Raeucherbare synthetische nahrungsmittelverpackungsfolie

RK 396,320 B the available invention refers to one r', 'ducherbare, synthetic food packing foil and in particular to a smokable, synthetic food packing foil, which sigkeit a Rauchdurchl and a Sanerstoff Gasundurchlässigkeit shows and which also an excellent smoking barness and a durable making effect without a secondary packing into plastic bags exhibit. Up to now the packing for food is implemented as to the Tünchern prepared meat by a Erstund a secondary packing. As Erstverpackang a packing material is selected, which is suitable for the education and maintenance of the form of the food, directly into the Verpackangsmaterial is packed and a fast permeation of the smoke components of w it-end the smoking process permitted. Examples of as first packing gewlthlte materials would be coverings, those from the Gedärmen of animals, like cows, S chweinen or bowls, to be made or Zeliulosehüllen, which are made from Viscosefolien. This smokable Erstverpackungsmaterialien shows gas permeability and is as packing materials for gew@hnliehe Nahnmgsmittellagerung unsuitable from there is necessary it to pack the food again in FoEe, which is gasandurchlässig, (secondary packing). Under the well-known Erstverpacknngsmateriafien foils of natural polymers, like Kollagene, are Chitine and Polysaceharide, or with Polyvinylalkohoiharz an impregnating paper [Japanese patent application No. 47-43198 (1972)], with ethyls/Vinylalkohol copolymer, which contains a softener, impregnated paper [Japanese patent application Offenlegnng (KOKAI) No. 52-57347 (1977)] and polyester copolymer foils, which contain Polyalkylenoxid [Japanese patent application No. 59-117530 (1984)]. This raueherbaren Erstverpackungsmaterialien does not show sufficient gas permeability and in such a way becomes a Zweitverpaektmg necessarily for the preservation of the food. Also Foñen, those to be mechanically perforated or porose foils for the improvement of the Ranchdurchlässigkeit suggested [British patent No. 1,397,472] also for these packing materials is necessary a secondary packing. Such, conventional, r', äucherbare Verpacknngsmaterialien requires a second packing process and as result results to error due to the Erh0hung of the processing steps, the packing materials and packaging machines and all increases the manufacturing costs. Admitted foils, which are gastmdurchHtssig for oxygen both smoke-permeable and, are foils from PP, like Polycaprolactam and to the Polymermischnngen of PP and at least a ionomeren resin, like modified ethyls/vinyl acetate copolymers and a modif'tzierten polyolefin [European patent application No. 139,888]. From the DE-A1 34 26 723 usuryable, thermoplasüsche plastic coverings are become known, which exist to the Polyhexamethylenadipamid or Polycaprolactam. Out these materials a good Methanoldurehlässigkeit and a high oxygen permeability have existing foils. From at-PS 375,814 Schlauchfolien from drawn plastic are become known for the packing and casing of pasty food as well as a procedure for their production. Such foils exhibit a good Elasüzitnt and flexibility. are not smokable however. The European patent application No. 139,888 suggests that foils, those from PP, which can take up at least 3% of their dead weight at water up to the Sättignng like e.g. Polycaprolactam, Polyarnino nheptylsäureamid, Polyhexumethylensebazinsäureamid, Polyhexamethylenadipinsäureamid and foils, which consist of polymer mixtures of PP, as described above, and exist of at least a ionomeren resin, like a modif'Lzierten ethyl vinyl acetate copolymers and modif'tziertem polyolefin, when smokable, thermoplastic, synthetic packing materials are used. However are the only, colorless, shrinkable coverings to the Polycaprolactam and Polyhexamethylenadipinsaureamid, transparent therein concretely geoffenbarten foils. The coverings from Polycaprolactam and Polyhexamethylenadipinsäureamid do not show sufficient Sanerstoff Gasundurehlässigkeit and the coverings from it are from there for longer storage times of food, in particular for food, which is sensitive to oxygen, not sufficient. Therefore it is the subject of the available invention, a food packing foil from a thermoplastic resin, which possesses a good smoke permeability and a oxygen Gasnndurchlässigkeit to manufacture. It is the subject of the available invention to manufacture a smokable food packing foil which shows a so good Räuehereffekt and a so good Sanerstoff GasundurchlEssigkeit that it is suitable during longer periods for the keeping of food sensitive to oxygen. When a result became from many investigations found that the Rauchdurchl stands sigkeit from a foil to the Nahrungsmittelverpackang during a smoking process in the close relationship with its permeability for methanol into the smoking components, and that a food, which is sensitive to oxygen is packed in this case in a smokable food packing foil from a thermoplastic resin, which a SauerstoffGasundurehlässigkeit sufficient for the practical use possesses and also a before determined permeability for methanol, under the condition, RK 396,320 B is dafl equal to the smoke permeability the Methanoldurehlässigkeit, can a food packing, which is well smokable and for a long time is anfbewahrbar, be received, without a secondary packing into plastic bags, necessary for the reaching of this goal, necessarily becomes. The available invention is based on these findings. A smokable food packing foil after the available invention contained at least one laminates % copolymer to a mixture from 50 to 90 the Gew,% PP and 10 to 50 thread out - Olefin and Vinylalkohol, S the toffeigenschaften do not laminate must a Durehlässigkeit up to a methanol concentration of 50% and less as 200 g/m2 day at a temperature of 60 °C and a relative humidity of 0% and a oxygen Gasdarchlässigkeit of no more than 50 cm3/m2 day at a temperature of *C and a relative humidity of 60% ensure. In the available invention those, Methanolkonzentraüon " the relative concentration, is if the concentration is accepted with the Sättigungsdampfdruck the temperature given by methanol at as 100%. The methanol permeability of a foil from a thermoplastic resin after the available invention can be consulted as standard for the Räuehereigenschaften. The smoke components formed with heating a material up during a Räncherprozesses penetrate usually through the food packing foil and into the food are transferred, thus the characteristic smell and taste develop after smoking. As result of the measurements of the Rauchdarchlässigkeit it was found that the Methanoldurchlttssigkeit is a suitable parameter for smoking characteristics. Pork sausage mass becomes into tubular coverings (thickness: 40 lam) from the material shown in table 1 filled and both ends of each covering is locked. This W/il'ste will become 75 min with 60 °C smoked and then it a sense test regarding the smell and the taste of its contents submitted and their permeability for Rauchbestandtelle (model substances) was measured. The results are shown in table 1. The evaluation of the sense test (commission test, accomplished by 10 Teilaehmem) is as follows: 0: no smoking barness (smoke has no effect) 1: weakly noticeable smoker flavour 2: clearly noticeable smoking flavour 3 " strongly noticeable smoking flavour 4: extremely strong smoking flavour the permeability for the smoke components it are in table 1 as relative relative which are based on the acceptance that the value of the permeability for all smoke components is with nylon 6 one, indicated. From these results it can be seen that the methanol permeability agrees with the evaluation of the sense test of the smoking barness. There different connections than methanol with the evaluation of the sense test of the Räueherbarkeit do not correlate are suitable it not than parameters of the evaluation of the smoking barness. Table 1 foil cellulose Nylon-6 polyethylene plasticized polyethylene material with low Vinylidenchlorid terephthalat density copolymer of Testpunkte sense test of the smoking barness 4,3,1,2,6,1,9,0,3 permeability (relative relative) water vapour 113< 1,0,1 0,04 0,3 Melhanol 1,7 1 0,2,0,1 0,01 RKs 396,320 B table 1 (continuation) foil cellulose material of Testpunkte permeability (relative relative) acetone 2 ethyl acetate 1 cresol oxygen 100< Nylon-6 polyethylene plasticized polyethylene with low Vinylidenchlorid terephthalat density copolymer 1 1 1 1 100,200 1 17 17 0,8,250 13 - 49,0,6,0,9 remarks (1) the steam permeability according to the method of JIS Z-0208 at a temperature of 40° and a relaUven humidity of 90% one determined. (2) around the methanol permeability to measure, becomes a piece of Foliein a cell the measurement of the gas permeability of the mark YANAKO GTR 10XL (of the company Yanagimoto Sasakusho CO. Ltd.) insertiert, by nitrogen on a concentration of 50% diluted methanol steam is determined with 60 °C and a relative humidity of 0% brought with a side the foil in contact, while on the other side of the foil a Süekstoffatmosphäre with a relative humidity of 0% and a temperature of 60 insists °C, the quantity methanol permeierte by the foil by means of gas chromatography. The permeability for other Rauchbestandteüe (model substances) is besUmmt with the same method. (3) the oxygen gas permeability at a temperature of 30 °C and a relative humidity of 60% using a piece of foil and equipment mark OXTRAN-100 (of the company Modern control CO.) was measured. The Durehlässigkeit of a methanol concentration of 50% may not be smaller than 200 g/m2 day at and preferably not smaller than 300 g/m2 day at., at a temperature of 60 °C and a relative humidity of 0%. A foil, which has a methanol permeability, which is smaller than 200 g/m2 day at, does not show also with food, which needs only a weak smell or taste after smoke, a smoking effect. Dam measured a foil after the invention a methanol permeability of at least 200 ghn2 day at. have and preferably from not less than 300 g/m2 day at. In order to achieve an average smoking taste, the foil a methanol permeability, which may not be as 1000 g/m2 day at, must possesses and around a strong Räuchergesehrnack, that as substantial is rauchig designated, to reach, a foil, whose methanol permeability is not smaller than 2000 g/m2 day at, is used. It is necessary that the foil shows the characteristic of an oxygen gas impermeability, which an oxygen gas permeability, which is smaller than a before certain value exhibits, in order to be able to conserve smoked food over long time. The oxygen gas permeability of a foil after the invention may not be larger than 50 cm3/m2 day at a temperature of 30 °C and a relaUven humidity of 60%. Although usual Nahnmgsmittel a secondary packing does not benöügen, if she is packed in a foil, whose SauerstoffGasdurchl amounts to, ässigkeit not less than 200 em3/m2 day at, can food, which is particularly sensitive to oxygen, not for long time in a such foil to be packed stored, so that then a secondary packing is necessary. In the special food, like e.g. Fleisehpaste, which are approximately empfmdiich in such a way that the Myoglobin contained in it loses od. such in contact with oxygen A COLOr, can, if them tssigkeit with foils, some oxygen Gasdurehl from more than 50 cm3/m2 day at. have, are packed, not long time to be stored, since the Myoglobin loses od. such its color. In a smokable food packing foil after the available invention, has the one laminate the packing material screen end PP material properties, which less do not ensure a methanol permeability of 50% and RK 396,320 B as 200 g/m3 day at a temperature of 60 °C and to a relative humidity of 0% and an oxygen gas permeability of no more than 50 cm3/m2 day at with one temperature of 30 °C and of a relative humidity of 60%, this PP has a portion of 50 to 90 Gew,%, preferably to 75 Gew,%, and the copolymer from o - Olef'm and Vinylalkohol a portion from 50 to 10 Gew,%, preferably from 45 to 25 Gew,%. If the portion of PP is below 50 Gew,%, then the mechanical firmness is, the creep resistance and the spatial stability of the packing foil as well as its ability to set itself on an article and decrease its smoking barness, so that it is difficult to make of it the desired Pancherbaren Nahrangsmittelverpaeknngsfolien. On the other hand, if the portion of PP lies over 90%, it is to be received with difficulty the desired oxygen gas impermeability. After Polyamld the available Erf'mdung is for example nylon 6, nylon 7, nylon 8, nylon 10, nylon 11, nylon 12, nylon 6-6, nylon 6-10, mixtures away or copolymers from the monomers. Copolymers out (x-Olefin and Vinylalkohol after the available invention are for example EthylenVinylalkohol of copolymers, propylene Vinylalkohol of copolymers or 1-Buten-Vinylalkohol of copolymers. The Vinylalkoholanteil in copolymers out “- Olefin and Vinylalkohol amount to 40 to 80 Mol,%, preferably 50 to 70 Mol,%. If the Vinylalkoholanteil is below 40%, it is difficult, the desired oxygen Gasnndurchl to reach 'lssigkeit whereas, if the Vinylalkoholanteil lies over 80 Mol,%, which is lowered thermal stability of the foil and is difficult it to manufacture a smoke-stable Nahrungsmittelverpackangsfolie. In another execution form of the available invention, a Nahrungsmittelverpaekungsfolie consists to one laminates a thermoplastic resin from a mixture from 50 to 90 Gew,% PP and 10 to Gew,% copolymer out “- Olefin and Vinylalkohol, this laminates shows sufficient smoking barness and oxygen gas impermeability and at least one laminates, selected of the group a) (x-Olef'm copolymer such as polyethylene, polypropylene or Poly l Buten, b) a copolymer from ethyls, propylene or 1-Buten and vinyl acetate or (metha) Aerylester, c) a copolymer from ethyls, propylene or 1-Briten and (metha) acrylic acid and a metal salt of it, d) an elastomer wieplastifiziertes polyvinyl chloride, polyester and a Styrolkautschttk, e) a cellulose and a f) in PP, which slgkeit a oxygen g sdurchl, which lies over the available invention corresponding the value (50 cm3/m2.Tag.atm). The thickness of the smokable food packing foil after the available invention amounts to 15 to 100 lam, in particular 20 to 60 lan. In a mehrsehiehtigen foil the thickness of the foil from thermoplastisehem resin, which is ducherbar r " and is oxygen gas impermeable, is 15 to 100 lan and the thickness of the others laminates (n) preferably 10 to 50 lam. Food, which is packed in Nahrungsmittelverpacknngsfolien after the available invention, needs a smoking process and a good preservation during extended Lagerzeitr " äume. , Meeresfrüehte pre-treated animal products such as ham, sausages, bacon and meat, dairy products such as cheese such as fish and pre-treated shellfish and eggs is mentioned as example. The food packing foil from a thermoplastic resin after the available invention is manufactured by a usual blow moulding and either a lengthened or ungedehnte foil (not shrinkable or shrinkable foil) depending upon whom-hire-SPC-hits a corner manufactured. A lengthened (shrinkable) foil can be received by stretching in a well-known procedure. In the Räueherprozeß, a packing, which is manufactured by a usual packing process and dried alternatively, is given to the available invention for a predetermined time of one temperature from 15 to 80 °C to a Räucherkammer (the duration hangs some minutes of the too räuehernden food starting from and betr, tgt until some hours). The smoking temperature can be selected in such a way that they 15 to 30 ° (2 (cold smoking method), 30 to 50 °C (warm smoking method) or 50 to 80 °C (hot smoking method) amounts to, but Warmund welfare] ränchermethode, which are suitable at high temperature and short time for the mass production, are preferred. Smoking can be accomplished with an electrical smoking method, whereby an electrical field affects a smoke atmosphere of hardwood such as Eiehenholz or after Kirschholz actually well-known way. A r'aucherbare Nahrungsmittelverpackangsfolie after the available invention has a good permeability for a methanol concentration of 50% and not less as 200ag/m2.Tag.atm, preferably not less as 300 g/m2.Tag.atm and in particular from not less than 1000 g/mZ.Tag.atm at a temperature of ° (2 and a relative humidity of 0%. Additionally a such foil has a good mechanical firmness, r'dnmliche stability, creep resistance, puts on itself well to an article in-wound therein and is also well r " aucherbar. In addition the foil can be used as packing material for smoked food, which is stored longer time. In the special it shows an excellent smoking barness and SauerstoffGasundurehlässigkeit regarding food, is sensitively approximately wiez. B. Ham, sausage, RK 396,320 B meat and cheese and it is able such food for long time, without conserving secondary packing. The available invention is more near described on the basis of examples. Example 1 to 3rd comparison example 1 a PP copolymers from the Monomeron a nylon 6 and nylon 6-6 (weight ratio 85:15), and a copolymer from ethyls and Vinylalkohol (molar ratio 43:57) is dargesteUt as follows. The PP and ethyls/Vinylalkohol copolymer becomes in a Mischangsverhältnis from 8 to 2 (example I), 7 3 (example 2) and 6 za 4 (example 3) mixed. Each of these mixtures is pressed with 230 °C in a Extmder with a round stamp at the point, into a röhrenißrmige form and stretched with 60 °C by a usual Aufblamveffahren, so that lengthened tubular foils with 40 will receive lan thickness and a width from 70 mm as examples a 1, 2 and 3. The permeability for a Methanolkonzentrafion of 50% at a temperature of 60 °C and einermlativea Feuehügkeit of 0% u.nd oxygen gas permeability with 30 °C and a relative humidity of 60% of the foils in example 1, 2 and 3 are determined according to the measuring method described above. The results are shown in table 2. The tubular Foüen in example 1, 2 and 3 is filled with 200 g Wursffleisch by the pig from 50 the Gew. - % pork, 20 Gew. - % fat, 6 Gew. - % strength, 2 Gew. - % salt and 22 Gew. - % water exists and both ends is locked, so that one receives sausages after example 1.2 and 3. Each sausage is dried in a Räucherkammer with 60 °C, 15 minutes with a relaäven humidity from 10 to 30% and smoked then 90 minutes at a temperature of 60 °C and a relative humidity from 40 to 60%. The Raueherbarkeit that foils of example 1.2 and 3 becomes by the sense test described above (Kommissastes0 examined and the results are shown in table 2. For the Vergleiehsbeispiel 1 become the Methanoldurehlässigkeit, the oxygen gas permeability and the smoking barness of a usual cellulose packing, which exhibits 30 lan thickness and 50 mm broad examined. The results are shown in table 2. Table 2 example 1 example 2 example 3 comparison example 1 sense test of smoking barness taste 2.5,2.2,2.4,3.0 smell 2.7,2.8,3.0,3.5 methanol Durchlässi keit (g/m2.Tag.atm) 6.600 4.700 3.800 2.600 oxygen Durchlässi keit (cm3/m2.Tag.atm) 41 36 26 1,000< Evaluation Räncherbarkeit A A A A durability B B B D RK 396,320 B remarks: 03 Kritefien for dio A lswcrtong (i) Raueherbarkeit (commission test accomplished of 10 persons) A: sturk noticeable Räueheraroma} B: relatively strongly noticeable smoking flavour C: noticeable smoking flavour (usable) D: weakly noticeable smoking flavour 1 E: not räueherbar (smoke shows; no result) 1 I.angzeit keeping A: very well (l more tnger than 60 days) B: well (longer than 30 days) (not usable) (usable) C: weakly (not usable) D: badly (not usable) (Il3 criteria for the smoking barness (of senses eSO group test accomplished of 10 persons 0: not räueherbar (smoke shows no result) 1: noticeable smoking flavour 2: clearly noticeable smoking flavour 3: strongly m of erkbares Räueheraroma 4: unusual smoking flavour as made of table 2 to be clearly seen knows, is the smokable food packing foil both excellently räueherbar and excellently after the available invention in the durable making. In the special one the oxygen Gasdurehlässigkeit can be attained low enough around extended Konserviemng with approximately oxygen-sensitive food. Vergleichsbeisoiele 2 to for the Vergleiehsheispiel 2 is formed a piece stretched Polyethylenterephthalaffolie (thickness 121am) to r lhrenförmigen foils with 50 mm broad using an adhesive. For the comparison examples 3, 4 and 5 polyethylene (density 0.92), nylon 6 and a copolymer from the monomers nylon 6 and nylon 6-6 in a Gewiehtsverhälmis, nngedehnte foils of 40, tubular from 85 to 15 used and, lam thickness and 50 mm broad is received according to the same method as in example 1. The results of measurement of the methanol permeability and the SauerstoffGasdurehlässigkeit of these foils, similarly to example 1 accomplished, are indicated in table 3. Table 3 see ex. 2 see ex.s 3 Vergl.Bsp. 4 Verg. Ex. Sense test for smoking barness taste 0,1.7,2.3,2.7 smell 0.3,1.8,2.4,2.4 methanol permeability (g/m2.Tag.atm) 13,910 4.500 5.900 oxygen Gasdurchlässi keit (em3) m2.Tag.atm 120,1.0 (O< 80,100 RKs 396,320 B table 3 (Fortsetzunu) see ex. 2 see ex.s 3 Vergl.Bsp. 4 Verg. Ex. Evaluation Rltucherbarkeit E B A A durability C D C C criteria for the evaluation and the sense test for the smoking barness: equal as table 2. Example 4 a mixture (weight ratio 60:40) from the same PP as in example I and a copolymer from ethyls and Vinylalkohol (MolverMltnis 31:69) is manufactured as outer one nschichte of a multilevel foil. A copolymer manufactured to ethyls and vinyl acetate, Gewichtsverhälmis 67:33 as inside laminate. The inside and the ltullere laminate with 230 °C injected around a tubular mehrschichüge foil to receive, afterwards with 70 °C are together stretched, so that a tubular, lengthened foil of 40 lma thickness (thickness of the ulleren laminate: 25 lam, and which laminates inside: 15 one receives lam) and 70 mm broad. The methanol permeability, which oxygen gas permeability and the smoking effect of in such a way received foil becomes in similar way as certainly in example 1. The results are shown in table 4. Tùbellc 4 example 4 Sinneste$ f@r 0i R@tlchCr kei Gemch 1.5 taste 1.8 Methanoldurchlässi keit (g/m3.Tag.atm) 1350 oxygen Durchlässi keit (cm3/m2.Tag.atm) 49 evaluation smoking barness B durability A criteria for the evaluation and the sense test for the smoking barness: equal as for table 2. RK 396,320 B as by table 4 is shown, is both well räucherhar and well preserving smokable food packing foils after the available invention and it is not necessarily so packed smoked food to oxygen is sensitive again with a foil for oxygen is impermeable to pack. To receive example the same mixture as in example 2 by an extrusion with circular stamp pressed over tubular foils ungedehnte at the point from 50 lam thickness. The Methanoldurehlässigkeit, which oxygen gas permeability and smoking bark ELT of in such a way received foil became as measured in example 1. The results are shown in table 5. Table example sense test of the Räucherbark¢it smell 3.1 taste 2.8 Methanoldurchl ssigkeit (g/m3.Tag.atm) 4800 oxygen Durchlitssiukeit (em3/m2.Tag.atm) evaluation smoking barness A durability B the criteria for the usefulness and the sense test of the smoking barness: equal as for table 2. How is shown by table 5, smokable Nahrungsmittelverpaekungsfolien is both well smokable and well preserving after the available invention, and it is not necessarily into such foils packed food even if it to oxygen is sensitive again into a foil is oxygen gas impermeable to pack. As here particularly selected Ausf'ührungen of of the available invention was described, it understands itself automatically that of it still most diverse modifications be implemented it can and it is intended that the following patent claims all such modifications fall into the range and the sense of the invention, with would fall asleep. RK 396,320 B