FR2705053A1 - Alimentary drawable film - Google Patents

Alimentary drawable film Download PDF

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Publication number
FR2705053A1
FR2705053A1 FR9305734A FR9305734A FR2705053A1 FR 2705053 A1 FR2705053 A1 FR 2705053A1 FR 9305734 A FR9305734 A FR 9305734A FR 9305734 A FR9305734 A FR 9305734A FR 2705053 A1 FR2705053 A1 FR 2705053A1
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FR
France
Prior art keywords
styrene
ethylene
layers
butadiene
copolymer
Prior art date
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Pending
Application number
FR9305734A
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French (fr)
Inventor
Martin Villarrubia Bernabe
Hennia Hadj
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.)
MARTIN VILLARRUBIA BARNABE
Original Assignee
MARTIN VILLARRUBIA BARNABE
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Filing date
Publication date
Application filed by MARTIN VILLARRUBIA BARNABE filed Critical MARTIN VILLARRUBIA BARNABE
Priority to FR9305734A priority Critical patent/FR2705053A1/en
Publication of FR2705053A1 publication Critical patent/FR2705053A1/en
Pending legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/51—Elastic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7244—Oxygen barrier
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging

Landscapes

  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Alimentary drawable film as 2 or more extruded layers made up of ethylene-octene copolymers and of a styrene-butadiene-styrene or styrene-ethylene-butadiene-styrene rubber copolymer, characterised because it is obtained by coextrusion of 2, 3 or more layers on an extrusion line with an annular die or an extrusion line with a slot die, or else by blowing, so that the external layers or one of the layers have a composition of 100 % by weight of an ethylene-octene copolymer or as a mixture with other ethylene, hexene, butene or vinyl acetate copolymer, with a variable density of between 0.890 and 0.925; the composition of the intermediate layer being: - 0.1-99.9 % of a styrene-butadiene-styrene block copolymer or polyester; and - 0.1-99.9 % of a styrene-butadiene-styrene or styrene-ethylene-butadiene-styrene thermoplastic rubber with a variable density of between 0.890 and 1.05. It is applicable to the alimentary industry for the packaging of alimentary products.

Description

TITRE DE L'INVENTION
Film étirable alimentaire en deux ou trois couches extrudées composées de copolymères d'éthylène hexène, butène ou vinyle acétate et d'un copolymère ou caoutchouc styrèneboutadiène-styrène ou styrène-éthylène-boutadiène-styrène.TITLE OF THE INVENTION
Food stretch film in two or three extruded layers composed of copolymers of ethylene hexene, butene or vinyl acetate and of a styrene-butadiene-styrene or styrene-ethylene-boutadiene-styrene copolymer or rubber.

CHAMP TECHNIQUE DE L'INVENTION
L'invention est encadrée dans le champ technique des produits applicables à l'industrie alimentaire pour l'emba-- liage de produits alimentaires. Elle concerne plus précisément un nouveau film étirable constitué de deux ou plus couches extrudées de copolymères dont la composition comprend des oléfines et du styrène suivant les couches.TECHNICAL FIELD OF THE INVENTION
The invention is framed in the technical field of products applicable to the food industry for the packaging of food products. More specifically, it relates to a new stretch film consisting of two or more layers extruded from copolymers, the composition of which comprises olefins and styrene depending on the layers.

ÉTAT DE LA TECHNIQUE AVANT L'INVENTION
Suite à différentes ordonnances européennes déconsei-liant l'utilisation de polymères PVC dans l'application des films alimentaires à contact direct, liées à des problèmes de concentration de chlore sur les aliments, beaucoup de transformateurs se sont lancés dans la course d'une fabrication d'un film étirable alimentaire à base de copolymères polyoléfines (PE,PP) comme substitut du PVC.PRIOR ART BEFORE THE INVENTION
Following various European ordinances advising against the use of PVC polymers in the application of direct contact food films, linked to problems of chlorine concentration on food, many processors have embarked on the manufacturing process a food stretch film based on polyolefin copolymers (PE, PP) as a substitute for PVC.

Plusieurs produits se trouvent actuellement sur le mar ché de conception, en majorité, obtenue par un mélange de copolymères polyéthylène, sur ligne d'extrusion ou de coex-trusion soufflage à filière annulaire ou sur ligne de coex-trusion "CAST" à filière plate, en mono couche ou multi couches. Several products are currently on the design market, the majority obtained by a mixture of polyethylene copolymers, on extrusion line or coex-trusion blow molding with annular die or on "CAST" coextrusion line with flat die , in single layer or multi layer.

Tout ceci en omettant de définir et d'approcher les caractéristiques techniques du film étirable alimentaire PVC, soit: - Excellentes propriétés optiques. All this while failing to define and approach the technical characteristics of the PVC food stretch film, namely: - Excellent optical properties.

- Facile mise en oeuvre sur machines automatiques.- Easy implementation on automatic machines.

- Mémoire élastique.- Elastic memory.

- Durée de conservation du produit emballé son utilisation en four micro-ondes est déconseillé, les ondes émisses favorisent la migration et la concentration de- certains additifs sur les aliments.- Shelf life of the packaged product its use in microwave oven is not recommended, the emitted waves favor the migration and the concentration of- certain additives on food.

D'autre part les films étirables alimentaires obtenus par un mélange de copolymères éthylène, ont aussi leurs inconvénients et n'apparaissent pas comme un substitut des films PVC, c'est à dire: - Aucune mémoire élastique - Mise en oeuvre sur machines automatiques impossible sans modifications importantes de celles-ci. On the other hand, food stretch films obtained by a mixture of ethylene copolymers also have their drawbacks and do not appear as a substitute for PVC films, that is to say: - No elastic memory - Implementation on automatic machines impossible without significant modifications of these.

- Déchirabilité difficile - Durée de conservation légèrement inférieure au PVC.- Difficult to tear - Shelf life slightly lower than PVC.

- Utilisation d'un additif collant dans le cas de fabrica-tion sur ligne d'extrusion ou coextrusion soufflage.- Use of a sticky additive in the case of manufacturing on an extrusion line or blowing coextrusion.

Une comparaison des différents produits et de leur adaptation à cette application montre que sur le marché en utilisation sur machines automatiques le film PVC reste le leader et qu'en utilisation manuelle le film PE prend une place de plus en plus prépondérante car il atteint des épaisseurs beaucoup plus faibles et respecte l'environnement. A comparison of the different products and their adaptation to this application shows that on the market in use on automatic machines the PVC film remains the leader and that in manual use the PE film takes an increasingly preponderant place because it reaches thicknesses much weaker and respects the environment.

Certains films étirables à base de polyoléfines produits par les sociétés ASAHI et MITSUBITCHI rivalisent avec les films PVC mais leur prix est un obstacle majeur. Certain stretch films based on polyolefins produced by the companies ASAHI and MITSUBITCHI compete with PVC films but their price is a major obstacle.

DESCRIPTION DÉTAILLÉE DE L'INVENTION
I1 fallait s'orienter vers un film répondant aux différents critères cités ci-dessus. Nos observations et nos réflexions nous ont permis de concevoir un film multicouches dont les couches extérieures avaient les avantages des films
PE et que la couche médiane celle du PVC soit:
- Pas de migration de substances dangereuses sur les
aliments.DETAILED DESCRIPTION OF THE INVENTION
It was necessary to move towards a film meeting the various criteria mentioned above. Our observations and our reflections allowed us to design a multilayer film whose outer layers had the advantages of films
PE and that the middle layer that of PVC is:
- No migration of dangerous substances on the
food.

- Collant obtenu sans additifs. - Tights obtained without additives.

- Excellentes propriétés optiques. - Excellent optical properties.

- Mémoire élastique. - Elastic memory.

- Durée de conservation des produits équivalente au
PVC.- Product shelf life equivalent to
PVC.

Un film ayant une faible perméabilité à la vapeur d'eau permet d'éviter le desséchement des aliments par évaporation d'eau. Ceci favorise la formation de goutellettes d'eau sur la surface interne du film et voile la transparence de celuici. A film having a low permeability to water vapor makes it possible to avoid drying of the food by evaporation of water. This promotes the formation of water droplets on the internal surface of the film and veils the transparency of this.

Pour cela nous intégrons un agent anti-buée.For this we integrate an anti-fog agent.

L'influence de l'oxygène sur le développement des bactéries pendant la durée de stockage des aliments emballés - peut être un inconvénient. The influence of oxygen on the development of bacteria during the storage time of packaged food - can be a disadvantage.

La présente invention, ainsi que son titre l'indique, a trait à un film étirable alimentaire en deux ou plus couches extrudées composées de copolymères éthylène-octène ou hexène et d'un copolymère ou d'un caoutchouc styrène-boutadiène-styrène ou styrène-éthylène-boutadiène-styrène. The present invention, as its title indicates, relates to a food stretch film in two or more extruded layers composed of ethylene-octene or hexene copolymers and of a styrene-boutadiene-styrene or styrene copolymer or rubber -ethylene-boutadiene-styrene.

Ce film étirable est spécialement indiqué pour l'emballage de produits alimentaires, pour ses bonnes caractéris-tiques optiques et mécaniques, ces aliments étant actualle-ment emballés avec des films de PVC. This stretch film is specially indicated for the packaging of food products, for its good optical and mechanical characteristics, these foods being currently packed with PVC films.

Les caractéristiques techniques les plus remarquables du film de cette invention sont les suivantes: de bonnesqualités optiques, une bonne perméabilité, une grande étirabi-lité, une bonne fabricabilité et l'absence de déformation résiduelle. The most remarkable technical characteristics of the film of this invention are as follows: good optical qualities, good permeability, great stretchability, good manufacturability and the absence of residual deformation.

Ce film peut être obtenu par coextrusion de deux ou trois couches ou plus sur ligne d'extrusion à filière annu-laire ou sur ligne d'extrusion à filière plate, ou bien par soufflage. This film can be obtained by coextrusion of two or three or more layers on an extrusion line with an annular die or on an extrusion line with a flat die, or else by blowing.

Les couches extérieures sont composées de 100% du poids d'un copolymère d'éthylène-octène ou mélangé avec d'autre copolymère éthylène hexène, butène ou vinyle acétate d'une densité variable comprise entre 0,890 et 0,925. La composition des couches intermédiaires étant un mélange constitué de: - 0,1-99,9% d'un copolymère bloc styrène-boutadiènetstyrène ou d'un polymère entièrement constitué d'unités monomériques de styrène; et - 0,1-99,9% d'un caoutchouc thermoplastique styrène-bouta-diène-styrène ou styrène-éthylène-boutadiène-styrène d'une densité variable comprise entre 0,890 et 1,05. The outer layers are made up of 100% by weight of an ethylene-octene copolymer or mixed with another ethylene hexene, butene or vinyl acetate copolymer with a variable density between 0.890 and 0.925. The composition of the intermediate layers being a mixture consisting of: - 0.1-99.9% of a styrene-boutadienstyrene block copolymer or of a polymer entirely made up of styrene monomer units; and - 0.1-99.9% of a styrene-bouta-diene-styrene or styrene-ethylene-boutadiene-styrene thermoplastic rubber of a variable density between 0.890 and 1.05.

Outre les caractéristiques générales du film ainsi obtenu qui ont été citées plus haut, cette invention permet la possibilité de modifier la perméabilité du film à l'oxygène en modifiant l'épaisseur des couches relatives, étant donné que le mélange de copolymère d'éthylène-oléfine présente une faible perméabilité à l'oxygène contrairement au mélange de styrène. In addition to the general characteristics of the film thus obtained which have been mentioned above, this invention allows the possibility of modifying the permeability of the film to oxygen by modifying the thickness of the relative layers, since the mixture of ethylene copolymer- olefin has low oxygen permeability unlike the styrene mixture.

D'autre part, l'utilisation du mélange composé d'un caoutchouc thermoplastique permet d'obtenir une étirabilité et une mémoire élastique résiduelle excellentes, si impor-tantes dans ce genre de films. On the other hand, the use of the mixture composed of a thermoplastic rubber makes it possible to obtain an excellent stretch and residual elastic memory, so important in this kind of film.

EXEMPLE
On a préparé un film étirable alimentaire, obtenu par coextrusion de trois couches sur ligne "CAST" à filière plate.EXAMPLE
A food stretch film was prepared, obtained by coextrusion of three layers on the "CAST" line with a flat die.

La composition des couches extérieures était de 100% du poids d'un copolymère éthylène-octène d'une densité de 0,912. La composition de la couche intermédiaire était la suivante: - 50% du poids d'un copolymère bloc styrène-boutadiène-styrène d'une densité de 1,01; - 50% du poids d'un caoutchouc thermoplastique styrène-boutadiène-styrène ou styrène-éthylène-boutadiène-styrène d'une densité variable entre 0,890 et 0,950
La coextrusion de ce film d'une épaisseur de 17 microns a permis d'obtenir les caractéristiques suivantes:
PROPRIETES UNITE TEST METHOD VALEURS
Densité: 0,936
Tension d'élongation Kg/cm2 ASTM D412 23
Elongation à la rupture % ASTM D412 1050
Dureté Shore A ASTM D2240 88
Résistance à l'allongement Kg/cm ASTM D624 35 dtune déchirure
Haze % ASTM D1003 1
Gloss % ASTM D2457 145 The composition of the outer layers was 100% by weight of an ethylene-octene copolymer with a density of 0.912. The composition of the intermediate layer was as follows: - 50% by weight of a styrene-boutadiene-styrene block copolymer with a density of 1.01; - 50% of the weight of a styrene-boutadiene-styrene or styrene-ethylene-boutadiene-styrene thermoplastic rubber with a variable density between 0.890 and 0.950
The coextrusion of this 17 micron thick film made it possible to obtain the following characteristics:
PROPERTIES UNIT TEST METHOD VALUES
Density: 0.936
Elongation tension Kg / cm2 ASTM D412 23
Elongation at break% ASTM D412 1050
Shore A hardness ASTM D2240 88
Elongation resistance Kg / cm ASTM D624 35 dt a tear
Haze% ASTM D1003 1
Gloss% ASTM D2457 145

Claims (1)

REVENDICATIONCLAIM 1. Film étirable alimentaire en deux ou plus couches avec de bonnes propriétés optiques et mécaniques, susceptible de pouvoir controler sa perméabilité à l'oxygène en fonction de l'épaisseur des couches externes et d'une étirabilité et d'une mémoire élastique résiduelle excellentes, caractérisé parce qu'il est obtenu par coextrusion de plusieurs couches sur ligne d'extrusion à filière annulaire ou sur ligne d'extrusion à filière plate; de sorte que les couches externes ont une composition de 100% du poids d'un copolymère éthylène-octène ou en mélange avec d'autre copolymère éthylène hexène, butène ou vinyle acétate et une densité variable comprise entre 0,890 et 0,925; et les couches intermédiaires présentent une composition de: - 0,1-99,9% d'un copolymère bloc styrène-boutadiène-styrène ou d'un polymère entièrement constitué d'unités monoméri-ques de styrène; et - 0,1-99,9% d'un caoutchouc thermoplastique styrène-boutadiène-styrène ou styrène-éthylène-boutadiène-styrène d'une densité variable comprise entre 0,890 et 1,05.  1. Food stretch film in two or more layers with good optical and mechanical properties, capable of controlling its oxygen permeability as a function of the thickness of the outer layers and of excellent stretch and residual elastic memory , characterized because it is obtained by coextrusion of several layers on an extrusion line with an annular die or on an extrusion line with a flat die; so that the outer layers have a composition of 100% by weight of an ethylene-octene copolymer or in admixture with other ethylene hexene, butene or vinyl acetate copolymer and a variable density between 0.890 and 0.925; and the intermediate layers have a composition of: - 0.1-99.9% of a styrene-boutadiene-styrene block copolymer or of a polymer entirely consisting of monomeric units of styrene; and - 0.1-99.9% of a styrene-boutadiene-styrene or styrene-ethylene-boutadiene-styrene thermoplastic rubber of a variable density between 0.890 and 1.05.
FR9305734A 1993-05-12 1993-05-12 Alimentary drawable film Pending FR2705053A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
FR9305734A FR2705053A1 (en) 1993-05-12 1993-05-12 Alimentary drawable film

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR9305734A FR2705053A1 (en) 1993-05-12 1993-05-12 Alimentary drawable film

Publications (1)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996023823A1 (en) * 1995-02-02 1996-08-08 Basf Aktiengesellschaft Flexible, transparent styrene polymer-based foil, in particular for food packaging, and process for its production
WO1997028964A1 (en) * 1996-02-07 1997-08-14 Cryovac, Inc. High modulus oxygen-permeable multilayer film, packaging process using same, and packaged product comprising same
WO1999033650A1 (en) * 1997-12-29 1999-07-08 Cryovac Inc. Multi-layer stretch film
US6060136A (en) * 1995-10-13 2000-05-09 Cryovac, Inc. High modulus oxygen-permeable multilayer film
WO2002064676A2 (en) * 2001-02-13 2002-08-22 Gls Corporation Removable seal of essentially gas-impermeable thermoplastic elastomer
EP1306209A1 (en) * 2001-10-25 2003-05-02 Nordenia Deutschland Gronau GmbH Multilayered film produced by co-extrusion
WO2004041538A1 (en) * 2002-10-31 2004-05-21 Kimberly-Clark Worldwide, Inc. Elastomeric film and laminates thereof
WO2005108069A1 (en) * 2004-05-07 2005-11-17 A.W.A.X. Progettazione E Ricerca S.R.L. Extensible multilayer film
FR2909075A1 (en) * 2006-11-28 2008-05-30 Patrick Gennesson Stretchable plastic film useful for packaging food products, comprises three layers i.e. two outer layers of low density polyethylene and an intermediate layer of high stretchable polyethylene

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6517950B1 (en) 1994-03-28 2003-02-11 Cryovac, Inc. High modulus oxygen-permeable multilayer film, packaging process using same, and packaged product comprising same
WO1996023823A1 (en) * 1995-02-02 1996-08-08 Basf Aktiengesellschaft Flexible, transparent styrene polymer-based foil, in particular for food packaging, and process for its production
US6060136A (en) * 1995-10-13 2000-05-09 Cryovac, Inc. High modulus oxygen-permeable multilayer film
WO1997028964A1 (en) * 1996-02-07 1997-08-14 Cryovac, Inc. High modulus oxygen-permeable multilayer film, packaging process using same, and packaged product comprising same
WO1999033650A1 (en) * 1997-12-29 1999-07-08 Cryovac Inc. Multi-layer stretch film
US6517936B1 (en) 1997-12-29 2003-02-11 Cryovac, Inc. Multi-layer stretch film
WO2002064676A2 (en) * 2001-02-13 2002-08-22 Gls Corporation Removable seal of essentially gas-impermeable thermoplastic elastomer
WO2002064676A3 (en) * 2001-02-13 2004-01-22 Gls Corp Removable seal of essentially gas-impermeable thermoplastic elastomer
US7056971B2 (en) 2001-02-13 2006-06-06 Gls Corporation Essentially gas-impermeable thermoplastic elastomer
EP1306209A1 (en) * 2001-10-25 2003-05-02 Nordenia Deutschland Gronau GmbH Multilayered film produced by co-extrusion
WO2004041538A1 (en) * 2002-10-31 2004-05-21 Kimberly-Clark Worldwide, Inc. Elastomeric film and laminates thereof
US8034440B2 (en) 2002-10-31 2011-10-11 Kimberly-Clark Worldwide, Inc. Elastomeric film and laminates thereof
WO2005108069A1 (en) * 2004-05-07 2005-11-17 A.W.A.X. Progettazione E Ricerca S.R.L. Extensible multilayer film
FR2909075A1 (en) * 2006-11-28 2008-05-30 Patrick Gennesson Stretchable plastic film useful for packaging food products, comprises three layers i.e. two outer layers of low density polyethylene and an intermediate layer of high stretchable polyethylene

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