• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention relates to a material suitable for use in packages comprising nano-sized cellulose and an ethylene scavenging or ethylene absorbing agent. The invention also relates to methods for manufacturing such material, which may be paper, label, paperboard, plastic or film products.
    公开号:SE1651029A1
    申请号:SE1651029
    申请日:2016-07-11
    公开日:2018-01-12
    发明作者:Backfolk Kaj；Saukkonen Esa；Lampainen Seppo；Andersson Marianne；Heiskanen Isto；SIITONEN Simo
    申请人:Stora Enso Oyj；
    IPC主号:
    专利说明:

    MATERIAL SUITABLE FOR USE IN PACKAGES AND PROCESSFOR MANUFACTURING THEREOF Technical field The present invention relates to a material suitable for use in packagescomprising nano-sized cellulose and an ethylene scavenging or ethyleneabsorbing agent. The invention also relates to methods for manufacturingsuch material, which may be paper, label, paperboard, plastic or filmproducts.
    Background Food and food products, including packaged foods and food products, aregenerally subject to two main problems: microbial contamination and qualitydeterioration.
    As some produces such as fruits and vegetables ripen, they release ethylene,a gas that accelerates ripening, causing fruit and vegetables become spottedand soft and decay. ln addition to changed texture, the taste, odor or nutrientbehavior of the produce might change. Ethylene-related problems cause alarge part of post-harvest losses in developing countries.
    There are various methods and products in the art, for preserving foodmaterial from negative effects of ethylene gas. The use of modifiedatmosphere or storage at lower temperature is often used although thesemight have a negative effect on at least some of the organoleptic behaviors ofthe produces. A method to introduce ethylene scavenging properties involves using potassium permanganate as an ethylene oxidizing agent as disclosed 2 in WO 2005/000369 A1 and EP 0 515 764 A2. Potassium permanganate isincorporated into absorbent materials having high surface area such asalumina, silica, clay and activated carbon. However potassium permanganateis prohibited in Europe and limited latitude exists in the U.S. as far as theabsorbent material is stored in sacs because of the toxicity of potassiumpermanganate. lncorporating different functional minerals into polymeric films,on the other hand is also well known and such products are already availablein the market.
    JP2242767 discloses a bag made of plastic film having defined airpermeability and a waterproofness of at least 30mm and containing freshvegetables and another film bag containing a gas adsorbent placed togetherin a corrugated fiberboard box, preferably in the box provided with a barrier inthe central groove of its corrugated surface. The plastic film may havedispersed therein a powder of a porous substance consisting of open cell orfine cellulose fibers.
    Many of the methods known in the art are based on absorbents including aethylene gas decomposing agent or catalyst. The existing solutions havebeen tested on various films, papers and carton board packaging solutionsetc.
    One problem with the existing solutions is the limited amount of availablesurface area. The use of nanomaterials often require a high amount ofbinders or retention chemicals, or must be added via coating. Anotherproblem is that often the maximum amount of added material is restrictedsince it affects e.g. the strength or barrier properties of the materialconcerned. For example, in polyethylene plastics, higher amounts ofabsorbents or carrier particles will affect the strength properties and hencethe convertability of the material. Therefore, the amount of ethylene scavenger that can be added with maintained mechanical properties of the 3 material is often insufficient to obtain the desired anti-ripening effects on the packaged fruits or vegetables.
    There is thus a need for improved products for packaging, particularlyproducts that can help address the issues related to quality deterioration of packaged food.
    Summarv of the invention lt has surprisingly been found that by incorporating nano-sized cellulose in amaterial suitable for use in packages, said material comprising an ethylenescavenging or ethylene absorbing agent, some of the problems described above can be overcome.
    The term nano-sized cellulose as used herein encompasses microfibrillated cellulose (MFC) and nanocrystalline cellulose.
    The material suitable for use in packages can be paper, a label, paperboard, plastic or a film or a coating. ln one embodiment of the present invention, the ethylene scavenging orethylene absorbing agent is incorporated into the material, i.e. the ethylenescavenging or ethylene absorbing agent is present at the time ofmanufacturing or preparing the nano-sized cellulose or is mixed with the nano-sized cellulose prior to forming a film or web.
    The material which comprises an ethylene scavenging agent and/or ethyleneabsorbing agent and nano-sized cellulose, can also be applied with a coating or printing process, either each component separately or together. 4 ln another embodiment of the present invention, the ethylene scavenging orethylene absorbing agent is incorporated into the material suitable for use in packages, by coating or impregnation.
    One embodiment of the present invention is a coating for use in or on thematerial suitable for use in packages, that comprises nano-sized celluloseand an ethylene scavenging and/or ethylene absorbing agent. The coatingwould typically comprise at least 1 g/m2, preferably at least 5 g/m2, morepreferably at least 10 g/m2 ethylene scavenging and/or ethylene absorbing agent.
    The material according to the present invention typically comprises at least1% of nano-sized cellulose, preferably at least 5% of nano-sized cellulose, more preferably at least 10% nano-sized cellulose. ln one embodiment of the present invention, the material according to thepresent invention comprises from 0.05 to 50 weight-% ethylene scavengingand/or ethylene absorbing agent, preferably from 0.1 to 20 weight-%. lt is also possible to modify the nano-sized cellulose with e.g. inorganiccatalysts through chemical vapor deposition or atomic layer depositionmethods. ln this case, it is preferably that the nano-sized cellulose materialhas a relatively high surface area which can be exposed to the deposition ofthe inorganic chemical.
    One aspect of the invention is a paper, label, paperboard, plastic or filmproduct comprising, coated with or impregnated with nano-sized cellulose andan ethylene scavenging or ethylene absorbing agent. The film can be madefrom a plastic material, biopolymer or cellulose or cellulose fibrils, regeneratedcellulose, bioplastic etc. The product can be a rigid packaging product or a flexible package such as a bag. 5 The final package prepared using a material according to the presentinvention may have by multiple layers of said paper, board or film accordingto the present invention. The layers may be laminated together. ln oneembodiment of the present invention, the ethylene scavenging agent orethylene absorbing agent is present in the final package in the form of a labelon which a top coating is optionally arranged. The top coating may comprisean adhesive on one side such that the top coating can be removed, such asbeing peeled off, thereby exposing and activating the ethylene scavengingagent or ethylene absorbing agent. Said top coating may be sensitive tohumidity and/or moisture so that the top coating may loose its gas barrierproperties at incresed humidity or moisture, thereby exposing and activatingthe ethylene scavenging agent or ethylene absorbing agent. ln oneembodiment of the present invention, this may be achieved by using a topcoating that comprises nano-sized cellulose, such as microfibrillated cellulose. ln one embodiment of the present invention, the material suitable for use inpackages has a high surface area and preferably high ethylene, C02 and 02permeability, which can be achieved by using absorbents, but also by usinge.g. alcohol or debonding agents or by microflocculating the nano-sized cellulose _ ln one embodiment of the present invention, the material suitable for use inpackages is thin, preferably <50 gsm (g/m2), more preferably <30 gsm. lnanother embodiment, the material is thicker, such as more than 50 gsm ormore than 100 gsm. ln one embodiment of the present invention, the gas permeability of thematerial suitable for use in packages is >50 cm3/m2/day determined at 50%relative humidity and at 23°C for a film with a thickness of 30 um. ln oneembodiment, the gas permeation as determined by the OTR value is >500,preferably >1000. ln one embodiment of the present invention, the material suitable for use inpackages has a high content of ethylene absorbing agent, preferably >10 wt% more preferably >30 wt%. ln one embodiment of the present invention, the ethylene scavenging agentor ethylene absorbing agent can be dosed to the wet end of a process formanufacturing a paper, label, or paperboard product or may be added to theby surface sizing, impregnation, coating or via printing. Alternatively, amicrofibrillated cellulose film may be functionalized through the use of atomiclayer deposition (ALD) or chemical vapor deposition or similar methods. ln one embodiment of the present invention, the nano-sized cellulose, such as microfibrillated cellulose in the material suitable for use in packages shouldhave SR >70, more preferably >80. SR denotes the Schopper Riegler numberwhich can be achieved as well as determined using methods known in the art. ln one embodiment of the present invention, the web used in the preparationof the material suitable for use in packages may also contain long fibers, e.g.<30% kraft fiber or more preferably <20% kraft fiber. ln one embodiment of the present invention, the material suitable for use inpackages has a high surface area, preferably BET >100 m2/g, mostpreferably > 200 m2/g.
    Detailed description The ethylene scavenging agent used in the present invention can for examplebe selected from potassium permanganate, iodic acid or potassium bromateon charcoal, potassium bromate and sulfuric acid, bromine liquids, silver 7 oxide , rare earth oxide, phosphate compounds , chlorate compounds ,ferrocyanin compounds, hypochlorite, hypochlorite salt and bromide or iodidesalts, chlorate, a chlorite, a certain metal and a metallic oxide, Kpermanganate, ascorbic acid, sodium citrate and water, peroxide, sodiumpermanganate (which may need a carrier such as a zeolite), periodic acid,calcium permanganate or potassium iodate, potassium peroxymanganate,tobermorite and silver, xonotlite and silver, Ferrous sulfate heptahydrate andcalcium hydroxide, brominated carbonaceous molecular sieves, hydrogenbromide and bromine adduct of vinyl pyridine resin, bromine-addedvinylquinoline-type resin, calcium hypochlorite, sodium hypochlorite,potassium hypochlorite, and magnesium hypochlorite. Catalytic chemicalsthat function as ethylene scavenging agents include ammonium molybdatecontaining palladium sulphate catalyst (for detection), electron-deficient dieneor triene incorporated in an ethylene-permeable substrate (benzene, pyridine,diazine, triazine or tetrazine having electron-withdrawing substituents,preferably a fluoroalkyl group, sulphone group and/or ester group, the estergroup being dicarboxylated or dicarboxymethylated), hydrophobic(hydrosilylation) catalyst with e.g. Pt, high-molecular complex made bycoordination of CuCl and AlClg, Ti-, Al-, Ni or Fe-oxide, palladium cpd.adsorbed on carbon black, metal oxide e.g. alumina and metal e.g. platinum,cyclodextrin and PEI, active carbon treated with palladium chloride, palladiumdoped Zeolite Socony Mobil (ZSM)-5, or a photosensitive agent obtaining itsethylene scavenging properties after exposure to light, such as UV light orsunlight. _ ln one embodiment of the present invention, the ethylene scavenging agent isa catalyst or catalytic chemical, such as a platinum-containing or palladium-containing catalyst.
    The catalyst can be prepared using methods known in the art. The catalystcan be in the form of a catalyst-doped zeolite or using another absorbent than a zeolite. ln one embodiment of the present invention, the ethylene scavenging agent isa platinum-containing or palladium-containing catalyst or a high-molecularcomplex made by coordination of CuCl and/or AlClg. ln one embodiment of the present invention, the nano-sized cellulose is MFC.
    The material suitable for use in packages can also made with a so called castprocess. The suspension of MFC or fine cellulose is deposited on a carriersubstrate, semipermeable or non-permeable, with or without the ethylenescavenging agent or ethylene absorbing agent (for example a catalyst or itsprecursors). Drying is then made in order to produce the free standing film orintermediate product thereof. One option is to dose the ethylene scavengingagent or ethylene absorbing agent in a second step through any of thementioned surface treatment steps. The cast coating is also more suitable forsolvent based process.
    The material can further be modified with additives such as low molecularcarbohydrates, such as hemicellulose sorbitol etc., which are sensitive towater and moisture, i.e. allows the structure to swell.
    One aspect of the present invention is a microfibrillated cellulose film intowhich an ethylene scavenging agent in the form of a catalyst, such as aplatinum-containing or palladium-containing catalyst has been absorbed.
    The ethylene absorbing agent used in the present invention can for examplebe selected from charcoal, zeolites, silica, modified silica, aluminium oxide, al-silicates, sepolite, montmorillonite, bentonite, travertite or permutite,cristobalite, viscid ore, clay, coral, rape oil, carbon fiber, feldspathicporphyritic andesite , carbon nanoparticle, vermiculite, germanium,attapulgite, graphite, humus, pearlite, brickblock, tobermorite and organic resins. ln one embodiment of the present invention, the ethylene scavenging orethylene absorbing agent is incorporated into the material suitable for use inpackages. ln this embodiment the ethylene scavenging or ethylene absorbingagent is present at the time of preparing the microfibrillated cellulose or ismixed with the microfibrillated cellulose prior to forming a web. Thisembodiment includes a process for producing a dispersion comprisingmicrofibrillated cellulose and an ethylene scavenging or ethylene absorbingagent wherein the process comprises the steps of providing a slurrycomprising optionally pre-treated cellulose fibers, adding an ethylenescavenging or ethylene absorbing agent to the slurry and treating the slurryby mechanical disintegration so that a dispersion comprising microfibrillatedcellulose is formed in which the ethylene scavenging or ethylene absorbingagent is being absorbed to the surface of the microfibrillated cellulose and/orbeing absorbed into the microfibrillated cellulose. By treating a slurrycomprising optionally pre-treated cellulose fibers and an ethylene scavengingor ethylene absorbing agent by mechanical disintegration it is possible to produce a stable dispersion.
    The mechanical disintegration is preferably done in a pressure homogenizer.lt has been shown that by using a pressure homogenizer it is possible toproduce microfibrillated cellulose with more open areas and at the same timedisperse the ethylene scavenging or ethylene absorbing agent of the dispersion in a very efficient way.
    The pressure used in the pressure homogenizer is preferably between 500-4000 Bar, more preferably between 1000-2000 Bar. The fiber or intermediateproduct can be fibrilled one or several times either with or without processadditives such as stabilizing agents or ethylene scavengers or precursorsthereof.
    The weight ratio between the microfibrillated cellulose and ethylenescavenging or ethylene absorbing agent of the dispersion is preferablybetween 10:90 to 90:10. Depending on what kind of microfibrillated celluloseand an ethylene scavenging or ethylene absorbing agent the dispersioncomprises, the ratio can vary. lt is preferred that a proportion of the ethylene scavenging or ethyleneabsorbing agent of the dispersion is being absorbed on the surface of or intothe microfibrillated cellulose.
    The dry content of the slurry to be treated by mechanical disintegration ispreferably between 0.05-30% by weight of fibers. The dry content of the slurrydepends on the ethylene scavenging or ethylene absorbing agent used, whatkind of MFC used as well as what kind of apparatus is used for the mechanical disintegration.
    The dry content of the dispersion after it has been treated by the mechanicaldisintegration is preferably above 50% by weight of fibers. The dispersion ispreferably dewatered after the mechanical disintegration in order to increasethe dry content. By increasing the dry content, transportation of the dispersionto other sites can be done a more efficient way. Furthermore, it has beenshown that by increasing the dry content of the dispersion the stabi|ity is even further increased. ln one embodiment. the process may further comprise washing of thedispersion after the mechanical disintegration. ln this way it is possible toremove any free ethylene scavenging or ethylene absorbing agent from thedispersion.
    The mechanical disintegration can be done in many different kinds ofmechanical treatment apparatus, for example refiners or grinders such asMasuko grinders or refiners or grinders used to manufacture MFC disclosed 11 in the prior art. However, it is preferred to use a pressure homogenizer whichin a very efficient way both will produce microfibrillated cellulose fibers frompre-treated fibers as well as potentially homogenize the ethylene scavengingor ethylene absorbing agent. A high pressure is used during mechanicaidisintegration, and the pressure is preferably between 500-4000 Bar,preferably between 1000-2000 Bar. The optimal pressure is often around1500 Bar. The pressure needed depends on the material being treated.However, too high pressures are often not beneficial to use since the wear ofthe equipment will be too high. One example of a specific pressure homogenizer is the so called microfluidizer. ln one embodiment of the present invention, a base film is formed in a papermaking machine or according to a wet laid production method, by providing asuspension or dispersion as described above onto a wire and dewatering theweb to form an intermediate thin substrate or said base film. A suspension ordispersion comprising microfibrillated cellulose as described above isprovided to form said base film. The suspension or dispersion may be entirelyaqueous or also contain other solvents than water such as alcohols, such as for example a co-solvent mixture of water and ethanol. ln one embodiment of the present invention, foam forming or foam coating is used in the manufacture of the material according to the present invention.
    The microfibrillated cellulose content of the suspension or dispersion may,according to one embodiment be in the range of from 60 to 99.9 weight-%based on the weight of solids of the suspension or dispersion. ln oneembodiment, the microfibrillated cellulose content of the suspension ordispersion may be in the range of 70 to 99 weight- %, in the range of 70 to 95weight- %, or in the range of from 75 to 90 weight-%.
    Microfibrillated cellulose (MFC) shall in the context of the patent application mean a nano scale cellulose particle fiber or fibril with at least one dimension 12 less than 100 nm. MFC comprises partly or totally fibrillated cellulose orIignocellulose fibers. The liberated fibrils have a diameter less than 100 nm,whereas the actual fibril diameter or particle size distribution and/or aspectratio (length/width) depends on the source and the manufacturing methods.
    The smallest fibril is called elementary fibril and has a diameter ofapproximately 2-4 nm (see e. g. Chinga-Carrasco, G., Cellulose fibres,nanofibrils and microfibrils,: The morphological sequence of MFCcomponents from a plant physiology and fibre technology point of view,Nanoscale research letters 2011, 6:417), while it is common that theaggregated form of the elementary fibrils, also defined as microfibril (Fengel,D., Ultrastructural behavior of cell wall polysaccharides, Tappi J., March 1970,Vol 53, No. 3.), is the main product that is obtained when making MFC e.g. byusing an extended refining process or pressure-drop disintegration process. Depending on the source and the manufacturing process, the lengthof the fibrils can vary from around 1 to more than 10 micrometers. A coarseMFC grade might contain a substantial fraction of fibrillated fibers, i.e.protruding fibrils from the tracheid (cellulose fiber), and with a certain amountof fibrils Iiberated from the tracheid (cellulose fiber).
    There are different acronyms for MFC such as cellulose microfibrils, fibrillatedcellulose, nanofibrillated cellulose, fibril aggregates, nanoscale cellulosefibrils, cellulose nanofibers, cellulose nanofibrils, cellulose microfibers,cellulose fibrils, microfibrillar cellulose, microfibril aggregrates and cellulosemicrofibril aggregates. MFC can also be characterized by various physical orphysical-chemical properties such as large surface area or its ability to form agel-like material at low solids (1-5 wt%) when dispersed in water. Thecellulose fiber is preferably fibrillated to such an extent that the final specificsurface area of the formed MFC is from about 1 to about 300 m2/g, such asfrom 1 to 200 m2/g or more preferably 50-200 m2/g when determined for a freeze-dried material with the BET method. 13 Various methods exist to make MFC, such as single or multiple pass refining,pre-hydrolysis followed by refining or high shear disintegration or liberation offibrils. One or several pre-treatment step is usually required in order to makeMFC manufacturing both energy efficient and sustainable. The cellulosefibers of the pulp to be supplied may thus be pre-treated enzymatically orchemically, for example to reduce the quantity of hemicellulose or lignin. Thecellulose fibers may be chemically modified before fibrillation, wherein thecellulose molecules contain functional groups other (or more) than found inthe original cellulose. Such groups include, among others, carboxymethyl(CM), aldehyde and/or carboxyl groups (cellulose obtained by N-oxylmediated oxydation, for example "TEMPO"), or quaternary ammonium(cationic cellulose). After being modified or oxidized in one of the above-described methods, it is easier to disintegrate the fibers into MFC or nanofibrillar size fibrils.
    The nanofibrillar cellulose may contain some hemicelluloses; the amount isdependent on the plant source. Mechanical disintegration of the pre-treatedfibers, e.g. hydrolysed, pre-swelled, or oxidized cellulose raw material iscarried out with suitable equipment such as a refiner, grinder, homogenizer,colloider, friction grinder, ultrasound sonicator, fluidizer such as microfluidizer,macrofluidizer or fluidizer-type homogenizer. Depending on the MFCmanufacturing method, the product might also contain fines, ornanocrystalline cellulose or e.g. other chemicals present in wood fibers or inpapermaking process. The product might also contain various amounts ofmicron size fiber particles that have not been efficiently fibrillated.
    MFC is produced from wood cellulose fibers, both from hardwood or softwoodfibers. lt can also be made from microbial sources, agricultural fibers such aswheat straw pulp, bamboo, bagasse, or other non-wood fiber sources. lt ispreferably made from pulp including pulp from virgin fiber, e.g. mechanical,chemical and/or thermomechanical pulps. lt can also be made from broke or recycled paper. 14 The above described definition of MFC includes, but is not limited to, the newproposed TAPPI standard W13021 on cellulose nanofibril (CMF) defining acellulose nanofiber material containing multiple elementary fibrils with bothcrystalline and amorphous regions.
    According to another embodiment, the suspension or dispersion maycomprise a mixture of different types of fibers, such as microfibrillatedcellulose, and an amount of other types of fiber, such as kraft fibers, fines,reinforcement fibers, synthetic fibers, dissolving pulp, TMP or CTMP, PGW, etc.
    The suspension or dispersion may also comprise other process or functionaladditives, such as fillers, pigments, wet strength chemicals, dry strengthchemicals, retention chemicals, cross-linkers, softeners or plasticizers,adhesion primers, wetting agents, biocides, optical dyes, fluorescentwhitening agents, de-foaming chemicals, hydrophobizing chemicals such asAKD, ASA, waxes, resins etc. Additives can also be added using a size press or a printing machine.
    The papermaking machine that may be used in the in the manufacture of amaterial according to the present invention may be any conventional type ofmachine known to the skilled person used for the production of paper, paperboard, tissue or similar products.
    Subsequent to the wet web being placed onto the wire, it is dewatered. Thedewatering on wire may, according to one embodiment be performed byusing known techniques with single wire or twin wire system, frictionlessdewatering, membrane-assisted dewatering, vacuum- or ultrasound assisteddewatering, etc. After the wire section, the wet web is further dewatered anddried by mechanical pressing including shoe press, hot air, radiation drying,convection drying, etc. The film might also be dried or smoothened by soft or hard nip (or various combinations) calenders etc.
    According to one embodiment the wet web is dewatered by vacuum, i.e.water, and other Iiquids, is sucked from the furnish when it is piaced on the wire. ln view of the above detailed description of the present invention, othermodifications and variations will become apparent to those skilled in the art.However, it should be apparent that such other modifications and variations may be effected without departing from the spirit and scope of the invention.
    权利要求:
    Claims (1)
    [1] 1. _ A material suitable for use in packages comprising nano-sized cellulose and an ethylene scavenging and/or ethylene absorbingagent. _ A material suitable for use in packages according to claim 1, wherein said material is or comprises a paper, label, film or paperboard orplastic product. _ A material suitable for use in packages according to claim 1 or 2, wherein the ethylene scavenging agent is a catalyst, such as aplatinum-containing or palladium-containing catalyst. _ A material according to any one of claims 1-3, wherein the material is a coating or is printed on a surface. _ A material according to any one of claims 1-4, wherein the ethylene scavenging agent and/or ethylene absorbing agent can be activated. _ A material according to any one of claims 1-5, wherein the ethylene scavenging agent and/or ethylene absorbing agent can be exposed byan increase in moisture or humidity which dissolves a protectivecoating or by removal of a top coating covering the ethylenescavenging agent and/or ethylene absorbing agent. _ A material according to any one of claims 1-6, wherein the nano-sized cellulose is microfibrillated cellulose. _ A process for producing a dispersion comprising microfibrillated cellulose and an ethylene scavenging or ethylene absorbing agentwherein the process comprises the steps: 17 a) providing a slurry comprising optionally pre-treated cellulosicfibers wherein the cellulosic fibers have optionally been pre-treated by mechanical treatment, enzymatic treatment,carboxy methylation, TEMPO oxidation, CMC grafting,chemical swelling or acid hydrolysis, b) adding an ethylene scavenging or ethylene absorbing agentto the slurry and treating the slurry by mechanicaldisintegration so that a dispersion comprising microfibrillatedcellulose is formed in which the ethylene scavenging orethylene absorbing agent is being absorbed to the surface ofthe microfibrillated cellulose and/or being absorbed into themicrofibrillated cellulose. 9. A process according to claim 8, wherein the mechanical disintegration is performed in a homogenizer. 10.A process according to claim 9, wherein the pressure in the homogenizer is from 500 to 2000 bar. 11.A process for preparing a material suitable for use in packagescomprising the step of forming a web using the dispersion obtained in step b) of claim 8 and dewatering and/or drying said web. 12.A dispersion prepared using the process according to any one ofclaims 8-10. 13. Use of a dispersion according to claim 12 for coating or impregnationof a paper, label, paperboard, plastic or film product.
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    同族专利:
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    SE1651029A|SE540667C2|2016-07-11|2016-07-11|Ethylene scavenging material suitable for use in packages and process for manufacturing thereof|SE1651029A| SE540667C2|2016-07-11|2016-07-11|Ethylene scavenging material suitable for use in packages and process for manufacturing thereof|
    US16/316,729| US20190291938A1|2016-07-11|2017-07-03|Ethylene scavenging material suitable for use in packages and process for manufacturing thereof|
    EP17827079.9A| EP3481740B1|2016-07-11|2017-07-03|Package comprising ethylene scavenging material|
    BR112019000105-0A| BR112019000105A2|2016-07-11|2017-07-03|ethylene cleaning material suitable for use in packaging and the process for its manufacture|
    CN201780041563.7A| CN109415152B|2016-07-11|2017-07-03|Ethylene scavenging material suitable for packaging and method of making same|
    PCT/IB2017/054004| WO2018011666A1|2016-07-11|2017-07-03|Ethylene scavenging material suitable for use in packages and process for manufacturing thereof|
    JP2019500502A| JP2019528219A|2016-07-11|2017-07-03|Ethylene scavenging materials suitable for use in packaging and methods for their production|
    CA3027321A| CA3027321A1|2016-07-11|2017-07-03|Ethylene scavenging material suitable for use in packages and process for manufacturing thereof|
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