NO314763B1 - Long-life polymer packaging containing a fruit and / or vegetable beverage, and use of a polymer layer for the manufacture of - Google Patents
Long-life polymer packaging containing a fruit and / or vegetable beverage, and use of a polymer layer for the manufacture of Download PDFInfo
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- NO314763B1 NO314763B1 NO19972321A NO972321A NO314763B1 NO 314763 B1 NO314763 B1 NO 314763B1 NO 19972321 A NO19972321 A NO 19972321A NO 972321 A NO972321 A NO 972321A NO 314763 B1 NO314763 B1 NO 314763B1
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- packaging
- fruit
- vegetable
- beverage
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- 238000004806 packaging method and process Methods 0.000 title claims abstract description 41
- 235000013361 beverage Nutrition 0.000 title claims abstract description 36
- 235000013311 vegetables Nutrition 0.000 title claims abstract description 26
- 235000013399 edible fruits Nutrition 0.000 title claims abstract description 25
- 229920000642 polymer Polymers 0.000 title claims description 29
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 229920001897 terpolymer Polymers 0.000 claims abstract description 18
- 239000002356 single layer Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 26
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 13
- 235000011389 fruit/vegetable juice Nutrition 0.000 claims description 12
- 235000005979 Citrus limon Nutrition 0.000 claims description 11
- 244000131522 Citrus pyriformis Species 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 240000007087 Apium graveolens Species 0.000 claims description 8
- 235000015849 Apium graveolens Dulce Group Nutrition 0.000 claims description 8
- 235000010591 Appio Nutrition 0.000 claims description 8
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 7
- 244000000626 Daucus carota Species 0.000 claims description 7
- 235000002767 Daucus carota Nutrition 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 235000021537 Beetroot Nutrition 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 230000035699 permeability Effects 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 244000291564 Allium cepa Species 0.000 claims description 4
- 235000002732 Allium cepa var. cepa Nutrition 0.000 claims description 4
- 240000000560 Citrus x paradisi Species 0.000 claims description 4
- 230000015556 catabolic process Effects 0.000 claims description 4
- 238000006731 degradation reaction Methods 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 4
- 240000008415 Lactuca sativa Species 0.000 claims description 3
- 235000003228 Lactuca sativa Nutrition 0.000 claims description 3
- 235000007688 Lycopersicon esculentum Nutrition 0.000 claims description 3
- 240000003768 Solanum lycopersicum Species 0.000 claims description 3
- 244000003416 Asparagus officinalis Species 0.000 claims description 2
- 235000005340 Asparagus officinalis Nutrition 0.000 claims description 2
- 240000007124 Brassica oleracea Species 0.000 claims description 2
- 235000003899 Brassica oleracea var acephala Nutrition 0.000 claims description 2
- 235000011299 Brassica oleracea var botrytis Nutrition 0.000 claims description 2
- 235000011301 Brassica oleracea var capitata Nutrition 0.000 claims description 2
- 235000004221 Brassica oleracea var gemmifera Nutrition 0.000 claims description 2
- 235000001169 Brassica oleracea var oleracea Nutrition 0.000 claims description 2
- 240000003259 Brassica oleracea var. botrytis Species 0.000 claims description 2
- 244000308368 Brassica oleracea var. gemmifera Species 0.000 claims description 2
- 240000004160 Capsicum annuum Species 0.000 claims description 2
- 235000008534 Capsicum annuum var annuum Nutrition 0.000 claims description 2
- 244000019459 Cynara cardunculus Species 0.000 claims description 2
- 235000019106 Cynara scolymus Nutrition 0.000 claims description 2
- 235000016622 Filipendula ulmaria Nutrition 0.000 claims description 2
- 244000046052 Phaseolus vulgaris Species 0.000 claims description 2
- 235000010627 Phaseolus vulgaris Nutrition 0.000 claims description 2
- 235000004478 Tragopogon dubius Nutrition 0.000 claims description 2
- 240000006060 Tragopogon pratensis Species 0.000 claims description 2
- 235000005699 Tragopogon pratensis Nutrition 0.000 claims description 2
- 235000016520 artichoke thistle Nutrition 0.000 claims description 2
- 239000001511 capsicum annuum Substances 0.000 claims description 2
- 239000012141 concentrate Substances 0.000 claims description 2
- 239000008267 milk Substances 0.000 claims description 2
- 235000013336 milk Nutrition 0.000 claims description 2
- 210000004080 milk Anatomy 0.000 claims description 2
- 235000009337 Spinacia oleracea Nutrition 0.000 claims 1
- 244000300264 Spinacia oleracea Species 0.000 claims 1
- 239000006185 dispersion Substances 0.000 claims 1
- 235000020400 fruit nectar Nutrition 0.000 claims 1
- 229920006254 polymer film Polymers 0.000 claims 1
- 235000020401 vegetable nectar Nutrition 0.000 claims 1
- SULYZTDOTDBHFD-UHFFFAOYSA-N buta-1,3-diene;methyl prop-2-enoate;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N.COC(=O)C=C SULYZTDOTDBHFD-UHFFFAOYSA-N 0.000 abstract 2
- -1 polyethylene terephthalate Polymers 0.000 description 12
- 239000010410 layer Substances 0.000 description 9
- 239000004698 Polyethylene Substances 0.000 description 8
- 229920000573 polyethylene Polymers 0.000 description 8
- 235000013305 food Nutrition 0.000 description 7
- 239000005020 polyethylene terephthalate Substances 0.000 description 7
- 229920000139 polyethylene terephthalate Polymers 0.000 description 7
- 229920001824 Barex® Polymers 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 230000004888 barrier function Effects 0.000 description 5
- 235000015203 fruit juice Nutrition 0.000 description 5
- 235000015205 orange juice Nutrition 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- 235000015192 vegetable juice Nutrition 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 235000019568 aromas Nutrition 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000009928 pasteurization Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000010101 extrusion blow moulding Methods 0.000 description 2
- 239000000796 flavoring agent Substances 0.000 description 2
- 235000019634 flavors Nutrition 0.000 description 2
- 235000021554 flavoured beverage Nutrition 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000000341 volatile oil Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 206010051246 Photodermatosis Diseases 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 229920003182 Surlyn® Polymers 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- 235000014171 carbonated beverage Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007705 chemical test Methods 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 239000008162 cooking oil Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000029142 excretion Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000012041 food component Nutrition 0.000 description 1
- 239000005417 food ingredient Substances 0.000 description 1
- 235000012055 fruits and vegetables Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 239000003845 household chemical Substances 0.000 description 1
- 238000010102 injection blow moulding Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- 230000002906 microbiologic effect Effects 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000008845 photoaging Effects 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 235000015067 sauces Nutrition 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 235000014348 vinaigrettes Nutrition 0.000 description 1
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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/18—Homopolymers or copolymers of nitriles
- C08J2333/20—Homopolymers or copolymers of acrylonitrile
Abstract
Description
Foreliggende oppfinnelse vedrører en ny polymerinnpakning med lang levetid og som inneholder en frukt- og/eller grønnsaksbasert drikkevare. Oppfinnelsen vedrører også anvendelse av et polymersjikt for fremstilling av en innpakning som skal være i kontakt med frukt- og/eller grønnsaksbaserte drikkevarer for å begrense forringelse av drikkevarene, og en fremgangsmåte for å begrense forringelse av frukt- og/eller grønnsaksbaserte drikkevarer inneholdt i polymerinnpakningen. The present invention relates to a new polymer packaging with a long life and which contains a fruit and/or vegetable-based beverage. The invention also relates to the use of a polymer layer for the production of a wrapper which is to be in contact with fruit and/or vegetable-based beverages in order to limit deterioration of the beverages, and a method for limiting deterioration of fruit- and/or vegetable-based beverages contained in the polymer wrapper .
Innpakninger for frukt- og/eller grønnsaksbaserte drikkevarer må være i stand til beholde drikkevarenes organoleptiske egenskaper. Glassinnpakningen er den mest anvendte innpakning på grunn av dens gassbarriere-egenskaper, men mer spesielt på grunn av dens høye kjemiske uvirksomhet. Den generelle tendens er imidlertid å erstatte dette materiale med polymerer, som har kjente fordeler i flere aspekter: letthet, uknusbarhet, osv. Packaging for fruit and/or vegetable-based beverages must be able to retain the beverage's organoleptic properties. The glass wrap is the most used wrap because of its gas barrier properties, but more especially because of its high chemical inertness. However, the general tendency is to replace this material with polymers, which have known advantages in several aspects: lightness, unbreakability, etc.
Imidlertid er anvendelsen av slike innpakninger begrenset på grunn av nevnte ulemper, spesielt på grunn av tap av organoleptiske egenskaper over tid, som er tilknyttet både permebiliteten og de fysiske/kjemiske gjensidige innflytelser mellom aromaene og polymerene. However, the use of such wrappers is limited due to the aforementioned disadvantages, especially due to the loss of organoleptic properties over time, which are associated with both the permeability and the physical/chemical mutual influences between the aromas and the polymers.
Anvendelse av polymerer for innpakning av matvarer medfører ofte problemer på grunn av gjensidig innflytelse mellom innholdet og beholderen. The use of polymers for packaging food often causes problems due to mutual influence between the contents and the container.
Problemene er beskrevet i litteraturen og består hovedsakelig av: The problems are described in the literature and mainly consist of:
Flåin<g> (" scalping" 1) : Dvs, adsorpsjon av matvarebestanddeler ved materialets overflate. Dette fører til lavere aromaintensitet og, hvis adsorpsjonen er selektiv, til endring i aroma og smak. Dette fenomen, som styres av stoffenes fordelingskoeffisienter mellom matvarene og materialet, vil være enda alvorligere ved vandige matvarer slik som fruktsaft. Flåin<g> ("scalping" 1): Ie, adsorption of food ingredients at the surface of the material. This leads to lower aroma intensity and, if the adsorption is selective, to a change in aroma and taste. This phenomenon, which is controlled by the substances' distribution coefficients between the food and the material, will be even more serious with watery foods such as fruit juice.
Absorpsjon: Etter adsorpsjonen kan det oppstå absorpsjon av aroma ved polymeren, diffusjon i polymeren og deretter utskilling i polymerens ytre overflate. I dette tilfelle vil det også oppstå tap av eller endring i aromaintensiteten. Absorption: After the adsorption, absorption of aroma by the polymer, diffusion in the polymer and then excretion in the outer surface of the polymer can occur. In this case, there will also be a loss of or change in aroma intensity.
Kjemisk reaksjon mellom smaksstoffer og polymeren: Det er mulig for polymeren å være både reagent og katalysator. Følgende forsøk viser delte fenomen: En modelloppløsning med omkring ti smaksstoffer ble plassert i kontakt med en polymer (PP). Ved gasskromatografi-analyse av oppløsningen ble det funnet mange flere stoffer tilstede enn de opprinnelige ti. Chemical reaction between flavors and the polymer: It is possible for the polymer to be both a reagent and a catalyst. The following experiments show shared phenomena: A model solution with about ten flavors was placed in contact with a polymer (PP). By gas chromatography analysis of the solution, many more substances were found present than the original ten.
Likeledes består ikke frukt- og/eller grønnsakssaft i en innpakning fremstilt av polyetylen tereftalat (PET) en aldringstest på seks måneder. Spesielt kan det observeres for tidlig oksydering av innpakningen. Likewise, fruit and/or vegetable juice in packaging made from polyethylene terephthalate (PET) does not pass an aging test of six months. In particular, premature oxidation of the packaging can be observed.
For å løse dette problem er det foreslått anvendelse av en flerlagsinnpakning omfattende et indre lag av en etylen-/vinylalkoholpolymer dekket på hver side av et polyetylensjikt og med et mellomliggende bindemiddel. Imidlertid er en slik innpakning ugjennomsiktig eller kan vise gjennomsiktighet ved kontakt hvis polyetylenmaterialet erstattes med polypropylen. In order to solve this problem, the use of a multi-layer packaging comprising an inner layer of an ethylene/vinyl alcohol polymer covered on each side by a polyethylene layer and with an intermediate binder has been proposed. However, such wrapping is opaque or may show transparency upon contact if the polyethylene material is replaced with polypropylene.
I tillegg er ekstruderingsmetoden anvendt for fremstilling av en slik innpakning komplisert og øker derved innpakningenes salgspris. In addition, the extrusion method used to produce such packaging is complicated and thereby increases the sales price of the packaging.
Anvendelse av en flerlagsinnpakning omfattende et indre lag av nylon (PA) eller av en etylen-/vinyla!koholpolymer dekket av to ytre lag av polyetylen tereftalat fremstilt ved co-injeksjonsblåsing er også foreslått. Imidlertid har denne innpakning svært høy salgspris på grunn av vanskelighetene ved fremstillingen, og den er nesten ikke i bruk. The use of a multilayer wrapper comprising an inner layer of nylon (PA) or of an ethylene/vinyl alcohol polymer covered by two outer layers of polyethylene terephthalate produced by co-injection blow molding has also been proposed. However, this packaging has a very high selling price due to the difficulties in its manufacture, and it is hardly used.
Anvendelse av enkeltlagsinnpakning basert på polyetylennaftalat (PEN) som har svært gode egenskaper vedrørende lagring og gjennomsiktighet, er også foreslått. Imidlertid er denne type innpakning også svært kostbar og derved begrenses dens utvikling. The use of single-layer packaging based on polyethylene naphthalate (PEN), which has very good properties regarding storage and transparency, is also proposed. However, this type of packaging is also very expensive and thereby limits its development.
Anvendelse av enkeltlags innpakning basert på PET + PA (polyamid) Application of single-layer packaging based on PET + PA (polyamide)
+ koboltsaltlegering, som har svært gode egenskaper vedrørende lagring, gjennomsiktighet og oksygenabsorpsjon, er også foreslått. Imidlertid har det aldri vært mulig å demonstrere anvendelsen av dette materiale i matvaresektoren. + cobalt salt alloy, which has very good properties regarding storage, transparency and oxygen absorption, is also proposed. However, it has never been possible to demonstrate the application of this material in the food sector.
I tillegg er det kjent å anvende en metylakrylat/akrylonitril/butadien kopolymer med varemerkenavn Barex 210® (B.P. Chemicals) på grunn av dens gassbarriereegenskaper. Et slikt materiale er allerede blitt anvendt som beholder for kullsyreholdige drikkevarer, som angitt ved f.eks. US-patenter US-A-3, 862, 288; US-A-3, 963, 399 og US-A-4, 054, 630. In addition, it is known to use a methyl acrylate/acrylonitrile/butadiene copolymer with the trade name Barex 210® (B.P. Chemicals) because of its gas barrier properties. Such a material has already been used as a container for carbonated beverages, as indicated by e.g. US Patents US-A-3, 862, 288; US-A-3,963,399 and US-A-4,054,630.
Imidlertid er gassbarriereegenskapene helt forskjellige fra egenskapene tilknyttet kjemisk inerthet overfor aroma. Som vist ved de ovennevnte publikasjoner er dette problem ikke løst, selv lenge etter innlevering av de ovennevnte amerikanske patenter. However, the gas barrier properties are completely different from the properties associated with chemical inertness to aroma. As shown by the above-mentioned publications, this problem has not been solved, even long after the filing of the above-mentioned US patents.
Mannheim et al., Food and Packaging Interaction, 1988, kapittel 6, s. 68-82 analyserer den gjensidige påvirkning mellom sitronbaserte produkter og laminære strukturer slik som polyetylen, polyetylenvinylalkohol, surlyn (ionomerisk harpiks) og lineær lavtetthetspolyetylen. Mannheim et al., Food and Packaging Interaction, 1988, Chapter 6, pp. 68-82 analyze the interaction between lemon based products and laminar structures such as polyethylene, polyethylene vinyl alcohol, surlyn (ionomeric resin) and linear low density polyethylene.
Gilbert et al., Instrumental Analysis of Foods, 1983, bind 1, side 405-411 analyserer barriereegenskapene til polymersjikt for forskjellige aromatiske damper (polypropylen, PVDC, polyetylen). Gilbert et al., Instrumental Analysis of Foods, 1983, Volume 1, pages 405-411 analyze the barrier properties of polymer layers for various aromatic vapors (polypropylene, PVDC, polyethylene).
Matsui et al., J. Agric. Food Chem. 1992, 40, 1902-1905, analyserer absorpsjonen av aroma ved innpakningssjikt slik som Matsui et al., J. Agric. Food Chem. 1992, 40, 1902-1905, analyzes the absorption of aroma by wrapping layers such as
middeltetthetspolyetylen og polyetylenalkohol. medium density polyethylene and polyethylene alcohol.
Benet et al., Analysis, (1992) 20, 391-396 analyserer den gjensidige påvirkning mellom høytetthetspolyetylenpropper og luftbårede organiske stoffer. Benet et al., Analysis, (1992) 20, 391-396 analyzes the interaction between high density polyethylene plugs and airborne organics.
Hensikten med den foreliggende oppfinnelse er å tilveiebringe en ny polymerbasert innpakning som tillater å oppbevare de organoleptiske egenskaper av frukt- og/eller grønnsaksbaserte drikkevarer for en svært lang periode, og som samtidig har følgende egenskaper: The purpose of the present invention is to provide a new polymer-based packaging that allows the organoleptic properties of fruit and/or vegetable-based beverages to be preserved for a very long period, and which at the same time has the following properties:
-gjenomsiktighet, -transparency,
-lave fremstillingskostnader. -low manufacturing costs.
Polymerinnpakningen ifølge oppfinnelsen består av et enkelt lag og enkeltlaget er dannet av en metylakrylat/akrylonitril/butadien terpolymer. The polymer wrapping according to the invention consists of a single layer and the single layer is formed from a methyl acrylate/acrylonitrile/butadiene terpolymer.
Uttrykket "frukt- og/eller grønnsaksbaserte drikkevarer" referer generelt til saft, fortynnet saft og drikkevarer med frukt- og/eller grønnsaksaroma. The term "fruit and/or vegetable based beverages" generally refers to juice, diluted juice and fruit and/or vegetable flavored beverages.
I foreliggende beskrivelse refererer uttrykket "frukt- og/eller grønnsakssaft" til vannoppløsninger som er resultatet av å presse, ved et hvilket som helst egnet middel, stoffet som er tilstede i frukter og/eller grønnsaker, eventuelt etter behandlingene som vanligvis anvendes i den tiknyttede industri, spesielt mikrobiologisk stabiliseringsbehandling (pasteurisering, sterilisering, tilføyelse av konserveringsmiddel), fortynningsbehandling, filtreringsbehandling, osv. I rekkefølge basert på kvaliteten skal det nevnes ren saft, saft basert på konsentrat, og nektar. In the present description, the term "fruit and/or vegetable juice" refers to aqueous solutions which are the result of pressing, by any suitable means, the substance present in fruits and/or vegetables, optionally after the treatments usually used in the industry, especially microbiological stabilization treatment (pasteurisation, sterilisation, addition of preservative), dilution treatment, filtration treatment, etc. In order based on quality, mention should be made of pure juice, juice based on concentrate, and nectar.
Uttrykket "frukt- og/eller grønnsaksaromadrikkevarer" refererer spesielt til rekonstruerte drikkevarer som inneholder mer enn én naturlig eller syntetisk aroma. The term "fruit and/or vegetable flavored beverages" specifically refers to reconstituted beverages containing more than one natural or synthetic flavoring.
Blant fruktbaserte drikkevarer kan man nevne drikkevarene basert på appelsin, sitron, tomat og grapefrukt. Among fruit-based beverages, one can mention the beverages based on orange, lemon, tomato and grapefruit.
Blant grønnsaksbaserte drikkevarer kan man nevne drikkevarene basert på Among vegetable-based beverages, one can mention the beverages based on
-selleri -gulrot - celery - carrot
-salat -rødbete -salad -beetroot
-artisjokk -løk - artichoke - onion
-rosenkål -asparges - Brussels sprouts - Asparagus
-paprika -blomkål - paprika - cauliflower
-hagegeiteskjegg -spinat -garden goat's beard -spinach
-grønn kål -broccoli -green cabbage -broccoli
-purre -erter -leek -peas
-aubergine -courgette -eggplant -courgette
-bete -fennikel -beetroot -fennel
-nepe -gresskar -turnip -pumpkin
-grønne bønner -green beans
Blant blandinger av forrskjellige frukter og grønnsaker kan det nevnes, uten å innføre begrensninger: Among mixtures of different fruits and vegetables, the following can be mentioned, without introducing limitations:
-gulrot, sitron -carrot, lemon
-tomat, gulrot, seleri, sitron, rødbeter, salat, løk -tomato, carrot, celery, lemon, beetroot, lettuce, onion
-tomat, seleri, sitron -tomato, celery, lemon
-gulrot, appelsin -carrot, orange
-tomat, gulrot, seleri, sitron, rødbeter, grapefrukt, -tomato, carrot, celery, lemon, beetroot, grapefruit,
appelsin. orange.
Nevnte drikkevarer kan også blandes med melk eller derivater derav. Said beverages can also be mixed with milk or derivatives thereof.
Uttrykket "innpakning" refererer til en hvilken som helst beholder som kan omfatte drikkevaren, utformet som en flaske, en kartong eller andre tilsvarende lukkede systemer, innbefattet poser og skinnflasker. The term "packaging" refers to any container that can contain the beverage, designed as a bottle, a carton or other similar closed systems, including bags and leather bottles.
Blant terpolymerene som egner seg for anvendelse inennfor rammen av foreliggende oppfinnelse, er terpolymerene med oksygenpermeabilitet lavere enn 0, 8 cm<3> x mm/m2 x dag x 10<5> Pa (1 bar = IO<5> Pa) ved 23 °C og med en relativ fuktighet på 100 % foretrukket. Among the terpolymers suitable for use within the scope of the present invention, the terpolymers with oxygen permeability lower than 0.8 cm<3> x mm/m2 x day x 10<5> Pa (1 bar = 10<5> Pa) at 23 °C and with a relative humidity of 100% preferred.
Disse materialer er tilgjengelige på markedet eller de kan tilveiebringes av en ekspert på området på kjent måte. These materials are available on the market or they can be provided by an expert in the field in a known manner.
Terpolymeren har fortrinnsvis et butadieninnhold på mellom 8 og 20 %. The terpolymer preferably has a butadiene content of between 8 and 20%.
Terpolymeren velges fortrinnsvis fra gruppen omfattende termopolymerer med butadientinnhold på omkring 10 % eller terpolymerer med butadieninnhold på omkring 18 %. The terpolymer is preferably selected from the group comprising thermopolymers with a butadiene content of about 10% or terpolymers with a butadiene content of about 18%.
Disse polymerer markedsføres av selskapet P.B. Chemicals med varemerkenavn henholdsvis Barex 210® og Barex 218®. These polymers are marketed by the company P.B. Chemicals with the brand names Barex 210® and Barex 218® respectively.
Polymeren Barex 210® har en oksygenpermeabilitet på 0, 3 cm x mm/m x dag x IO5 Pa ved 23°C. The polymer Barex 210® has an oxygen permeability of 0.3 cm x mm/m x day x 105 Pa at 23°C.
Polymeren Barex 218® har en oksygenpermeabilitet på 0, 6 cm<3> x mm/m2 x dag x 10<5>Paved23°C. The polymer Barex 218® has an oxygen permeability of 0.6 cm<3> x mm/m2 x day x 10<5>Paved23°C.
Disse polymerer anvendes allerede for innpakning av flere produkter slik som kosmetiske produkter, husholdningskjemiske produkter og artikler for medisinsk anvendelse. These polymers are already used for packaging several products such as cosmetic products, household chemical products and articles for medical use.
De anvendes også for enkelte forbruksprodukter slik som matolje, essensoije, krydder og vinaigrettesauser. Imidlertid kreves ikke oppbevaring av aromaene tilhørende frukt- og/eller grønnsakssafter ved produktene hittil innpakket ved hjelp av slike polymerer. They are also used for certain consumer products such as cooking oil, essential oils, spices and vinaigrette sauces. However, storage of the aromas associated with fruit and/or vegetable juices is not required for the products hitherto wrapped using such polymers.
Faktisk er problemet tilknyttet innpakking av fruktbaserte og/eller grønnsaksbaserte drikkevarer et spesifikt problem på grunn av den hovedsakelig vanndige natur av væsken der stoffene, spesielt aromastoffene, er tilstede. In fact, the problem associated with the packaging of fruit-based and/or vegetable-based beverages is a specific problem due to the predominantly aqueous nature of the liquid in which the substances, especially the flavoring substances, are present.
Siden essensoljene er lite oppløselige i vann er de tilbøyelige til å migrere i polymerene, konsekvensene av dette er: Since the essential oils are poorly soluble in water, they tend to migrate in the polymers, the consequences of this are:
-generell reduksjon av aromaintensiteten på -general reduction of the aroma intensity on
grunn av sorpsjonen av blandingen av aromatiske sammensetninger, -endring i aroma, på grunn av foretrukket sorpsjon av bestemte bestanddeler i aromaen, due to the sorption of the mixture of aromatic compounds, -change in aroma, due to preferential sorption of certain constituents of the aroma,
-nedbryting av aromabestanddeler med dannelse, -decomposition of aroma components with formation,
ved kontakt med polymeren, av nye molekyler som berøver produktet dets organoleptiske profil. Dette kan oppstå enten i direkte kjemiske reaksjoner med substrater eller i reaksjoner der substratet er katalysatoren. upon contact with the polymer, of new molecules that rob the product of its organoleptic profile. This can occur either in direct chemical reactions with substrates or in reactions where the substrate is the catalyst.
Disse fenomener er alvorligere ved drikkevarer inneholdende aromaer som er tungtoppløselige i vann og som har sterk affinitet med polymerene. These phenomena are more serious with beverages containing aromas that are poorly soluble in water and that have a strong affinity with the polymers.
Implementering av slike polymerer utføres i en vanlig Implementation of such polymers is carried out in a regular
ekstruderingsblåsingsmaskin slik som anvendes for PVC med eller uten bi-orientering. extrusion blow molding machine as used for PVC with or without bi-orientation.
Implementeringen er således rimelig idet den ikke krever anvendelse av en maskin som er spesifikk for produktet. The implementation is thus reasonable in that it does not require the use of a machine that is specific to the product.
Innpakningene består av et enkeltlagsmateriale fremstilt ved ekstrudering. Tykkelse av enkeltlaget varierer med type innpakning, men den vil fortrinnsvis ligge på mellom 200 og 500 um. The wraps consist of a single-layer material produced by extrusion. The thickness of the single layer varies with the type of packaging, but it will preferably be between 200 and 500 µm.
Tykkelsen ligger mellom 300 og 400 um, men den kan reduseres til 50 um for sjiktene og den kan nå opp til 1 mm eller mer for store beholdere (tønner osv.) The thickness is between 300 and 400 um, but it can be reduced to 50 um for the layers and it can reach up to 1 mm or more for large containers (barrels, etc.)
Innpakningen ifølge oppfinnelsen kan lagre en frukt- og/eller grønnsaksbasert drikkevare slik som frukt- og/eller grønnsakssaft i 12 måneder under samme forhold som en glassflaske, dvs. uten merkverdig nedbryting av drikkevarens organoleptiske egenskaper. The packaging according to the invention can store a fruit and/or vegetable-based beverage such as fruit and/or vegetable juice for 12 months under the same conditions as a glass bottle, i.e. without significant degradation of the beverage's organoleptic properties.
I tillegg er innpakningene gjennomsiktige, enkle å omforme og rimelige. In addition, the wrappers are transparent, easy to reshape and affordable.
Oppfinnelsen vedrører også anvendelse av metylakrylat/akrylonitril/butadien terpolymerer som beskrevet ovenfor i enkeltlagsform for fremstilling av en innpakning i kontakt med frukt- og/eller grønnsaksbaserte drikkevarer med den hensikt å begrense nedbryting av disse drikkevarer. The invention also relates to the use of methyl acrylate/acrylonitrile/butadiene terpolymers as described above in single-layer form for the production of a wrapper in contact with fruit and/or vegetable-based beverages with the intention of limiting degradation of these beverages.
Oppfinnelsen vedrører også en fremgangsmåte for å begrense nedbryting av frukt- og/eller grønnsaksbaserte drikkevarer inneholdt i The invention also relates to a method for limiting the degradation of fruit and/or vegetable-based beverages contained in
polymerinnpakninger, karakterisert ved at innpakningen er utformet som et enkelt lag og består av en metylakrylat/akrylonitril/butadien terpolymer som beskrevet ovenfor. polymer wraps, characterized in that the wrap is designed as a single layer and consists of a methyl acrylate/acrylonitrile/butadiene terpolymer as described above.
Oppfinnelsen er kjennetegnet ved det som angis i de vedlagte patentkrav. Oppfinnelsen vil nå beskrives ved hjelp av eksempler. The invention is characterized by what is stated in the attached patent claims. The invention will now be described by means of examples.
Eksempel 1 Example 1
Flasker bestående av et enkelt lag Barex 218® (markedsført av selskapet BP Chemicals) med en gjennomsnittstykkelse på 350 um, ble fremstilt ved omforming i en maskin for bi-orienteringsekstrusjonsblåsing av PVC. Bottles consisting of a single layer of Barex 218® (marketed by the company BP Chemicals) with an average thickness of 350 µm were produced by reforming in a PVC bi-orientation extrusion blow molding machine.
Flaskene ble fylt med kald Pampryl® appelsinsaft etter høypasteurisering og tilføyelse av en bakteriostat. Saften var avgasset på forhånd ved å boble nitrogen i den før pasteuriseringen, og flaskene ble skylt med nitrogen før fylling. Den opprinnelige oksygeninnhold i oppløsningen er derfor veldig lav, under 0.5 ppm. The bottles were filled with cold Pampryl® orange juice after high pasteurization and the addition of a bacteriostat. The juice was pre-degassed by bubbling nitrogen into it before pasteurization, and the bottles were flushed with nitrogen before filling. The initial oxygen content in the solution is therefore very low, below 0.5 ppm.
Eksempel 2 ( sammenligning) Example 2 (comparison)
En glassflaske med tilsvarende utforming som i eksempel 1 ble fylt på samme måte med ovennevnte appelsinsaft. Flaskens <g>jennomsnittstykkelse var 3 mm. A glass bottle with a similar design as in example 1 was filled in the same way with the above-mentioned orange juice. The <g>average thickness of the bottle was 3 mm.
Eksempel 3 ( sammenligning) Example 3 (comparison)
En polyetylentereftalat flaske med tilsvarende utforming som i eksempel 1 ble fylt på samme måte med ovennevnte appelsinsaft. Flaskens gjennomsnittlige tykkelse var 300 um. A polyethylene terephthalate bottle with a similar design as in example 1 was filled in the same way with the above-mentioned orange juice. The average thickness of the bottle was 300 µm.
Alle flasker ble lukket med en hette med en PE/ALU/PE skjøt. All bottles were closed with a cap with a PE/ALU/PE joint.
Flere fysiske-kjemiske prøver ble utført på flaskene i eksemplene 1, 2 og 3 for å undersøke egenskapene til de forskjellige innpakninger. Several physico-chemical tests were carried out on the bottles in examples 1, 2 and 3 to investigate the properties of the different wrappers.
Eksempel 4 - organoleptisk profil Example 4 - organoleptic profile
Flaskene ble lagret i 12 måneder i 20 °C og de organoleptiske egenskaper ble deretter målt. Saften som lå i innpakningen av polyetylentereftalat (eksempel 3) ble avvist, med dominerende koking- og oksideringstrekk. I tillegg ble det observert reduksjon av aromaintensiteten og tap av appelsinegenskaper. The bottles were stored for 12 months at 20 °C and the organoleptic properties were then measured. The juice contained in the polyethylene terephthalate wrapper (Example 3) was rejected, with dominant boiling and oxidation features. In addition, a reduction of the aroma intensity and a loss of orange characteristics were observed.
Appelsinsaften inneholdt i innpakningen ifølge eksempel 1 avvek ikke betraktelig fra appelsinsaften inneholdt i glassflasken (eksempel 2), som dannet referansen. The orange juice contained in the packaging according to example 1 did not differ significantly from the orange juice contained in the glass bottle (example 2), which formed the reference.
Eksempel 5 - endring i redokspotensialet Example 5 - change in the redox potential
Den vedlagte figur 1 representerer utviklingen av andelen totale reduserende enheter i mikrogram/liter som funksjon av tid for prøver tatt 1, 3, 6, 9 og 12 måneder etter begynnelsen av undersøkelsen. Innpakningen i eksempel 1 (ifølge oppfinnelsen) og eksempel 2 (glass) fulgte tilsvarende utvikling, mens innpakningen i eksempel 3 (PET) viste en betraktelig glidning (slippage) etter 6 måneders aldring, og derved svært høyt oksideringsnivå. The attached figure 1 represents the development of the proportion of total reducing units in micrograms/litre as a function of time for samples taken 1, 3, 6, 9 and 12 months after the start of the investigation. The packaging in example 1 (according to the invention) and example 2 (glass) followed a similar development, while the packaging in example 3 (PET) showed considerable slippage after 6 months of ageing, and thereby a very high level of oxidation.
Denne undersøkelse angir en utmerket korrelering med endringene i de organoleptiske egenskaper målt i eksempel 4. This investigation indicates an excellent correlation with the changes in the organoleptic properties measured in example 4.
Eksempel 6 - fotoaldrinestest Example 6 - photoaging test
Saftens fotosensitivitet er en veldig viktig faktor, som fastsetter saftens kvalitet. Følgelig var barrieregenskaper av innpakningsmaterialet i eksemplene 1 og 2 vurdert med ultrafiolett stråling og resultatene vises i figur 2, der transmisjonen angis som funksjon av bølgelengden. The photosensitivity of the juice is a very important factor, which determines the quality of the juice. Consequently, the barrier properties of the wrapping material in examples 1 and 2 were assessed with ultraviolet radiation and the results are shown in figure 2, where the transmission is indicated as a function of the wavelength.
Innpakningene ble underkastet sollys i 48 timer og 7 dager respektivt og sammenlignes med en glassinnpakning lagret i mørket (kontroll). The wrappers were subjected to sunlight for 48 hours and 7 days respectively and are compared with a glass wrapper stored in the dark (control).
Etter utsetningen til ultrafiolett stråling i 7 dager, økte terpeninnholdet i saften inneholdt i innpakningen ifølge eksempel 1, men kokte og oksiderte trekk var ikke sterkere enn i kontrollprøven. Saften i innpakningen ifølge eksempel 2 mistet appelsinfargen og var den mest negativt påvirket. After the exposure to ultraviolet radiation for 7 days, the terpene content of the juice contained in the wrapper according to Example 1 increased, but boiled and oxidized features were not stronger than in the control sample. The juice in the packaging according to example 2 lost its orange color and was the most negatively affected.
Claims (15)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9511104A FR2739081B1 (en) | 1995-09-21 | 1995-09-21 | LONG-TERM PACKAGING OF POLYMERIC MATERIAL CONTAINING A FRUIT-BASED BEVERAGE, USE OF A POLYMERIC FILM FOR PRODUCING SUCH PACKAGING |
| FR9604854A FR2739082B1 (en) | 1995-09-21 | 1996-04-18 | LONG-TERM PACKAGING OF POLYMERIC MATERIAL CONTAINING A BEVERAGE BASED ON FRUITS AND / OR VEGETABLES, USE OF A POLYMERIC FILM FOR THE PRODUCTION OF SUCH PACKAGING |
| PCT/FR1996/001457 WO1997010997A1 (en) | 1995-09-21 | 1996-09-19 | Long-life polymeric packaging containing a fruit and/or vegetable beverage, and use of a polymeric film for making same |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| NO972321D0 NO972321D0 (en) | 1997-05-21 |
| NO972321L NO972321L (en) | 1997-07-21 |
| NO314763B1 true NO314763B1 (en) | 2003-05-19 |
Family
ID=26232220
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO19972321A NO314763B1 (en) | 1995-09-21 | 1997-05-21 | Long-life polymer packaging containing a fruit and / or vegetable beverage, and use of a polymer layer for the manufacture of |
Country Status (13)
| Country | Link |
|---|---|
| EP (1) | EP0793601B2 (en) |
| JP (1) | JPH10509679A (en) |
| AT (1) | ATE181888T1 (en) |
| AU (1) | AU7088996A (en) |
| CA (1) | CA2206145A1 (en) |
| DE (1) | DE69603152T3 (en) |
| DK (1) | DK0793601T4 (en) |
| ES (1) | ES2134004T5 (en) |
| FR (1) | FR2739082B1 (en) |
| GR (1) | GR3030750T3 (en) |
| MX (1) | MX9703713A (en) |
| NO (1) | NO314763B1 (en) |
| WO (1) | WO1997010997A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2799222B1 (en) | 1999-09-30 | 2003-03-07 | Newmat Sa | PRINTED WELDABLE FLEXIBLE POLYMER MATERIAL FOR MAKING TENSIONED STRUCTURES, STRUCTURES OBTAINED WITH SUCH MATERIAL AND METHOD FOR PRODUCING SUCH STRUCTURES |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4826861A (en) * | 1971-08-12 | 1973-04-09 | ||
| US3862288A (en) * | 1971-08-12 | 1975-01-21 | Continental Can Co | Creep stabilization of plastic articles |
| US3979491A (en) * | 1971-11-24 | 1976-09-07 | Continental Can Company, Inc. | Process for the manufacture of an oriented container |
| US3963399A (en) * | 1971-11-24 | 1976-06-15 | Continental Can Company, Inc. | Injection-blow molding apparatus with parison heat redistribution means |
| US4054630A (en) * | 1976-01-22 | 1977-10-18 | American Can Company | Hot pin parison injection molding technique |
| US4899517A (en) * | 1986-10-13 | 1990-02-13 | Mitsui Toatsu Chemicals, Inc. | Storage, transporation method, packaging material, and package for agricultural products |
-
1996
- 1996-04-18 FR FR9604854A patent/FR2739082B1/en not_active Expired - Fee Related
- 1996-09-19 DE DE69603152T patent/DE69603152T3/en not_active Expired - Fee Related
- 1996-09-19 CA CA002206145A patent/CA2206145A1/en not_active Abandoned
- 1996-09-19 EP EP96931874A patent/EP0793601B2/en not_active Expired - Lifetime
- 1996-09-19 AU AU70889/96A patent/AU7088996A/en not_active Abandoned
- 1996-09-19 ES ES96931874T patent/ES2134004T5/en not_active Expired - Lifetime
- 1996-09-19 WO PCT/FR1996/001457 patent/WO1997010997A1/en active IP Right Grant
- 1996-09-19 JP JP9512441A patent/JPH10509679A/en active Pending
- 1996-09-19 DK DK96931874T patent/DK0793601T4/en active
- 1996-09-19 MX MX9703713A patent/MX9703713A/en not_active IP Right Cessation
- 1996-09-19 AT AT96931874T patent/ATE181888T1/en not_active IP Right Cessation
-
1997
- 1997-05-21 NO NO19972321A patent/NO314763B1/en unknown
-
1999
- 1999-07-14 GR GR990401835T patent/GR3030750T3/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| GR3030750T3 (en) | 1999-11-30 |
| ATE181888T1 (en) | 1999-07-15 |
| DE69603152T3 (en) | 2003-07-24 |
| CA2206145A1 (en) | 1997-03-27 |
| ES2134004T3 (en) | 1999-09-16 |
| DE69603152T2 (en) | 1999-11-25 |
| AU7088996A (en) | 1997-04-09 |
| EP0793601A1 (en) | 1997-09-10 |
| DK0793601T3 (en) | 2000-01-10 |
| JPH10509679A (en) | 1998-09-22 |
| DE69603152D1 (en) | 1999-08-12 |
| EP0793601B1 (en) | 1999-07-07 |
| NO972321L (en) | 1997-07-21 |
| WO1997010997A1 (en) | 1997-03-27 |
| FR2739082A1 (en) | 1997-03-28 |
| MX9703713A (en) | 1998-02-28 |
| DK0793601T4 (en) | 2003-04-07 |
| ES2134004T5 (en) | 2003-04-16 |
| EP0793601B2 (en) | 2002-12-18 |
| NO972321D0 (en) | 1997-05-21 |
| FR2739082B1 (en) | 1998-06-12 |
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