou du butene et de 10 a 40% en poids d'un ou plusieurs comonomeres differents que l'on choisit de preference parmi les olefines en C5 a C0 [par exemple, les copolymeres de ltethylene et du 1-octene, en une quantite telle afin d'obtenir du polyethylene basse densite lineaire (LLDPE), du polyethylene tres basse densite (VLDPE) ou du polyethylene ultra basse densite (ULDPE)] et les groupes acide carboxylique ou ester, par exemple ['acetate de vinyle, l'acrylate de methyle, ethyle, ou butyle, et le methacryl ate de methy l e o u le mono xyde de carb one, ou p armi - les copolymeres elastomeres avec des sequences de styrene et d'une olefine (par exemple, les copolymeres du type styrene/butadiene/styrene, styrene/ethylene/butylene/styrene ou styrene/ethylene/propylene/styrene et analogues) ou parmi - les homopolymeres tres ramifies [par exemple, le polyethylene basse densite (LDPE), ou le polyethylene moyenne densite (MDPE)]  In addition, the melt index of the s-PP used is advantageously less than 10 g / 10 min. preferably less than 6 g / 10 min (measurement according to standard ASTM D1238, under 190 C / 2.16 kg conditions for ethylene polymers and butene copolymers and under 230 C / 2.16 kg conditions for propylene polymers and butene homopolymers). In the composition according to the present invention, s-PP is generally present in an amount of 1% or more, or even 10% or more (by weight relative to the total weight of the mixture), while the content of COP of the mixture is generally 70% or more, or even 80% or more. Generally, s-PP is present in an amount of 30% or less, or even 20% or less, while S that the COP is present in an amount of 99% or less, or even 90% or less. In addition to the s-PP resin and the COP, the composition according to the present invention may comprise other thermoplastic polymers. These other polymers are advantageously chosen from polyolefins or slightly crystalline or amorphous hydrocarbons of the following types: - olefinic copolymers consisting of at least two alkenes comprising at least 60% by weight of ethylene and / or propylene and / or butene , but not comprising more than 90% by weight of the same comonomer, or from - olefinic copolymers comprising ethylene and / or propylene and / or butene and from 10 to 40% by weight of one or more comonomers different which are preferably chosen from C5 to C0 olefins [for example, copolymers of ethylene and 1-octene, in such an amount in order to obtain low linear density polyethylene (LLDPE), very low polyethylene density (VLDPE) or ultra low density polyethylene (ULDPE)] and the carboxylic acid or ester groups, for example [vinyl acetate, methyl acrylate, ethyl, or butyl, and methacryl ate de methy leou mono carb one x, or pa rmi - elastomeric copolymers with sequences of styrene and an olefin (for example, copolymers of the type styrene / butadiene / styrene, styrene / ethylene / butylene / styrene or styrene / ethylene / propylene / styrene and the like) or among - highly branched homopolymers (for example, low density polyethylene (LDPE), or medium density polyethylene (MDPE)]

- les hydrocarbures hydrogenes tels que la paraffine ou l'huile de paraffine.  - hydrogenated hydrocarbons such as paraffin or paraffin oil.

- 6 Avantageusement, la composition selon la presente invention comprend en plus, au mo ins une re sine cho i s i e p armi le s cop o lymere s styrene/ethylene/butylene/styrene (SEBS), incluant eventuellement du styrene/ethylene/butylene (SEB), les copolymeres styrene/ethylene/propylene/ styrene (SEPS), incluant eventuellement du styrene/ethylene/propylene (SEP), et les copolymeres ethylene-l-octane (de preference fabriques a ['aide d'une technologie metallocene). On prefere les SEBS et/ou SEPS pcisqutils permettent d'obtenir a la fois des soudures permanentes et des soudures pelables (a une plus  - 6 Advantageously, the composition according to the present invention further comprises, at least one resine is is armi s cop o lymere s styrene / ethylene / butylene / styrene (SEBS), possibly including styrene / ethylene / butylene (SEB) ), styrene / ethylene / propylene / styrene copolymers (SEPS), optionally including styrene / ethylene / propylene (SEP), and ethylene-l-octane copolymers (preferably made using metallocene technology). We prefer SEBS and / or SEPS pcisqutils allow to obtain both permanent welds and peelable welds (at a more

faible temperature) avec le film et parce qu'ils ameliorent sa resistance au choc.  low temperature) with the film and because they improve its impact resistance.

La concenkation totale de ces resines est generalement egale ou superieure a 1% (en poids par rapport a la composition entiere) et de preference egale ou superieure a 10%. Generalement elle est inferieure ou egale a 29%, de preference  The total concentration of these resins is generally equal to or greater than 1% (by weight relative to the entire composition) and preferably equal to or greater than 10%. Generally it is less than or equal to 29%, preferably

a 20%.at 20%.

On peut facilement transformer la composition selon la presente invention en toutes sortes d'objets, partant d'un objet plat (tel qu'un film ou feuille) jusqu'a un obj et tridimensionnel (comme un recipient) et en une structure  The composition according to the present invention can easily be transformed into all kinds of objects, starting from a flat object (such as a film or sheet) up to a three-dimensional object (such as a container) and into a structure.

monocouche ou en une structure multicouches.  monolayer or in a multilayer structure.

- Dans une forme de realisation preferee, la presente invention a trait a un film comprenant au moins une couche de base incluant la composition decrite ci  - In a preferred embodiment, the present invention relates to a film comprising at least one base layer including the composition described above

dessus.above.

! On emploie le terme "film" pour designer une structure plate mince, ou une structure tubulaire (dans le cas de films souffles) qui presente generalement une epaisseur de 1 000 m ou moins, de preference 500 1lm ou moins, ou meme 250 1lm ou moins. En pratique, une epaisseur de 100,um ou plus convient, ou  ! The term "film" is used to designate a thin flat structure, or a tubular structure (in the case of blown films) which generally has a thickness of 1000 m or less, preferably 500 1lm or less, or even 250 1lm or less. In practice, a thickness of 100 µm or more is suitable, or

meme 150,um ou plus.even 150, um or more.

Le film selon la presente invention comporte generalement au moins une autre couche, en plus de celle de base comprenant la composition a base de s-PP et de COP. Puisque les COP vent sensibles a la graisse, meme en de falbles quantites, tel que lorsqu'on le touche ou qu'on le manipule, le film selon la presente invention comprend de preference au moins une couche externe qui ne - 7  The film according to the present invention generally comprises at least one other layer, in addition to the base layer comprising the composition based on s-PP and COP. Since the COP are sensitive to grease, even in small quantities, such as when it is touched or when it is handled, the film according to the present invention preferably comprises at least one outer layer which does not - 7

comprend pas de COP et de preference meme deux de ces couches externes.  includes no COP and preferably even two of these outer layers.

Dans ce cas, les couches vent disposees de chaque cOte de la couche de base. La ou les couches supplementaires comprennent de preference au moins 30% de PP obtenu par une technologie metallocene (soit syndiotactique soit isotactique, soit homopolymere soit copolymere, par exemple avec ['ethylene). Le choix de resines PP obtenues par une technologie a catalyseurs metallocenes, ameliore la purete (teneur en matieres extractibles et en residue catalytiques) de la structure entiere. Selon une forme de realisation preferee de la presente invention, le film comprend au moins sur un cOte de la couche de base, une couche comprenant du s-PP et/ou de l'i-PP fabriques a ['aide d'une technologie metallocene et au moins une resine choisie parmi les copolymeres SEBS, SEBS avec SEB, SEPS, SEPS avec SEP, et les copolymeres ethylene-1-octane fabriques a ['aide d'une technologie metallocene, pour la meme raison qu'expliquee ci-dessus. La  In this case, the wind layers are arranged on each side of the base layer. The additional layer or layers preferably comprise at least 30% of PP obtained by a metallocene technology (either syndiotactic or isotactic, or homopolymer or copolymer, for example with ethylene). The choice of PP resins obtained by a technology with metallocene catalysts improves the purity (content of extractable materials and catalytic residue) of the entire structure. According to a preferred embodiment of the present invention, the film comprises at least on one side of the base layer, a layer comprising s-PP and / or i-PP manufactured using a technology. metallocene and at least one resin chosen from the copolymers SEBS, SEBS with SEB, SEPS, SEPS with SEP, and ethylene-1-octane copolymers manufactured using metallocene technology, for the same reason explained above. above. The

concentration totale en ces resines est generalement inferieure ou egale a 70%.  total concentration of these resins is generally less than or equal to 70%.

Afin d'ameliorer encore ['aptitude au scellage du film selon ['invention, il est avantageux stil comprend au moins une couche externe (la couche de scellage) comprenant du s-PP et/ou de l'i-PP fabriques a ['aide d'une technologie metallocene, au moins une resine choisie parmi les copolymeres SEBS, SEBS avec SEB, SEPS, SEPS avec SEP, et les copolymeres ethylene-1-octane fabriques par une technologie metallocene); et au moins une polyolefine peu cristalline ou amorphe choisie parmi les copolymeres ethylene/acetate de vinyle (EVA), ethylene/acrylate de methyle (EMA), ethylene/acrylate d'ethyle (EEA), ou ethylene/acrylate de butyle (EBA). Parmi les derniers copolymeres cites, on ne prend naturellement en consideration que ceux qui presentent une teneur en comonomere(s) d'au moins 10%, a titre de constituents supplementaires. La concentration en ces copolymeres est generalement egale ou superieure a 0,1%  In order to further improve the sealing ability of the film according to the invention, it is advantageous if it comprises at least one outer layer (the sealing layer) comprising s-PP and / or i-PP made in [ using a metallocene technology, at least one resin chosen from the copolymers SEBS, SEBS with SEB, SEPS, SEPS with SEP, and the ethylene-1-octane copolymers produced by a metallocene technology); and at least one poorly crystalline or amorphous polyolefin chosen from ethylene / vinyl acetate (EVA), ethylene / methyl acrylate (EMA), ethylene / ethyl acrylate (EEA), or ethylene / butyl acrylate (EBA) copolymers . Among the last copolymers mentioned, naturally only those which have a content of comonomer (s) of at least 10% are taken into account, as additional constituents. The concentration of these copolymers is generally equal to or greater than 0.1%

(en poids, par rapport a la composition entiere), et de preference superieure a 1%.  (by weight, relative to the entire composition), and preferably greater than 1%.

Wile est generalement inferieure ou egale a 15%, de preference inferieure a 10% et de maniere tout particulierement preferee inferieure a 7%. Un melange d' EVA et d' EMA, de preference en une quantite totale d'au moins 1%, ou meme d'au -8 moins 5%, donne de bons resultats. A savoir, il permet de produire des soudures avec des resistances au pelage tres reproductibles, ce qui est tres utile pour la fabrication d'articles ayant une soudure pelable, tels que les sacs ou poches multicompartimentes comportant une soudure externe permanente et au moins une soudure pelable. Hormis les couches citees ci-dessus, il peut etre interessant d'un point de vue economique, dtinclure une couche constituee de dechets de decoupe (de films selon la presente invention), sous forme de couche interne dans les films decrits ci-dessus. Le film selon la presente invention peut etre graine (a savoir, peut porter un motif en relief) a ['aide de toute technique connue, aDm d'empecher un blocage. Le film selon la presente invention, peut comporter en plus une couche  Wile is generally less than or equal to 15%, preferably less than 10% and in particular most preferably less than 7%. A mixture of EVA and EMA, preferably in a total amount of at least 1%, or even of -8 at least 5%, gives good results. Namely, it makes it possible to produce welds with very reproducible peel resistances, which is very useful for the manufacture of articles having a peelable weld, such as multi-compartment bags or pockets comprising a permanent external weld and at least one weld. peelable. Apart from the layers mentioned above, it may be interesting from an economic point of view, to include a layer consisting of cutting waste (of films according to the present invention), in the form of an internal layer in the films described above. The film according to the present invention can be grained (ie, can bear an embossed pattern) using any known technique, so as to prevent blockage. The film according to the present invention may additionally comprise a layer

barriere comprenant une resine telle que EVOH, PA...  barrier comprising a resin such as EVOH, PA ...

Une structure preferee pour le film selon la presente invention, comprend les couches suivantes: 1. une couche A (couche externe) comprenant au moins 60% de s-PP et/ou d'i-PP fabriques par une technologie a metallocene, et de O a 40% d'au moins une resine choisie parmi les copolymeres SEBS,SEBS avec SEB, SEPS, SEPS avec SEP et les copolymeres ethylene-1-octane fabriques par une technologie metallocene, 2. une couche B (couche de base) comprenant un melange s-PP/COP comprenant au moins 70% de COP, au moins 1% de s-PP, et de O a 29% d'au moins une resine choisie parmi les copolymeres SEBS,SEBS avec SEB,SEPS, avec SEPS avec SEP et les copolymeres ethylene-1-octane fabriques par une technologie metallocene, 3. une couche C (couche de scellage) comprenant au moins 50% de s-PP et/ou d'i-PP fabriques par une technologie metallocene; de O a 49% d'au moins une resine choisie parmi les copolymeres SEBS,SEBS avec SEB, SEPS, SEPS avec SEP, et les copolymeres ethylene-1-octane fabriques par une technologie metallocene; et au moins 1% d'un melange d' EVA et d' EMA, et une couche de dechets de decoupe entre les couches A et B. Eventuellement, ce film prefere peut comprendre une couche supplementaire (B') entre les couches B et C, laquelle couche comprend au moins % en poids de s-PP et/ou de i-PP fabriques par une technologie metallocene, et de 0 a 70% d'au moins une resine choisie parmi les copolymeres SEBS, SEBS avec SEB, SEPS, SEPS avec SEP, et les copolymeres ethylene-l-octane  A preferred structure for the film according to the present invention comprises the following layers: 1. a layer A (outer layer) comprising at least 60% of s-PP and / or i-PP produced by a metallocene technology, and from 0 to 40% of at least one resin chosen from the copolymers SEBS, SEBS with SEB, SEPS, SEPS with SEP and the ethylene-1-octane copolymers produced by a metallocene technology, 2. a layer B (base layer) comprising an s-PP / COP mixture comprising at least 70% of COP, at least 1% of s-PP, and from O to 29% of at least one resin chosen from the copolymers SEBS, SEBS with SEB, SEPS, with SEPS with SEP and the ethylene-1-octane copolymers produced by a metallocene technology, 3. a layer C (sealing layer) comprising at least 50% of s-PP and / or i-PP produced by a metallocene technology; from O to 49% of at least one resin chosen from the copolymers SEBS, SEBS with SEB, SEPS, SEPS with SEP, and the ethylene-1-octane copolymers manufactured by a metallocene technology; and at least 1% of a mixture of EVA and EMA, and a layer of cutting waste between layers A and B. Optionally, this preferred film may comprise an additional layer (B ') between layers B and C, which layer comprises at least% by weight of s-PP and / or i-PP produced by a metallocene technology, and from 0 to 70% of at least one resin chosen from the copolymers SEBS, SEBS with SEB, SEPS , SEPS with SEP, and ethylene-l-octane copolymers

fabriques par une technologie metallocene.  manufactured by metallocene technology.

Le film selon la presente invention est tres facile a souder et par consequent peut avantageusement etre utilise pour fabriquer des sacs. En consequence, la presente invention a trait egalement a un sac constitue du film decrit ci-dessus. De preference, ce sac est un sac multicompartimente comportant au moins une soudure externe permanente et au moins une soudure pelable. On entend par soudure permanente une soudure que l'on ne peut pas facilement peler manuellement et qui presente en general une resistance au pelage d'au moins 2 000 N/m (selon ASTM/OSO F88), ou meme d'au moins 3 000 N/m, tandis qu'une soudure pelable est une soudure facile a peler manuellement et qui presente en general une resistance au pelage inferieure a 2 000 N/m. L'homme de metier peut tres facilement determiner les gammes optimales de temperature, pression et duree de soudage, afin d'obtenir respectivement une soudure permanente et une soudure pelable, avec une structure donnee. Generalement, on realise les soudures permanentes et pelables en utilisalt le soudage par un gaz  The film according to the present invention is very easy to weld and therefore can advantageously be used to make bags. Accordingly, the present invention also relates to a bag made of the film described above. Preferably, this bag is a multi-compartment bag comprising at least one permanent external weld and at least one peelable weld. By permanent welding is meant a weld which cannot be easily peeled manually and which generally has a peel strength of at least 2,000 N / m (according to ASTM / OSO F88), or even at least 3 000 N / m, while a peelable weld is a weld which is easy to peel manually and which generally has a peel strength of less than 2000 N / m. Those skilled in the art can very easily determine the optimal ranges of temperature, pressure and duration of welding, in order to obtain respectively a permanent weld and a peelable weld, with a given structure. Generally, permanent and peelable welds are made using gas welding.

chaud ou un outil chaud, ce dernier etant prefere.  hot or a hot tool, the latter being preferred.

On peut utiliser le film et le sac selon la presente invention pour toute application ou leurs souplesse, aptitude au scellage, transparence, capacite de sterilisation et proprietes barriere vent precieuses. Le domaine medical constitue un tel domaine d' application. En effet, le sac s elon la presente invention convient en particulier p our contenir de s fluides medicaux tel s que les solutions de dialyse, de perfusion, de nutritionEn raison de ces excellentes proprietes - 10 barriere, notamment aux alcools et aux acides, on peut souder le film selon la presente invention en un sac destine au stockage d'acide et d'alcool que l'on emploie par exemple pour rincer ou nettoyer certains materiels medicaux. Une application qui donne de bons resultats est le stockage de l'acide acetique dans un sac a double compartiment, l'un contenant une solution concentree d'acide acetique (jusqu'a 50% en poids) et l'autre de l'eau. Les deux compartiments vent separes par une soudure pelable, que lton doit rompre juste avant utilisation afin d'amener la solution d'acide acetique a la bonne concentration. Le sac selon la presente invention permet d'obtenir une duree de conservation beaucoup plus  The film and the bag according to the present invention can be used for any application or their flexibility, sealability, transparency, sterilization capacity and valuable wind barrier properties. The medical field constitutes such a field of application. Indeed, the bag according to the present invention is particularly suitable for containing medical fluids such as dialysis solutions, infusion, nutrition. Due to these excellent barrier properties, in particular to alcohols and acids, it is can weld the film according to the present invention into a bag intended for the storage of acid and alcohol which is used for example to rinse or clean certain medical materials. One application which gives good results is the storage of acetic acid in a double compartment bag, one containing a concentrated solution of acetic acid (up to 50% by weight) and the other water. . The two compartments are separated by a peelable weld, which must be broken just before use in order to bring the acetic acid solution to the right concentration. The bag according to the present invention makes it possible to obtain a much longer shelf life.

longue que ccux selon l'art anterieur, a savoir, il se produit moins d'evaporation.  long than that according to the prior art, that is to say, less evaporation takes place.

Finalement, on peut egalement utiliser avec avantage la composition de polymere selon la presente invention dans les articles moules par injection. Ainsi, dans la plupart des domaines d'application des films et sacs precites, ces derniers doivent etre relies a un certain type d'appareil (tel qu'un appareil de perfusion ou de dialyse, par exemple) et pour realiser cette connexion, on utilise souvent des tubes ou des pieces de raccordement similaires que l' on fabrique generalement au moyen du moulage par injection. Afin de disposer d'un systeme complet a base des memes ingredients de polymere, et de beneficier de leurs avantages tels qutexposes ci-dessus, ces articles moules par injection comportent  Finally, the polymer composition according to the present invention can also be advantageously used in injection molded articles. Thus, in most of the fields of application of the aforementioned films and bags, the latter must be connected to a certain type of device (such as an infusion or dialysis device, for example) and to make this connection, Often tubes or similar fittings are used, which are generally produced by injection molding. In order to have a complete system based on the same polymer ingredients, and to benefit from their advantages as set out above, these injection molded articles include

avantageusement la meme composition polymere que celle decrite ci-dessus.  advantageously the same polymer composition as that described above.

ExemplesExamples

Dans les exemples suivants: - i-PP est la qualite EOD 9421 de chez ATOFINA (indice de fluidite a l'etat fondu (MFI) de 5 selon ASTM D1238) - SEBS est la qualite KRATON G 1657 de chez SHELL - EVA et EMA vent les qualites UL00218 et 16 MA03 de chez ATOFINA (MFI autour de 3 et environ 18% de VA ou MA) - COP est la qualite TOPAS 8007 de chez TICONA (MFI de 30 (ISO 1133, 260 C, 2,16 kg)) 3 0 - le trouble et la transparence (= le facteur de transmission lumineuse total) - 11  In the following examples: - i-PP is the EOD 9421 quality from ATOFINA (melt fluidity index (MFI) of 5 according to ASTM D1238) - SEBS is the KRATON G 1657 quality from SHELL - EVA and EMA sells the qualities UL00218 and 16 MA03 from ATOFINA (MFI around 3 and around 18% of VA or MA) - COP is the quality TOPAS 8007 from TICONA (MFI of 30 (ISO 1133, 260 C, 2.16 kg) ) 3 0 - haze and transparency (= the total light transmission factor) - 11

ont ete mesures selon la norme ASTM D 1003 - 00.  have been measured according to ASTM D 1003 - 00.

Exemple comparatif 1: On a co-extrude un film multicouches ayant des caracteristiques de soudure pelable comportant les couches suivantes: Couche A (couche externe): melange de i-PP (90% en poids) et de SEBS (10%  Comparative Example 1: A multilayer film having peelable welding characteristics was co-extruded comprising the following layers: Layer A (outer layer): mixture of i-PP (90% by weight) and SEBS (10%

en poids).in weight).

Couche B 1: i-PP (lpO% en poids).Layer B 1: i-PP (lpO% by weight).

Couche B2: melange constitue de i-PP (75% en poids) et de SEBS (25% en poids). Couche C (couche de scellage): melange constitue de copolymere iPP (75% en  Layer B2: mixture consisting of i-PP (75% by weight) and SEBS (25% by weight). Layer C (sealing layer): mixture consisting of iPP copolymer (75%

poids), SEBS (22% en poids), EV-A (2% en poids) et EMA (1% en poids).  by weight), SEBS (22% by weight), EV-A (2% by weight) and EMA (1% by weight).

L'epaisseur totale du film etait de 200 1lm, avec une couche B 1 de 40 1lm.  The total film thickness was 200 µl, with a layer B 1 of 40 µl.

Son kouble etait de 4% et sa kansparence de 96%.  Its kouble was 4% and its kansparence was 96%.

Exemple comparatif 2: Identique a l'exemple comparatif 1 sauf que la couche B 1 est constituee  Comparative example 2: Identical to comparative example 1 except that the layer B 1 is constituted

de COP (100% en poids).of COP (100% by weight).

L'epaisseur totale du film total est de 200 1lm, avec une couche B 1 de 40  The total thickness of the total film is 200 1lm, with a layer B 1 of 40

m. Son trouble etait de 5% et sa transparence, de 95,5%.  m. Its haze was 5% and its transparency 95.5%.

Exemple 3: un film selon la presente invention: Identique a ltexemple comparatif 1, sauf que la couche B 1 est constituee  Example 3: a film according to the present invention: Identical to Comparative Example 1, except that the layer B 1 is formed

d'un melange de COP (95% en poids) et de s-PP (15% en poids).  a mixture of COP (95% by weight) and s-PP (15% by weight).

L'epaisseur totale du film est de 200,um au total, avec une couche B 1 de  The total thickness of the film is 200 μm in total, with a layer B 1 of

m. Son kouble etait de 6,2% et sa transparence de 95%.  m. Its kouble was 6.2% and its transparency was 95%.

Sterilisation a la vapeur d'eau et essai de chute: On a fabrique 10 sacs respectivement des films de l'exemple comparatif 2 et de l'exemple 3, et on les a remplis avec 3 likes d'eau; on a sterilise a la vapeur d'eau, 5 sacs de chaque serie (121 C/250 F, 30 min). Apres sterilisation a la vapeur d'eau, les sacs fabriques a partir de l'exemple comparatif 2 ont presente une exfoliation. Les sacs selon la presente invention (exemple 3) n'ont pas presente d'exfoliation. Des essais de chute des deux echantillons sterilises et non - 12 sterilises ont montre que les sacs fabriques selon la presente invention ont survecu a un essai de chute a partir d'une hauteur de 2 metres sur un simple plancher, tandis que les sacs fabriques a partir de l'exemple comparatif 2 n'ont  Steam sterilization and drop test: 10 bags of films of Comparative Example 2 and of Example 3 were respectively made and filled with 3 likes of water; 5 bags of each series (121 C / 250 F, 30 min) were steam sterilized. After steam sterilization, the bags made from Comparative Example 2 showed exfoliation. The bags according to the present invention (Example 3) have no exfoliation. Drop tests of the two sterilized and non-sterilized samples showed that the bags made according to the present invention survived a drop test from a height of 2 meters on a single floor, while the bags made with from comparative example 2 did

pas survecu a l'essai.not survived the test.

Stockage d'acide acetique aqueux: On a rempli les sacs fabriques a partir du film selon l'exemple 3, avec 50 ml de solution aqueuse ayant des pourcentages variables d'acide acetique (0, 24, 48, 74, 96%). La surface specifque totale de tous les sacs etait de 150 cm2. On a entrepose les sacs a la fois a 23 C et a 40 C pendant 135 jours. On indique les  Storage of aqueous acetic acid: The bags made from the film according to Example 3 were filled with 50 ml of aqueous solution having variable percentages of acetic acid (0, 24, 48, 74, 96%). The total specified area of all bags was 150 cm2. The bags were stored at both 23 C and 40 C for 135 days. We indicate the

resultats (moyenne sur 2 echantillons) dans le tableau 1.  results (average over 2 samples) in Table 1.

Tableau 1: Perte ponderale en grammes a 23 C et a 40 C de melanges d'eau et  Table 1: Weight loss in grams at 23 C and 40 C of water mixtures and

d'acide acetique apres 135 jours de stockage.  acetic acid after 135 days of storage.

23 C 23 C 40 C 40 C23 C 23 C 40 C 40 C

% Hac Ex. comp. 1 Exemple 3 Ex. comp. 1 Exemple 3  % Hac Comp. Ex. 1 Example 3 Comp. Ex. 1 Example 3

-0,298 -0,244 - 3,66 -2,851-0.298 -0.244 - 3.66 -2.851

0 -0,302 -0,317 - 3,772 -3,3330 -0.302 -0.317 - 3.772 -3.333

24 -0,26 -0,208 - 3,521 -2,4924 -0.26 -0.208 - 3.521 -2.49

24 -0,281 -0,235 - 3,521 -2,96524 -0.281 -0.235 - 3.521 -2.965

48 -0,263 -0,168 - 4,136 -2,29648 -0.263 -0.168 - 4.136 -2.296

48 -0,265 -0,198 - 4,143 -2,5448 -0.265 -0.198 - 4.143 -2.54

74 -0,271 -0,098 - 5,075 -1,61474 -0.271 -0.098 - 5.075 -1.614

74 -0,289 -0,116 - 5,292 -1,9174 -0.289 -0.116 - 5.292 -1.91

96 -0,402 0,114 - 9,862 -0,18896 -0.402 0.114 - 9.862 -0.188

96 -0,46 0,146 -10,327 -0,17196 -0.46 0.146 -10.3327 -0.171

avec %Hac = le pourcentage ponderal d'acide acetique dans les solutions.  with% Hac = the percentage by weight of acetic acid in the solutions.

Comme on peut constater d'apres les resultats du tableau 1, les sacs/films/compositions fabriques selon la presente invention ont presente de maniere significative une perte ponderale plus faible, en consequence, il y a  As can be seen from the results in Table 1, the bags / films / compositions manufactured according to the present invention significantly showed a lower weight loss, therefore, there is

! 2839976! 2839976

- 13- 13

moins d'acide acetique qui suinte et par consequent moins d'odeur.  less acetic acid that oozes and therefore less odor.

Proprietes mecaniques: Le film selon l'exemple comparatif 2 presente une deformation a la rupture d'environ 50%, et celui selon ltexemple 3 presente One deformation a la rupture de 150% et une diminution du module elastique (selon ASTM D- 882/IS0 178/DIN 53457) de 70 MPa par rapport au film selon ltexemple comparatif 2. Ceci indique que les sacs/films/compositions fabriques selon la  Mechanical properties: The film according to comparative example 2 has a deformation at break of around 50%, and that according to example 3 has a deformation at break of 150% and a reduction in elastic modulus (according to ASTM D- 882 / IS0 178 / DIN 53457) of 70 MPa with respect to the film according to comparative example 2. This indicates that the bags / films / compositions produced according to the

presente invention vent plus souples que ceux de l'art anterieur.  present invention wind more flexible than those of the prior art.

- 14- 14

R E V E N DIC A TIO N SR E V E N DIC A TIO N S

1 - Composition polymere comprenant un polymere olefinique cyclique  1 - Polymer composition comprising a cyclic olefinic polymer

(COP) et un polypropylene syndiotactique (s-PP).  (COP) and a syndiotactic polypropylene (s-PP).

2 - Composition polymere selon la revendication 1, dans laquelle le COP est un homo- ou copolymere du norbornene avec ou sans chane laterale.  2 - Polymer composition according to claim 1, in which the COP is a homo- or copolymer of norbornene with or without side chain.

3 - Composition polymere selon l'une quelconque des revendications  3 - polymer composition according to any one of claims

precedentes, qui comprend en plus au moins une resine choisie parmi les copolymeres SEBS, SEBS avec SEB,SEPS,SEPS avec SEP, et les  above, which additionally comprises at least one resin chosen from the copolymers SEBS, SEBS with SEB, SEPS, SEPS with SEP, and the

copolymeres ethylene-1 -octene fabriques par une technologie metallocene.  ethylene-1-octene copolymers produced by metallocene technology.

4 - Film ayant au moins une couche de base comprenant une composition  4 - Film having at least one base layer comprising a composition

polymere selon l'une quelconque des revendications precedentes.  polymer according to any one of the preceding claims.

- Film selon la revendication 4, qui comprend au moins sur un cOte de la couche de base, une couche comprenant du s-PP et/ou du i-PP (polypropylene isotactique) fabriques par une technologie metallocene et au moins une resine choisie parmi les copolymeres SEBS, SEBS avec SEB, SEPS,SEPS avec SEP,  - Film according to claim 4, which comprises at least on one side of the base layer, a layer comprising s-PP and / or i-PP (isotactic polypropylene) manufactured by a metallocene technology and at least one resin chosen from the SEBS, SEBS with SEB, SEPS, SEPS with SEP copolymers,

et les copolymeres ethylene-l-octane, fabriques par une technologie metallocene.  and ethylene-l-octane copolymers, produced by metallocene technology.

6 - Film selon la revendication 4 ou 5, qui comprend au moins une couche externe comprenant du s-PP et/ou du i-PP fabriques par une technologie metallocene; au moins une resine choisie parmi les copolymeres SEBS, SEBS avec SEB,SEPS,SEPS avec SEP, et les copolymeres ethylene-l-octane fabriques par une technologie metallocene; et au moins une resine choisie parmi  6 - Film according to claim 4 or 5, which comprises at least one outer layer comprising s-PP and / or i-PP manufactured by a metallocene technology; at least one resin chosen from the SEBS, SEBS with SEB, SEPS, SEPS with SEP copolymers and the ethylene-l-octane copolymers produced by metallocene technology; and at least one resin chosen from

les copolymeres EVA et EMA.EVA and EMA copolymers.

7 - Film selon l'une quelconque des revendications 4 a 6, qui comprend les  7 - Film according to any one of claims 4 to 6, which comprises the

couches suivantes: 1. couche A (couche externe) comprenant au moins 60% de s-PP et/ou de i-PP, fabriques par une technologie metallocene, et de O a 40% d'au moins une resine choisie parmi les copolymeres SEBS, SEBS avec SEB,SEPS,SEPS avec SEP, et les copolymeres ethylene-1 -octene fabriques par une - technologie metallocene, 2. couche B (couche de base) comprenant un melange s-PP/COP comprenant au moins 70% de COP, au moins 1% de s-PP et de O a 29% d'au moins une - 15 resine choisie parmi les copolymeres SEBS, SEBS avec SEB, SEPS, SEPS avec SEP, et les copolymeres ethylene-l-octane fabriques par une technologie metallocene, 3. couche C (couche de scellage) comprenant au moins 50% de s-PP et/ou de i-PP fabriques par une technologie metallocene; de O a 49% d'au moins une resine choisie parmi les copolymeres SEBS, SEBS avec SEB, SEPS, SEPS avec SEP, et les copolymeres ethylene-l-octane fabriques par une technologie metallocene; et au moins 1% d'un melange de copolymeres EVA et EMA, et une couche de dechets de decoupe entre les couches A et B. 8 - Sac fabrique en soudant un film selon l'une quelconque des  following layers: 1. layer A (outer layer) comprising at least 60% of s-PP and / or i-PP, manufactured by a metallocene technology, and from O to 40% of at least one resin chosen from copolymers SEBS, SEBS with SEB, SEPS, SEPS with SEP, and ethylene-1-octene copolymers manufactured by - metallocene technology, 2. layer B (base layer) comprising an s-PP / COP mixture comprising at least 70% of COP, at least 1% of s-PP and from O to 29% of at least one - 15 resin chosen from the copolymers SEBS, SEBS with SEB, SEPS, SEPS with SEP, and the ethylene-l-octane copolymers manufactured by a metallocene technology, 3. layer C (sealing layer) comprising at least 50% of s-PP and / or i-PP produced by a metallocene technology; from 0 to 49% of at least one resin chosen from the copolymers SEBS, SEBS with SEB, SEPS, SEPS with SEP, and the ethylene-l-octane copolymers produced by a metallocene technology; and at least 1% of a mixture of EVA and EMA copolymers, and a layer of cutting waste between layers A and B. 8 - Bag produced by welding a film according to any one of the

revendications 4 a 7.claims 4 to 7.

9 - Sac selon la revendication 8 qui constitue un sac a plusieurs compartiments comportant au moins une soudure externe permanente et au  9 - Bag according to claim 8 which constitutes a bag with several compartments comprising at least one permanent external weld and at

moins une soudure pelable.minus a peelable weld.

- Sac selon la revendication 8 ou 9, qui est rempli avec une solution  - Bag according to claim 8 or 9, which is filled with a solution

aqueuse d'acide acetique.aqueous acetic acid.

11 - Article moule par injection comprenant une composition polymere  11 - Injection molded article comprising a polymer composition

selon l'une quelconque des revendications 1 a 3.  according to any one of claims 1 to 3.

FR0204644A 2002-05-21 2002-05-21 POLYMER COMPOSITION COMPRISING A OLEFINIC CYCLIC COPOLYMER Expired - Fee Related FR2839976B1 (en)

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FR0204644A FR2839976B1 (en) 2002-05-21 2002-05-21 POLYMER COMPOSITION COMPRISING A OLEFINIC CYCLIC COPOLYMER
JP2004506407A JP4209384B2 (en) 2002-05-21 2003-05-12 Polymer composition comprising a cyclic olefin copolymer
EP03752732A EP1509569A1 (en) 2002-05-21 2003-05-12 Polymer composition including a cyclic olefin copolymer
AU2003232758A AU2003232758A1 (en) 2002-05-21 2003-05-12 Polymer composition including a cyclic olefin copolymer
US10/515,061 US20050238830A1 (en) 2002-05-21 2003-05-12 Polymer composition including a cyclic olefin copolymer
PCT/EP2003/004953 WO2003097739A1 (en) 2002-05-21 2003-05-12 Polymer composition including a cyclic olefin copolymer
CNB038113856A CN1303148C (en) 2002-05-21 2003-05-12 Polymer composition including a cyclic olefin copolymer
KR1020047018695A KR100933434B1 (en) 2002-05-21 2003-05-12 Polymer composition comprising a cyclic olefin copolymer
TW092113240A TW200400212A (en) 2002-05-21 2003-05-15 Polymer composition including a cyclic olefin copolymer

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US20050238830A1 (en) 2005-10-27
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JP2005526162A (en) 2005-09-02
KR100933434B1 (en) 2009-12-23
FR2839976B1 (en) 2004-07-30
CN1653129A (en) 2005-08-10
JP4209384B2 (en) 2009-01-14
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EP1509569A1 (en) 2005-03-02
TW200400212A (en) 2004-01-01

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