WO2019012564A1 - Film étirable en pvc plastifié destiné à être utilisé sur une machine d'emballage automatique - Google Patents

Film étirable en pvc plastifié destiné à être utilisé sur une machine d'emballage automatique Download PDF

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Publication number
WO2019012564A1
WO2019012564A1 PCT/IT2018/000090 IT2018000090W WO2019012564A1 WO 2019012564 A1 WO2019012564 A1 WO 2019012564A1 IT 2018000090 W IT2018000090 W IT 2018000090W WO 2019012564 A1 WO2019012564 A1 WO 2019012564A1
Authority
WO
WIPO (PCT)
Prior art keywords
stretch film
film made
polyesters
plasticized pvc
esters
Prior art date
Application number
PCT/IT2018/000090
Other languages
English (en)
Inventor
Davide PAVARELLI
Laura PIRONDINI
Simona VALENTINI
Original Assignee
Gruppo Fabbri Vignola S.P.A.
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 Gruppo Fabbri Vignola S.P.A. filed Critical Gruppo Fabbri Vignola S.P.A.
Priority to EP18749880.3A priority Critical patent/EP3652243A1/fr
Publication of WO2019012564A1 publication Critical patent/WO2019012564A1/fr

Links

Classifications

    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0016—Plasticisers
    • 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
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08J2327/06—Homopolymers or copolymers of vinyl chloride
    • 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
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

  • the present invention refers to a stretch film made of plasticized PVC, to be used with automatic packaging machines, wherein the plasticizers are of a renewable origin (raw materials from vegetable or animal source) .
  • Stretch plastic films are aimed to package fresh and perishable food products placed in a tray, in particular: meats, fruits and vegetables, fish products and cheeses.
  • Fresh food products are arranged in a tray made of various materials (foamed polystyrene, cardboard and the like) , wrapping then everything with a stretch and transparent film. It is a known and widespread packaging technique, aimed in particular to foodstuff stored under refrigerated conditions, at a temperature generally included between 0°C and 8°C; the shelf life of the thereby packaged product, in particular meat products, generally ranges around 4 ⁇ 7 days.
  • the currently used plasticizers comprise esters such as adipates, benzoates, citrates, cyclo- esanoates, ortho-phtalates , sebacates, terephtalates and trimellitates .
  • Machines are known to automatically form this type of packages, equipped with means which unwind a section of film from a roll and arrange it on a plane, subjecting it to a known stretching.
  • the tray containing the product is lifted and forced against the section of plane film, which simultaneously offers a slackening, known as “pandering step", to adjust the film tension on the tray itself.
  • the film edges are stretched and overlapped in a suitable sequence on the bottom of the tray, which, when wound, is discharged, while in the correct step, the winding film is cut and separated from the film coming from the roll.
  • Known packaging machines are set to optimize the film consumption and to self-adapt some of their movements depending on features, sizes and shape of the product to be packaged.
  • the stretch plastic film In order to prevent sealing and package appeal from being impaired, the stretch plastic film must not be subjected to any relaxation after its stretching, keeping the wrapping toughness unchanged.
  • Object of the present invention is solving the above prior art problems, by providing a stretch film made of plasticized PVC wherein the contribution of the plasticizers is not of a fossil origin, but of a renewable origin (raw materials from plant or animal sources) , and therefore with low environmental impact, simultaneously satisfying the requirements for its use on automatic packaging machines .
  • FIG. 2 shows a diagram along the transverse direction of the film for the comparison of PVCp biobased TD and the reference "KOEX 818".
  • the invention therefore deals with a stretch film made of plasticized PVC, to be used with automatic packaging machines having as feature an elongation at break in the transverse direction of the film equal to 330% (+ 20%) for a film thickness ranging from 11 to 19 ⁇ ;
  • such film contains plasticizers based on esters, polyesters and natural oils of a renewable origin, namely raw materials from plant or animal sources, wherein, with respect to the total film weight:
  • esters are in an amount ⁇ 25%
  • the polyesters are in an amount ⁇ 15%; the natural oils are in an amount ⁇ 15%,
  • the composition of the mixture of the plasticized PVC according to the invention provides for the presence of esters, polyesters and natural oils .
  • esters used in the formulation of the invention are obtained from fatty acids of a renewable origin with alcohols or poly-alcohols, always of a renewable origin (glycerin, ethanol, hetero-cyclic compounds derived from glucose) . Moreover, they are obtained from the purification and/or transformation of natural oils of a renewable origin (from seeds of soy, palm, castor oil, flax, cotton, olive, etc.) in an amount ⁇ 25%.
  • esters are:
  • polyesters used in the formulation of the invention are obtained through reaction of bi and tri-functional carboxylic acids of a renewable origin (citric acid, succinic acid, sebacic acid, azelaic acid, etc.) with glycols and poly-glycols of a renewable origin, in an amount ⁇ 15%.
  • a renewable origin citric acid, succinic acid, sebacic acid, azelaic acid, etc.
  • polyesters More in detail, such polyesters are:
  • polyesters of adipic acid and 1 , 3-butanediol , 1, 2-propanediol and 2-ethyl-l-esanol are examples of polyesters of adipic acid and 1 , 3-butanediol , 1, 2-propanediol and 2-ethyl-l-esanol .
  • the natural oils used in the formulation of the invention are of a renewable origin, epoxidized and/or hydrogenated (soy, palm, castor oil, flax, cotton, olive, etc.) in an amount ⁇ 15%.
  • the formulation of the invention is completed with components such as: anti-fogging agents (typically esters of fatty acids) in an amount on the order of 1-3%; stabilizers in an amount on the order of 1-2% and lubricants in an amount on the order of 0.1-0.3%.
  • anti-fogging agents typically esters of fatty acids
  • stabilizers typically in an amount on the order of 1-2%
  • lubricants in an amount on the order of 0.1-0.3%.
  • the above mentioned film is obtained through a preliminary mixing step of PVC resin and the various components composing the "dry Blend” mixture, where the “compounding” process occurs producing a PVC compound which must be left at rest to allow its cooling and its complete homogenization .
  • the following step implies the horizontal extrusion of a tubular from the above compound which, through an extruding head, forms an air- inflated bubble which, suitably contained and compressed through rollers, is collected in rolls of double-layered thin films with thickness on the order of 8 ⁇ 35 ⁇ (the range between 20 and 35 ⁇ being dedicated to frozen products) .
  • the film thickness is given by the size of the gap on the extrusion head and the air inflation, which stretches the walls of the material forming the bubble.
  • the orientation in a thin film is therefore bidirectional and is determined by the stretch due to the film winder (machine direction) and by the side stretch determined by the inflation, to define the bubble diameter (transversal direction) .
  • the particular combination of the mixture of the plasticxzers and the specific mixing conditions used in the plasticizing step guarantee the homogeneity of the melt materials .
  • the bidirectional orientation imparted during the extrusion step cooperates to define the features and the final performances of the resulting plastic film in terms of chemical, physical, mechanical, thermal and optical characteristics.
  • additives incorporated and characterizing the above compound are those that allow conferring to the film the above desired properties, and in particular :
  • the mechanical properties are the physical properties satisfying the mechanical performances of the packaging material, including the friction and resistance properties.
  • the anti-fogging properties refer to a particularly appreciated feature, which allows avoiding the micro-condensation of humidity, which fogs up the packages of fresh and refrigerated products, typically meat and vegetable products.
  • the gas transmission refers to the phenomenon of the permeation of gas and vapors through a packaging material, and it is extraordinarily important for the quality of the packaged food product, allowing breathing and natural metabolism of fresh products.
  • the low migration of additives is the property that defines the low release of additives from the plastic film to the wrapped product, thus guaranteeing food safety.
  • the anti-static property due to a reduction of the surface resistance, ensures that the film is not statically charged during its production and use .
  • Puncture resistance is the property for which the package is capable of resisting to the penetration of objects having a sharpened shape, with which it should accidentally get in contact.
  • Transparency, gloss and capability of being colored are properties which refer to the package appeal .
  • a first formulation has been prepared, with the following composition:
  • PVC resin 67.4% monomeric plasticizer based on capric and caprilic acid triglyceride 6.7% polymeric plasticizer based on polyesters of 1, 2-propandiol and/or 1,3- and/or 1, 4-butandiol and/or polypropyleneglycol with adipic acid
  • di-butyl sebacate 3.4% mixtures of esters of fatty acids 2.7% - fatty acid salts of Ca/Zn in epoxidized soybean oil 1.4% - stearic acid 0.2%.
  • a second formulation has been prepared, having the following composition:
  • a third formulation has been prepared, having the following composition:
  • acetyl tri-n-butyl citrate 10.1% epoxidized soybean oil 4.0% di-butyl sebacate 4.0% mixtures of esters of fatty acids 2.7% fatty acid salts of Ca/Zn in epoxidized soybean oil 1.3% stearic acid 0.1%.
  • Table 1 includes the optical properties ("haze” and “gloss”) , the gas transmission properties (0 2 , C0 2 and WV-water vapor) and the mechanical properties (elongation at break and tensile strength at break) of the three formulations in Examples 1, 2 and 3, and of "KOEX 814", such properties having been obtained according to the cited ASTM standards.
  • the present invention provides for an amount in weight of mixture of plasticizers from a renewable source between 10% and 40% and, preferably, between 20% and 30%.
  • such mixture of plasticizers from renewable source comprises:
  • esters from a renewable source in an amount in weight ⁇ 25%, and preferably included between 10% and 20%;
  • polyesters from a renewable source in an amount in weight ⁇ 15%, and preferably between 2% and 12%; natural oils from a renewable source in an amount in weight ⁇ 15%, and preferably included between 3% and 8%.
  • such mixture of plasticizers from a renewable source comprises a mixture of:
  • esters from a renewable source in an amount in weight ⁇ 25%, and preferably included between 10% and 15%;
  • polyesters from a renewable source in an amount in weight ⁇ 15%, and preferably included between 9% and 11%;
  • the transverse direction (TD) is the most stressed one, and as shown in Figure 1 which reproduces the stress and strain curve, the composition described in Example 3, proposed in a thickness of 13 ⁇ (with a reduction over 7% compared to the reference thickness) , faithfully reproduces of the performances of the reference material, called "KOEX 814".
  • the behavior of the stress and strain curve of Figure 1 points out a mechanical behavior of the packaging material suitable to satisfy quite high functional performances during packaging, such as to be particularly suitable also for automatic machines aimed for industrial production lines, capable of wrapping up to 90 trays per minute (Automac 75 and Automac 95 of the Applicant) .
  • Example 3 and its related mixture show mechanical properties satisfying the operating conditions on Automac packaging machines with reduced thicknesses (13 ⁇ ) with respect to the reference one (KOEX 814, 14 ⁇ ) .
  • the 17- ⁇ thickness exactly replicates the "KOEX818" reference with a thickness of 18 ⁇ , as pointed out by the diagram in Figure 2.
  • analyses have been performed about the contents of carbon-14 in the film.
  • the analyses with carbon-14 are used to univocally measure in a reproducible way the exact percentage of carbon derived from renewable sources (or biomass) : in particular, such analyses, described in the ASTM D6866 method, distinguish between modern carbon, derived from biomass, and carbon derived from fossil fuels.
  • the biomass contains a certain amount of carbon-14 which makes it easily distinguishable from other materials, such as fossil fuels, which do not contain carbon-14. Since the amount of carbon-14 present in the biomass is known, the percentage of carbon derived from renewable resources can be easily computed on the total carbon in the sample.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un film étirable en PVC plastifié, destiné à être utilisé avec des machines d'emballage automatique, les plastifiants étant d'une origine renouvelable (matières premières provenant de sources végétales ou animales). Le film contient des esters, des polyesters et des huiles naturelles, d'origine renouvelable, les esters étant présents dans une quantité ≤ 25 %, les polyesters étant présents dans une quantité ≤ 15 % et les huiles naturelles étant présentes dans une quantité ≤ 15 % par rapport au poids total du film.
PCT/IT2018/000090 2017-07-10 2018-06-26 Film étirable en pvc plastifié destiné à être utilisé sur une machine d'emballage automatique WO2019012564A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP18749880.3A EP3652243A1 (fr) 2017-07-10 2018-06-26 Film étirable en pvc plastifié destiné à être utilisé sur une machine d'emballage automatique

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT102017000077244 2017-07-10
IT102017000077244A IT201700077244A1 (it) 2017-07-10 2017-07-10 Film estensibile in PVC plastificato, in particolare per utilizzo su macchina confezionatrice automatica

Publications (1)

Publication Number Publication Date
WO2019012564A1 true WO2019012564A1 (fr) 2019-01-17

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PCT/IT2018/000090 WO2019012564A1 (fr) 2017-07-10 2018-06-26 Film étirable en pvc plastifié destiné à être utilisé sur une machine d'emballage automatique

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Country Link
EP (1) EP3652243A1 (fr)
IT (1) IT201700077244A1 (fr)
WO (1) WO2019012564A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT202000015022A1 (it) 2020-06-23 2021-12-23 Novamont Spa Pellicole per l’imballaggio con agente antiappannante

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59168012A (ja) * 1983-03-15 1984-09-21 Mitsui Toatsu Chem Inc 食品包装用ストレツチフイルム
JPS60108453A (ja) * 1983-11-16 1985-06-13 Adeka Argus Chem Co Ltd 食品包装用塩化ビニル樹脂組成物
JPH0625292B2 (ja) * 1985-10-17 1994-04-06 旭電化工業株式会社 食品包装フイルム用塩化ビニル樹脂組成物
JPH0788973A (ja) * 1993-09-28 1995-04-04 Shin Etsu Polymer Co Ltd ポリ塩化ビニル系ストレッチフィルムの製造方法
WO2011021400A1 (fr) * 2009-08-20 2011-02-24 三井化学ファブロ株式会社 Film étirable en polychlorure de vinyle
IT1392800B1 (it) 2009-01-27 2012-03-23 Manuli Stretch Spa Film estensibile biodegradabile
IT1392986B1 (it) 2009-02-23 2012-04-02 Eberle Dispositivo per il recupero energetico.
IT1402747B1 (it) 2010-10-27 2013-09-18 Novamont Spa Poliestere biodegradabile e pellicole aderenti per l'imballaggio con esso realizzate
EP3009373A1 (fr) * 2013-06-12 2016-04-20 Mitsubishi Plastics, Inc. Film à base de chlorure de vinyle pour emballage alimentaire

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59168012A (ja) * 1983-03-15 1984-09-21 Mitsui Toatsu Chem Inc 食品包装用ストレツチフイルム
JPS60108453A (ja) * 1983-11-16 1985-06-13 Adeka Argus Chem Co Ltd 食品包装用塩化ビニル樹脂組成物
JPH0625292B2 (ja) * 1985-10-17 1994-04-06 旭電化工業株式会社 食品包装フイルム用塩化ビニル樹脂組成物
JPH0788973A (ja) * 1993-09-28 1995-04-04 Shin Etsu Polymer Co Ltd ポリ塩化ビニル系ストレッチフィルムの製造方法
IT1392800B1 (it) 2009-01-27 2012-03-23 Manuli Stretch Spa Film estensibile biodegradabile
IT1392986B1 (it) 2009-02-23 2012-04-02 Eberle Dispositivo per il recupero energetico.
WO2011021400A1 (fr) * 2009-08-20 2011-02-24 三井化学ファブロ株式会社 Film étirable en polychlorure de vinyle
IT1402747B1 (it) 2010-10-27 2013-09-18 Novamont Spa Poliestere biodegradabile e pellicole aderenti per l'imballaggio con esso realizzate
EP3009373A1 (fr) * 2013-06-12 2016-04-20 Mitsubishi Plastics, Inc. Film à base de chlorure de vinyle pour emballage alimentaire

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
LEDA COLTRO ET AL: "Performance evaluation of new plasticizers for stretch PVC films", POLYMER TESTING, vol. 32, no. 2, 1 April 2013 (2013-04-01), AMSTERDAM, NL, pages 272 - 278, XP055511903, ISSN: 0142-9418, DOI: 10.1016/j.polymertesting.2012.11.009 *
MELISSA GURGEL ADEODATO VIEIRA ET AL: "Synthesis and application of natural polymeric plasticizer obtained through polyesterification of rice fatty acid", MATERIALS RESEARCH, vol. 17, no. 2, 18 February 2014 (2014-02-18), BR, pages 386 - 391, XP055461820, ISSN: 1516-1439, DOI: 10.1590/S1516-14392014005000017 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT202000015022A1 (it) 2020-06-23 2021-12-23 Novamont Spa Pellicole per l’imballaggio con agente antiappannante
WO2021260031A1 (fr) 2020-06-23 2021-12-30 Novamont S.P.A. Films d'emballage avec agent antibuée

Also Published As

Publication number Publication date
IT201700077244A1 (it) 2017-10-10
EP3652243A1 (fr) 2020-05-20

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