CN101415343A - Composition for controlling exposure to oxygen - Google Patents
Composition for controlling exposure to oxygen Download PDFInfo
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- CN101415343A CN101415343A CNA2007800121945A CN200780012194A CN101415343A CN 101415343 A CN101415343 A CN 101415343A CN A2007800121945 A CNA2007800121945 A CN A2007800121945A CN 200780012194 A CN200780012194 A CN 200780012194A CN 101415343 A CN101415343 A CN 101415343A
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Abstract
Compositions comprise a polymer having less than 5 aliphatic carbon-carbon double bonds per 100 copolymerized monomer units, an oxidizable metal, and a compound selected from the group consisting of ferrous salts having an anion selected from the group consisting of ascorbate, nitrate, citrate, gluconate, lactate and mixtures thereof are effective oxygen-scavenging compositions. The compositions are suitable for use as components of food and pharmaceutical packaging materials. In addition, compositions consisting essentially of a polymer having a less than 5 aliphatic carbon-carbon double bonds per 100 copolymerized monomer units, an oxidizable metal and a ferrous sulfate salt exhibit rapid uptake of oxygen in compositions substantially free of electrolytes having halide anions.
Description
Invention field
The present invention relates to the composition that absorbs oxygen and be used to make container, lid and other packaging products.The invention still further relates to goods by described preparation of compositions.
Background of invention
When in the presence of oxygen, storing, numerous food product and medicine there is adverse influence.Alleviating or eliminate the method that the oxygen of these oxygen sensitive materials exposes in packaging process or in storage process is the theme of many researchs.A strategy that addresses this is that is to spray by inert gas to remove deoxidation from product.Additive method relates to and uses parcel that contains the aerobic absorbing material or the pouch be placed in the packing.
By United States Patent (USP) 4,992,410 is known, and Xiang Tiezhong adds reaction promoter (for example sodium chloride), produces the oxygen absorbing material of the pouch use that is applicable to packaging for foodstuff.Other of this composition open patent disclosure 56-121634 (1981) and Japan Patent 54158386 (1979) referring to Japanese unexamined, wherein disclose the oxygen-absorbing composition that comprises iron powder, sodium chloride and filler, and in the open 56-148272 (1981) of the patent application of Japanese unexamined, disclose five component oxygen-absorbing compositions: a) iron or molysite, b for the mixture of following material) metal halide, c) carbonate, d) to the solid and the e of responding property of glassware for drinking water) amino acid.United States Patent (USP) 4,908,151 disclose the oxygen absorbent that is used for dried foods that comprises following material: a) unrighted acid and/or comprise fat oil, the b of unrighted acid) transition metal and/or transistion metal compound and c) alkaline matter calcium carbonate for example.
The vector resin that having described on the other hand of prior art is suitable for adding to the each several part that can be used for packaging material itself is to absorb the composition of headspace.The example of this composition can be referring to United States Patent (USP) 5,364,555, and it has described the oxygen-scavenging compositions of the compound that comprises vector resin, salicylic acid chelating agent or transition metal and ascorbic acid ester compounds.The patent disclosure 2002-80647 of Japanese unexamined discloses the sheet material that is used for packaging for foodstuff, and it comprises vistanex, iron, metal halide and mineral sulfates.United States Patent (USP) 5,274,024 also discloses such composition, and it is in conjunction with iron and various oxidation accelerator (comprising for example mixture of calcium chloride and magnesium chloride of sodium chloride and sodium chloride and other electrolyte).In addition, United States Patent (USP) 5,744,056 discloses oxygen removes material, the souring ingredients that it comprises fluoropolymer resin, oxidable metal, first electrolyte and only slightly be dissociated into the positive and negative ion in the aqueous solution.
United States Patent (USP) 5,211,875 disclose the packing articles that combines the layer that comprises oxidizable organic compound (comprising oxidable polymer, for example polyamide) and transition-metal catalyst.By composition is exposed to radiation, causes oxygen and remove.United States Patent (USP) 5,021,515 disclose the another kind of system that the packing wall is provided, and it comprises oxidable polymer (preferred polyamide) and metallic catalyst (for example cobalt).
The open 56-148272 (1981) of the patent application of above-mentioned Japanese unexamined discloses and has used the substitute of ferrous sulfate as elemental iron in the oxygen-scavenging compositions.At United States Patent (USP) 6,960, disclose in 376, in the oxygen-absorbing composition that does not comprise oxidable metal, use inorganic ferrous compound for example ferrous sulfate, frerrous chloride, ferrous nitrate, ferrous bromide and iron iodide, and the organic acid ferrous salt for example gallic acid is ferrous, ferrous malate and ferrous fumarate.Equally, United States Patent (USP) 6,037,022 discloses in not containing the oxygen of oxidable metal-removing composition and has used ferrous carbonate.The patent disclosure 2002-80647 of Japanese unexamined discloses the combination of using ferrous sulfate and metallic iron in oxygen-scavenging compositions, the open 1506718A1 of European patent discloses the combination of using the iron that scribbles lewis acid, comprises that frerrous chloride is as oxygen-scavenging compositions.United States Patent (USP) 4,299,719 disclose and contain ferrous carbonate, iron powder and metal halide and be used for the deodorizing packaged composition.
Neither one is omnipotent acceptable in these systems, there remains a need in the art in the packaging for foodstuff and can economical and effectively control composition and the system that oxygen exposes.What be concerned about in addition is, when as contact food or pharmaceutical packing system a part of, absorbent must be observed relevant Food Contact standard.
Summary of the invention
First embodiment of the present invention relates to a kind of oxygen-scavenging compositions, and described composition comprises:
A. has polymer less than 5 aliphatic carbon-to-carbon double bond/100 comonomer units;
B. oxidable metal; With
C. have anionic ferrous salt that is selected from ascorbic acid root, nitrate anion, citrate, glucose acid group and lactic acid anion and composition thereof, wherein said ferrous salt solubility in water under 25 ℃ is 1g/100g water at least.
The invention still further relates to a kind of laminated material, described laminated material comprises:
A. ground floor, described ground floor comprises:
1. at least a polymer that has less than 5 aliphatic carbon-to-carbon double bond/100 comonomer units;
2. oxidable metal; With
3. have anionic ferrous salt that is selected from ascorbic acid root, nitrate anion, citrate, glucose acid group and lactic acid anion and composition thereof, wherein said ferrous salt solubility in water under 25 ℃ is 1g/100g water at least; With
B. at least one deck other the layer.
The invention still further relates to a kind of composition, described composition is made up of following material basically:
A. has polymer less than 5 aliphatic carbon-to-carbon double bond/100 comonomer units;
B. oxidable metal; With
C. ferrous sulfate,
Described composition does not contain the electrolyte with halide anions substantially.
The invention still further relates to a kind of laminated material, described laminated material comprises:
A. ground floor composition, described composition is made up of following material basically:
1. at least a polymer that has less than 5 aliphatic carbon-to-carbon double bond/100 comonomer units;
2. oxidable metal; With
3. ferrous sulfate,
Described composition does not contain the electrolyte with halide anions substantially; With
B. at least one deck other the layer.
The invention still further relates to a kind of oxygen-scavenging compositions, described composition comprises:
A. has polymer less than 5 aliphatic carbon-to-carbon double bond/100 comonomer units;
B. oxidable metal; With
C. be selected from compound with the cationic molysite of ferrous ammonium and composition thereof, wherein said molysite solubility in water under 25 ℃ is 1g/100g water at least.
The invention still further relates to a kind of laminated material, described laminated material comprises:
A. ground floor, described ground floor comprises:
1. at least a polymer that has less than 5 aliphatic carbon-to-carbon double bond/100 comonomer units;
2. oxidable metal; With
3. be selected from compound with the cationic molysite of ferrous ammonium and composition thereof, wherein said molysite solubility in water under 25 ℃ is 1g/100g water at least; With
B. at least one deck other the layer.
Detailed Description Of The Invention
The present invention relates to the oxygen-scavenging compositions that has particular utility as the component that is used for the packaging material of the food that influences sensitivity, medicine and other materials of oxygen.Term used herein " oxygen-scavenging compositions " is meant and can reacts with the oxygen in the container that is present in sealing or combine, thereby reduction is present in the material or the compound of the oxygen content of internal tank.
Effective and the common fast Absorption oxygen of composition of the present invention.Can be used for making the component (for example being used as the component of one or more layers container cover) and the chamber wall composition of container and packaging structure.When using by this way, the inclusion that described composition can be controlled packing is exposed to oxygen.Oxygen-scavenging compositions of the present invention also is applicable to be placed on and is used for pouch or the parcel that oxygen absorbs in the container.
The polymers compositions of oxygen-scavenging compositions of the present invention usually but need not to be oxygen is had infiltrative polymer.Also must be to the relative inertness of oxidation own.That is to say, be applicable to that the aliphatic degree of unsaturation of polymer of the present composition is low.Particularly, described polymer has less than 5 two key/100 carbon atoms.Preferred described polymer has less than 1 two key/100 carbon atom.The blend of two or more this polymer also is applicable to composition of the present invention.Therefore, composition of the present invention can comprise other polymer that are different from first polymer (being selected from the polymer that has less than 1 aliphatic carbon-carbon bond/100 comonomer unit).Preferred described one or more polymer also have permeability to water vapour.Can use thermoplastic resin, thermosetting resin or thermoplastic elastomer (TPE).Any polymer that can add other components (being oxidable metal and molysite) of the present composition of effective dose is suitable.The example of available thermoplastic resin comprises polyamide, polyester, polystyrene, Merlon, polyvinyl acetate, polyvinyl chloride, polyolefin homopolymer and copolymer be polyethylene for example, polypropylene, ethylene is LLDPE for example, ethylene propylene copolymer, ethylene-butylene copolymer and POE, the copolymer of ethene and polar comonomers is EVAc for example, ethylene alkyl acrylate copolymer, the ethylene methacrylic acid alkyl ester copolymer, ethylene acrylic acid co polymer, ethylene methacrylic acid copolymer, EMA copolymer and slaine be ethylene acrylic acid co polymer for example, the ionomer of ethylene methacrylic acid copolymer and EMA copolymer.Preferred thermoplastic resin be those materials, particularly polypropylene of being usually used in packaging applications, polyethylene, EVAc, ethene (methyl) acrylic copolymer for example
The slaine of ethylene copolymer, ethene (methyl) acrylic copolymer for example
The polyolefin of ionomer resin, maleic anhydride graft for example
But the adhesive resin of co-extrusion, ethylene alkyl acrylate copolymer are for example
The AC acrylate copolymer all derives from Duponal curtain that company (E.I.du Pont de Nemours and Company); Polyamide homopolymer or copolymer, for example MXD-6 poly hexamethylene adipamide benzene dimethylamine, nylon 6 and the nylon 66 of Mitsubishi's aerochemistry (Mitsubishi Gas Chemical) production, PETG are for example
Mylar and derive from Kuraray Co., the ethylene-vinyl alcohol copolymer of Ltd.
The thermosetting resin that is suitable for use as polymers compositions comprises epoxides, oleo-resins, unsaturated polyester resin, unsaturated ethylene alpha olefin copolymer, for example EPDM, silicon rubber, neoprene, nitrile rubber, fluoroelastomer, Perfluoroelastomer and other elastomers.Preferred thermosetting resin is suitable for those compositions that Food Contact is used for the regulations according to U.S. food and drug administration.Most preferred back one type for being lower than those resins of 1 aliphatic double bond/100 comonomer unit finishing or solidify the back degree of unsaturation.
All oxygen-scavenging compositions of the present invention comprise at least a oxidable metal component.Suitable metal component is for providing and can comprise with one or more oxidable metal of the electrolyte reaction that other of composition must component with fine dispersion or particle form.Term used herein " electrolyte " is meant the compound that can be dissociated into the positive and negative ion in the aqueous solution.The example that is applicable to the oxidable metal of the present composition comprises iron, copper, manganese and cobalt.Because iron when promoting the oxygen cleaning reaction very effectively and easily the particle form with fine dispersion obtain, so iron is preferred oxidable metal.
In theory, the reaction between oxidable metal, electrolyte and oxygen is an electrochemical reaction, and reaction takes place for the two to need moisture and electronic conductor (being metal itself).The electrochemical properties of reaction allows only to avoid moisture by the protection component and controls reaction.It is common using in the industrial operation of resin as component that protective material is avoided moisture.
Other components of the present composition are the electrolyte with metal reaction.In one embodiment, described electrolyte is a solid iron salt, particularly has ferrous salt of the anion (being inorganic anion or acylate anion) that is selected from ascorbic acid root, nitrate anion, citrate, glucose acid group and lactic acid anion and composition thereof.These electrolytical other characteristics are that they are highly soluble in water.That is to say that molysite solubility in water under 25 ℃ is 1g/100g water at least, preferred 10g/100g at least, most preferably 20g/100g water at least.Therefore, comprise ferrous ascorbate, ferrous nitrate, ferrous gluconate, ferrous lactate and composition thereof.Also comprise tetrasodium biscitrate ferrate and have multiple cationic other ferrous salts.In composition of the present invention, preferably only has ferrous ion as cationic ferrous salt.Also can use the mixture of two or more this ferrous salts.
In another embodiment of the invention, described electrolyte is a ferrous sulfate, comprises having multiple cationic ferrous sulfate, for example ferrous sulfate potassium and ferromanganous sulfate.In various ferrous sulfates, owing to be easy to get ferrous and six ferrous sulfate hydrates of preferably sulfuric acid.
Especially effectively electrolyte is those electrolyte for ferrous ammonium salts.Wherein, iron ammonium sulfate is preferred electrolyte.These electrolytical other characteristics are that they are highly soluble in water.That is to say that the ferrous ammonium salts that is applicable to present composition solubility in water under 25 ℃ is 1g/100g water at least, preferred 10g/100g at least, most preferably 20g/100g water at least.Also can use the mixture of two or more this ferrous ammonium salts.The optional anion from wide region of described anion for example comprises sulfate radical, ascorbic acid root, nitrate anion, citrate, glucose acid group and lactate.
When dissolving, ferrous salt is dissociated into the positive and negative ion basically.In many cases, they dissociate fully.
Oxygen-scavenging compositions of the present invention can comprise the additive that does not influence the oxygen scavenging capacity of composition in significant mode in addition.For example, some common additives that are used for polymer formulations comprise various fillers, for example diatomite, kaolin or montmorillonitic clay, splitting, zeolite, molecular sieve etc.Plasticizer can be used for changing modulus or its toughness of polymer.Can add pigment (for example titanium dioxide or carbon black) makes composition painted.Preferred anti-oxidant (being present in the industrial copolymer sometimes) exists with enough low amount, makes the Oxygen scavenging performance significantly do not weaken composition, and for example content is less than 1,000ppm.
The oxygen scavenging capacity of the present composition is owing to the clean reaction between gaseous oxygen and the oxidable metal (net reaction).Such reaction is an electrochemical properties, and comprises that the electronics between the reactant class (being oxygen and oxidable metal) shifts.
For example, if iron is oxidable metal, thinks and cause two half-cell electrochemical reactions of global purge effect to be:
Anodic half-cell: Fe → 2e+Fe
++
Cathode half-cell: Fe
+++ 3/4O
2+ 1/2H
2O+2e → FeOOH
According to acidity and available oxygen, determine generable other cathode half-cell reactions, and see M.Stratmann, The Atmospheric Corrosion of Iron-A Discussion of thePhysico-Chemical Fundamentals of this Omnipresent CorrosionProcess (discuss on the physical-chemical basis of the atmospheric corrosion of iron-this ubiquitous corrosion process), Phys.Chem., the 94th volume, the 6th phase, the 626-619 page or leaf, the discussion in 1990.
Under the situation of iron, when there being Fe
++(ferrous) ion is and if think in anode reaction the Fe that forms continuously
++Ion easily migrates to the position that the cathode half-cell reaction takes place by reaction medium from the position that the anodic half-cell reaction takes place, and then electrochemical reaction (oxygen cleaning reaction thus) is carried out fast.
Relating to iron and being dispersed in most of oxygen removing systems of the electrolytical combination in the polymer, when composition is exposed in moisture and the air a few hours in the past after, airborne oxygen content begins to descend.Think that this initiating stage is owing to form some essential chemical processes that replace of ferrous ion.But, when a small amount of above-mentioned ferrous salt is used as one or more components of the present composition, need not initiating stage, and begin the oxygen removing immediately.
In addition, by the moisture that utilize to exist, be present in the oxygen scavenging capacity that concrete ferrous salt electrolyte in the present composition or the electrolytical mixture of ferrous salt can improve oxidable metal component.Provide conducting path with the liquid water layer of oxidable Metal Contact for the ion that in anode reaction, forms.
The oxidable composition of first kind of embodiment of the present invention also can comprise the another kind of electrolyte that is not ferrous salt in addition.But, adding second electrolyte and choose wantonly fully, this is owing to when using the combination of ferrous salt of the present invention and oxidable metal, obtain of short duration induction period.Under the situation of the combination of ferrous sulfate and metallic iron, this point is significant especially.
In some cases, according to selected concrete ferrous salt, absorb by using second electrolyte can improve oxygen.Some examples of available other suitable electrolyte components are the compound that is selected from the salt of organic acid salt and inorganic acid.Suitable salt is solid under room temperature, and has the cationic cation of transition-metal cation, quaternary ammonium cation He quaternary phosphine that is selected from alkali metal cation, alkaline earth metal cation, is different from ferrous ion.Salt with mixed-cation of these types also is suitable for use as second electrolyte components.Described salt solubility in water under 25 ℃ is 1g/100g water at least, is preferably 10g/100g water at least.The salt that the example of this salt comprises inorganic acid is alkali metal, alkaline-earth metal and transition metal halide, sulfate, nitrate, carbonate, bicarbonate, iodide, iodate, sulphite and phosphate for example.Spendable organic acid salt comprises alkali metal, alkaline-earth metal and transition metal tartrate, lactate, citrate, acetate, alginates.The concrete kind that can be used as other electrolyte components comprises potassium tartrate, potassium alginate, saleratus, KBr, potash, potassium chloride, potassium citrate, potassium hydroxide, Potassiumiodate, KI, potassium lactate, potassium sulfate, sodium acetate, mosanom, Sodium Benzoate, sodium acid carbonate, sodium carbonate, natrium citricum, sodium chloride, sodium diacelate, NaOH, sodium hypophosphite, sodium lactate, sodium chloride potassium, potassium sodium tartrate, sodium propionate, sodium sesquicarbonate, sodium tartrate, sodium thiosulfate, calcium acetate, calcium alginate, calcium chloride, calcium gluconate, calcium glycerophosphate, calcium lactate, calcium pantothenate, calcium propionate, magnesium chloride, magnesium sulfate, copper gluconate, copper sulphate, copper nitrate, iron chloride, ferric sulfate, manganese chloride, managanese gluconate, manganese sulfate, ammonium alginate, carbonic hydroammonium, ammonium carbonate, ammonium chloride, dibasic ammonium citrate, ammonium hydroxide, Diammonium phosphate (DAP), MAP and ammonium sulfate.Also can use this combination of compounds, for example sodium chloride and calcium chloride.Owing to be easy to get and it has been generally acknowledged that it is safe using for Food Contact, so sodium chloride is preferred electrolyte.
Can be used as the second electrolytical another kind of electrolyte is some organic acid, comprises saturated aliphatic series and aromatic acid, particularly has those materials that are less than 20 carbon atoms.Can be used for concrete organic acid of the present invention including, but not limited to acetate, aconitic acid, adipic acid, alginic acid, benzoic acid, caproic acid, sad, capric acid, laurate, stearic acid, isostearic acid, behenic acid, malic acid, butanedioic acid, tartaric acid, citric acid, ethylenediamine tetra-acetic acid, palmitic acid, stearic acid and composition thereof.Wherein, preferred ethylenediamine tetra-acetic acid.Preferred acid is saturated species.Unsaturated acids can produce smell in composition.
Equally, can use these organic acid salt.Particular certain cancers and sylvite.
Under any circumstance, the component that is present in the oxygen-scavenging compositions should make, if soluble in water, does not form the height alkaline aqueous solution." height alkaline aqueous solution " is meant that pH is greater than 9.The pH of the aqueous solution of one or more components of the preferred present composition is 8 or lower, and for the aqueous solution of each component, more preferably pH is 7 or lower.The hydroxide ion with high concentration oxidable metal component association in any water layer can be present in and the complexing or the sequestering power of electrolyte ion can be competed and influence.Think when iron is used as oxidable metal, promote the ability that forms ferrous ion complex compound or chelating agent to promote electrochemical oxidation reactions.Some electrolyte combination is effective especially in this, and comprises the combination of ethylenediamine tetra-acetic acid and ferrous sulfate.
The electrolyte of suction is preferred for oxygen-scavenging compositions.Provide the component of moisture to improve electrochemical reaction.Come the quantitative assay wettability power by the equilibrium moisture content of measuring material, it is the relative humidity under poised state between the saturated solution of compound and the upper space thereof.The balance moisture constant of lithium bromide (for deliquescent compound) is 7% relative humidity.Therefore, when 7% relative humidity, form water in its surface.Some preferred electrolyte comprises calcium chloride, potassium acetate, sodium bromide and zinc nitrate.
In second kind of embodiment of the present invention, ferrous sulfate or another kind of ferrous sulfate are as electrolyte components.Find, comprise ferrous sulfate and substantially not the composition of the present invention of halide salt be especially effective oxygen-scavenging compositions." do not contain " amount that is meant the halide salts existence substantially and be not more than 20% of polymer, oxidable metal and ferrous sulfate gross weight, preferably be not more than 5%, most preferably be not more than 0.5%.This point is different with disclosing of prior art, and prior art proposes must have halide salts so that ferrous sulfate effectively works.
In another preferred embodiment, ferrous ammonium salts (particularly iron ammonium sulfate) is as electrolyte.Comprise this ferrous ammonium salts and can comprise other electrolyte of any kind, but described other electrolytical existence are chosen wantonly fully as electrolytical oxygen-scavenging compositions of the present invention.
The amount that is present in the polymers compositions in the oxygen-scavenging compositions of the present invention can be composition than small part, for example less than 1% weight.But many useful compositions contain the polymer of higher concentration, particularly are designed for those compositions that melt forms lid, cap and container.In this case, the amount of polymer is generally the 20-99% of oxygen-scavenging compositions gross weight.The amount of preferred polymers is the 30-70% of composition total weight.
Described oxygen-scavenging compositions can be the concentrate form.Concentrate is used for melt method, for example comprises the method for extruding the thermoplastic resin that is generally used for making packaging material (for example film and container).Preferred concentrate comprises the polymer of combination/100 weight portions of the oxidable metal and the molysite of at least 80 weight portions.Usually concentrate comprises combination/100 parts by weight polymer of the oxidable metal and the molysite of at least 50 weight portions.
Oxygen-scavenging compositions of the present invention can add or not add other components to be used, to make goods, and single thin film or be used for laminate ply, lid, cap, label, liner, container and other packaging material of multi-layer sheet, film or other structures for example.The thermosetting polymer that is mixed with oxygen-scavenging compositions can be used for rubber applications usually, for example pipe or as the coating on other grounds.
When hope removes deoxidation fast from packing, preferably has the infiltrative polymer of hyperoxia.In some applications, for example when the composition that comprises polymer and oxygen-scavenging compositions serves as a contrast (cap liner) as the lid in the packing articles, wish that oxygen is from the inner fast moving of container (for example bottle), to contact with oxygen-scavenging compositions.Because manufacturing process, oxygen can be present in the packing, or in some cases, oxygen can diffuse in the packing in storage process.Oxygen permeability is represented with OPV (oxygen permeability value).Low density polyethylene (LDPE) is the polymer that easily permeates, and the OPV value under environment temperature and 50% relative humidity is about 450cc oxygen mil/100in
2It atm (centimetre
3Oxygen mil/100 inch
2It atmospheric pressure).For having those ranks of the highest vinyl acetate content, ethylene vinyl acetate resin (for example
The EVA resin derives from E.I.du Pont deNemours and Company) the OPV value be up to 1000cc oxygen mil/100in
2It atm.Therefore,
The value of EVA vector resin is beneficial to oxygen than polyethylene height and removes.OPV is 450cc oxygen mil/100in under environment temperature and 50% relative humidity
2The resin of it atm is useful especially in some container application.For having low equilibrium moisture content or do not have those compositions at water source in removing composition itself, the water permeability of resin is for promoting that quick oxygen absorption is important.Measure water permeability, and represent with steam permeable speed (WVTR).The WVTR of low density polyethylene (LDPE) is about 1.5g water/100in
2My god, think to only slightly infiltration of water vapour.Some the level other
The WVTR value of resin is 4g water/100in
2My god, therefore have water infiltration rate faster than low density polyethylene (LDPE).Therefore,
Resin and WVTR value are 4g water/100in
2It or other higher resins are the preferred vector resin that is used to have the oxygen-scavenging compositions of the present invention of low equilibrium moisture content.
In other are used, be present in polymer in the oxygen-scavenging compositions stop oxygen from the packaging material external penetration to packaging material inside.In this application, wish to utilize to have low oxygen-permeability but the polymer of high water permeability.The copolymer (EVOH) that an example of this polymer is ethene and vinyl alcohol derives from kuraray company (Kuraray Company Ltd).The EVOH of comonomer unit with ethylene copolymer of 32% weight has low OPV value under 90% relative humidity, be about 0.3cc oxygen mil/100in
2It atm, and WVTR is about 3.8g watertight ear/100in
2My god.
When oxygen-scavenging compositions of the present invention is manufactured thin polymer film, no matter be single or multiple lift, to produce loose structure, can improve Oxygen scavenging performance by orientation or stretching polymer film.
Think that the active basic principles of chemistry that form oxygen-scavenging compositions of the present invention comprise the consumption of each component.For example, to use metallic iron as an example, in oxidation reaction, consume iron.According to iron environment of living in, the ability of its oxygen consumed is 100cc oxygen-300cc oxygen/g metallic iron.Contain oxygen-scavenging compositions polymer product design and in polymer the selection of iron content depend on the designing requirement of avoiding the packing material of oxygen to be protected.For example, the oxidable metal of the higher percent in polymer is used for reducing the speed of oxygen quickly and/or is used for the oxygen content of packing is reduced to low-down level.The combined content of oxidable metal and molysite is that the polymers compositions of 1% weight/100 weight portions can be enough to produce oxygen and removes effect in composition.But, preferred at least 10% weight/100 parts by weight polymer of using.Concrete content depends on concrete final use and oxygen-scavenging compositions polymer to be mixed.Use high level can produce various effects, the embrittlement of for example undesirable high melt viscosity, high density and increase.But in some cases, the oxidable metal component of combination and the content of molysite can be up to 90% weight of polymers compositions.
Can easily prepare composition of the present invention by common hybrid technology.For example, each component can be mixed in extruder.Polymer for the mixture of producing continuously the oxidable metal that comprises abundant dispersion and ferrous salt can use double screw extruder, for example Werner ﹠amp; The Pfleiderer double screw extruder.Can from independent hole, add each component or add each component from a charging aperture to do the form of mixing thing.Nitrogen purges charging aperture can make pre-reaction degree minimum slight between iron and the oxygen.Each component can be heated to temperature in extruder, and on the moving belt of drying, extrude, with cooling and granulation subsequently with the form of wire rod above the melt temperature of polymer.Pellet can be packed subsequently, in the sack of the band paper tinsel lining of preferably packing into so that minimum level ground is exposed to oxygen and water, or in the high density polyethylene (HDPE) sack of packing into to be protected from the influence of water.
Other embodiments of the present invention are single thin film and laminated material (being meant sandwich construction).Laminated material of the present invention can comprise two-layer or more multi-layered.Oxygen-scavenging compositions of the present invention constitutes ground floor.This composition can comprise one or more other polymer to form the material that constitutes this ground floor.As mentioned above, described oxygen-scavenging compositions also can comprise other components that do not influence the oxygen cleaning reaction.The second layer can be formed by any material, comprises the composition identical with ground floor.But the second layer can comprise adhesive phase, hot melt adhesive layer, the adhesive phase based on solvent, fabric or other porous layers of another polymeric layer, metal level or metal foil layer, pottery or glassy layer co-extrusion, for example
Industrial packaging.The example of the available laminated material of these types comprises the flexible thin rete with following structure: polypropylene/adhesive tie layer/oxygen-scavenging compositions/adhesive tie layer of the present invention/ionomer polymer; Polyethylene/adhesive tie layer/ethylene-vinyl alcohol/adhesive tie layer/oxygen-scavenging compositions/adhesive tie layer of the present invention/polypropylene; Metallized
Polyester film/adhesive tie layer/oxygen-scavenging compositions/adhesive tie layer of the present invention/sealant layer.First kind of these structures can be used as and contain polypropylene as outer field lid stock.Second kind is applicable to blister-pack.The third be suitable for use as contain metallized
Polyester film is as outer field lid stock.The laminate structures that is used for valve protection cap with polypropylene as outer and oxygen-scavenging compositions of the present invention (wherein polymer is an ethylene vinyl acetate) as the second layer.Be used for three of valve protection cap and press material structure for having aluminium layer by layer as skin, oxygen-scavenging compositions of the present invention (wherein polymer is an ethylene vinyl acetate) as the second layer and ethylene vinyl acetate as internal layer.Laminated material as cup or tray material is formed by following: outer is polypropylene, the second layer is an adhesive tie layer, and the 3rd layer is EVOH, and the 4th layer is adhesive phase, layer 5 is oxygen-scavenging compositions of the present invention (wherein polymer is a polyethylene), and internal layer is a polyethylene.Another kind of laminated material as lid stock is formed by following: skin is
Polyester film, but the second layer is the adhesive of coextrusion, the 3rd layer is oxygen-scavenging compositions of the present invention (wherein polymer is a polyethylene), internal layer is
The lid resin.
The typical polymer that is used for the packaging film layer comprises polypropylene, low density polyethylene (LDPE), PLA, PETG and high density polyethylene (HDPE).But for example by the adhesive of coextrusion
The tack coat that adhesive resin forms is generally used for this structure.
Can be for example oxygen-scavenging compositions of the present invention and laminated material of the present invention be manufactured moulded products or be used for the film of packaging applications by melt processing.
In certain embodiments, described composition adopts from the material of packing and removes oxygen except that the mode of deoxidation.Active in order to provide long oxygen to remove, described removing composition should be by stoping oxygen permeable barrier and the outer air insulated of packing.A kind of method provides thick container wall layer, for example the polypropylene layer of 10 mil thick.Perhaps, the thin layer that oxygen is had a polymer of hypotonicity can provide the long service life of removing composition.For example, the ethylene-vinyl alcohol copolymer of 0.2 mil thick (EVOH) provides with 20 mils and has more the identical protection of infiltrative polypropylene layer.When protection exempted to be exposed to external oxygen, the position of oxygen scavenger layer can change in packing.For example, the laminate ply that comprises oxygen-scavenging compositions can be the layer of the chamber wall of independent label, the layer in the lid of cup or plate, bottle cap lining or lamination on the inwall that is attached to packing.The latter's example be polypropylene,
But the adhesive resin of coextrusion, EVOH,
But the laminated material of the adhesive resin of coextrusion, comprise oxygen-scavenging compositions layer,
Adhesive resin, polypropylene, evoh layer is between skin and oxygen scavenger layer.
The form of all right pouch of oxygen-scavenging compositions of the present invention or parcel is used, and is included in separately in the packing articles, to absorb headspace.When being used for this purpose, described composition can be the powder type in the parcel.Described composition can comprise other components in addition, and for example fluoropolymer resin, and formation is included in the interior pellet of parcel.
Can use composition of the present invention protection packing oxygen sensitive materials including, but not limited to milk, sour milk, cheese, soup, beverage for example wine, beer and fruit juice, the cooking in advance meals, medicine and be difficult to powder by the nitrogen purge or material for example flour or noodles.In addition, oxygen-scavenging compositions of the present invention and laminated material of the present invention protection packing articles are avoided the secondary effect of oxygen, for example insect damage, fungus growth, mould and bacterial growth.
Embodiment
Embodiment 1
It is that 18% weight and fusing point are that the blend sample of 90 ℃ ethylene vinyl acetate resin, 27% weight metallic iron (H200 iron derives from ARSTechnologies Inc.) and 5.4% weight, six ferrous sulfate hydrates (Aldrich Chemical Co.) is introduced in the Haake Model 9000 plastometer mixers (plastograph mixer) that 68g is comprised 67.6% weight vinyl acetate content.Under 160 ℃, 100rpm, melt mixed is 7 minutes in the Haake mixer with material, injects stainless steel disc subsequently under nitrogen atmosphere, and cooling 15 minutes under nitrogen atmosphere.Under nitrogen atmosphere, store chilled sample.A part of sample in 140 ℃ of following compression moulding, and is quickly cooled to environment temperature adding to depress.Under nitrogen atmosphere, store the disk of 5 inches of resulting thick 15-20 mils, diameter.The disk sample of the heavily about 1g of test is removed characteristic to determine its oxygen.10 layers of 1 square inch of hygenic towelette are placed on the bottom of 50ml Kjeldahl reaction flask, to produce 100% relative humidity atmosphere.Test sample is placed on the wet tissue.When flask is open to atmosphere, the graded tube of 50ml Kjeldahl flask is reduced in the flask of water, and clogs the Kjeldahl flask with glass stopper.Along with the consumption of oxygen, the liter waterborne in graded tube.By with the variation of sample comparison Kjeldahl flask of water that hygenic towelette and about 1g do not contain the ethylene vinyl acetate resin of other components be housed proofread and correct the barometer pressure and temperature.After 3 and 20 hours, the explanation of the height of water rises in the graded tube height have respectively 1.0 and 2.8cc oxygen remove in the about 125ml air from flask-graded tube device.
Embodiment 2
It is that 18% weight and fusing point are that the blend sample of 90 ℃ ethylene vinyl acetate resin, 25% weight metallic iron (H200 iron derives from ARSTechnologies Inc.), 1% weight trisodium citrate (tribasic sodium citrate) and 5% weight, six ferrous sulfate hydrate ammoniums (City Chemical Co.) is introduced in the HaakeModel9000 plastometer mixer that 71.5g is comprised 69% weight vinyl acetate content.Under 160 ℃, 100rpm, melting mixing is 7 minutes in the Haake mixer with material, injects stainless steel disc subsequently under nitrogen atmosphere, and cooling 15 minutes under nitrogen atmosphere.Under nitrogen atmosphere, store chilled sample.A part of sample in 140 ℃ of following compression moulding, and is quickly cooled to environment temperature adding to depress.Under nitrogen atmosphere, store the disk of 5 inches of resulting thick 15-20 mils, diameter.The disk sample of the heavily about 1g of test is removed characteristic to determine its oxygen.10 layers of 1 square inch of hygenic towelette are placed on the bottom of 50ml Kjeldahl reaction flask, to produce 100% relative humidity atmosphere.Test sample is placed on the wet tissue.When flask is open to atmosphere, with the graded tube of 50ml Kjeldahl flask fall to a flask of water, and clog the Kjeldahl flask with glass stopper.Along with the consumption of oxygen, the liter waterborne in the graded tube.By relatively being housed, the variation of Kjeldahl flask of water of sample that hygenic towelette and about 1g do not contain the ethylene vinyl acetate resin of other components proofreaies and correct the barometer pressure and temperature.1, after 6 and 24 hours, in the graded tube height explanation that rises to waterborne have respectively 0.3,1.2 and 3.3cc oxygen from about 125ml is with air the graded tube flask device, remove.
Embodiment 3
Use the method for embodiment 2 to prepare the ethylene vinyl acetate resin that comprises 67.6% weight, the composition of six ferrous sulfate hydrate ammoniums of the metallic iron of 27% weight and 5.4% weight.1, after 4 and 20 hours, in the graded tube height explanation that rises to waterborne have respectively 0.2,0.9 and 3.5cc oxygen from about 125ml is with air the graded tube flask device, remove.
Embodiment 4
Use method research of embodiment 2 to comprise the composition of the green vitriol (Aldrich) of the metallic iron of ethylene vinyl acetate resin, 27% weight of 67.6% weight and 5.4% weight.After 3 and 20 hours, in the graded tube height explanation that rises to waterborne have respectively 1.0 and 2.8cc oxygen from about 125ml is with air the graded tube flask device, remove.
Claims (37)
1. oxygen-scavenging compositions, described composition comprises:
A. has polymer less than 5 aliphatic carbon-to-carbon double bond/100 comonomer units;
B. oxidable metal; With
C. have anionic ferrous salt that is selected from ascorbic acid root, nitrate anion, citrate, glucose acid group and lactic acid anion and composition thereof, wherein said ferrous salt solubility in water under 25 ℃ is 1g/100g water at least.
2. the oxygen-scavenging compositions of claim 1, wherein said oxidable metal chosen from Fe, copper, manganese and cobalt.
3. the oxygen-scavenging compositions of claim 2, wherein said oxidable metal is an iron.
4. the oxygen-scavenging compositions of claim 1, wherein said polymer is selected from the copolymer of polyamide, polyester, polystyrene, Merlon, polyvinyl acetate, polyvinyl chloride, polyolefin homopolymer and copolymer, ethene and polar comonomers, the ionomer of ethylene acrylic acid co polymer, the ionomer of ethylene methacrylic acid copolymer and the ionomer of EMA copolymer.
5. the oxygen-scavenging compositions of claim 1, wherein said polymer is a thermoplastic resin.
6. the oxygen-scavenging compositions of claim 1, described composition also comprises the electrolyte of the salt that is selected from organic acid salt and inorganic acid, the cation of wherein said salt is selected from alkali metal cation, alkaline earth metal cation, is different from the transition-metal cation of ferrous ion, quaternary ammonium cation is with quaternary phosphine cation and composition thereof, and wherein said electrolyte solubility in water under 25 ℃ is 1g/100g water at least.
7. the oxygen-scavenging compositions of claim 1, wherein said ferrous salt is selected from ferrous citrate, ferrous gluconate, ferrous lactate and composition thereof.
8. the oxygen-scavenging compositions of claim 1, described composition also comprises other polymer of the polymer that is different from component A, and described other polymer are selected from the polymer that has less than 5 aliphatic carbon-to-carbon double bond/100 comonomer units.
9. laminated material, described laminated material comprises:
A. ground floor, described ground floor comprises:
1. has polymer less than 5 aliphatic carbon-to-carbon double bond/100 comonomer units;
2. oxidable metal; With
3. have anionic ferrous salt that is selected from ascorbic acid root, nitrate anion, citrate, glucose acid group and lactic acid anion and composition thereof, wherein said ferrous salt solubility in water under 25 ℃ is 1g/100g water at least; With
B. at least one deck other the layer.
10. the laminated material of claim 9, other layers of one deck at least of wherein said laminated material comprise thermoplastic polymer.
11. the laminated material of claim 10, the thermoplastic polymer of wherein said other layers of one deck at least is selected from polypropylene, polyethylene and ethylene-vinyl alcohol.
12. single thin film, described single thin film comprises and at least aly has less than polymer, the oxidable metal of 5 aliphatic carbon-to-carbon double bond/100 comonomer units and have anionic ferrous salt that is selected from ascorbic acid root, nitrate anion, citrate, glucose acid group and lactic acid anion and composition thereof, and wherein said ferrous salt solubility in water under 25 ℃ is 1g/100g water at least.
13. goods, described goods comprise and at least aly have less than polymer, the oxidable metal of 5 aliphatic carbon-to-carbon double bond/100 comonomer units and have anionic ferrous salt that is selected from ascorbic acid root, nitrate anion, citrate, glucose acid group and lactic acid anion and composition thereof, and wherein said ferrous salt solubility in water under 25 ℃ is 1g/100g water at least.
14. an oxygen-scavenging compositions, described composition is made up of following material basically:
A. has polymer less than 5 aliphatic carbon-to-carbon double bond/100 comonomer units;
B. oxidable metal; With
C. ferrous sulfate,
Described composition is halide salt not substantially.
15. the oxygen-scavenging compositions of claim 14, wherein said oxidable metal chosen from Fe, copper, manganese and cobalt.
16. the oxygen-scavenging compositions of claim 15, wherein said oxidable metal is an iron.
17. the oxygen-scavenging compositions of claim 14, wherein said polymer are selected from the copolymer of polyamide, polyester, polystyrene, Merlon, polyvinyl acetate, polyvinyl chloride, polyolefin homopolymer and copolymer, ethene and polar comonomers, the ionomer of ethylene acrylic acid co polymer, the ionomer of ethylene methacrylic acid copolymer and the ionomer of EMA copolymer.
18. the oxygen-scavenging compositions of claim 14, wherein said polymer are thermoplastic resin.
19. the oxygen-scavenging compositions of claim 14, described composition also comprise other polymer of the polymer that is different from component A, described other polymer are selected from the polymer that has less than 5 aliphatic carbon-to-carbon double bond/100 comonomer units.
20. a laminated material, described laminated material comprises:
A. ground floor composition, described composition is made up of following material basically:
1. has polymer less than 5 aliphatic carbon-to-carbon double bond/100 comonomer units;
2. oxidable metal; With
3. ferrous sulfate,
Described composition is halide salt not substantially; With
B. at least one deck other the layer.
21. the laminated material of claim 20, wherein other layers of one deck comprise thermoplastic polymer at least.
22. the laminated material of claim 21, the thermoplastic polymer of wherein said other layers of one deck at least is selected from polypropylene, polyethylene and ethylene-vinyl alcohol.
23. a single thin film, described single thin film have basically by at least a and have a layer of forming less than the polymer of 5 aliphatic carbon-to-carbon double bond/100 comonomer units, oxidable metal and ferrous sulfate, described layer is halide salt not substantially.
Have a component of forming less than the polymer of 5 aliphatic carbon-to-carbon double bond/100 comonomer units, oxidable metal and ferrous sulfate 24. goods, described goods comprise basically by at least a, described component is halide salt not substantially.
25. an oxygen-scavenging compositions, described composition comprises:
A. has polymer less than 5 aliphatic carbon-to-carbon double bond/100 comonomer units;
B. oxidable metal; With
C. be selected from compound with the cationic molysite of ferrous ammonium and composition thereof, wherein said molysite solubility in water under 25 ℃ is 1g/100g water at least.
26. the oxygen-scavenging compositions of claim 25, wherein said oxidable metal chosen from Fe, copper, manganese and cobalt.
27. the oxygen-scavenging compositions of claim 26, wherein said oxidable metal is an iron.
28. the oxygen-scavenging compositions of claim 25, wherein said polymer are selected from the copolymer of polyamide, polyester, polystyrene, Merlon, polyvinyl acetate, polyvinyl chloride, polyolefin homopolymer and copolymer, ethene and polar comonomers, the ionomer of ethylene acrylic acid co polymer, the ionomer of ethylene methacrylic acid copolymer and the ionomer of EMA copolymer.
29. the oxygen-scavenging compositions of claim 25, wherein said polymer are thermoplastic resin.
30. the oxygen-scavenging compositions of claim 25, described composition also comprises the electrolyte of the salt that is selected from organic acid salt and inorganic acid, the cation of wherein said salt is selected from alkali metal cation, alkaline earth metal cation, is different from the transition-metal cation of ferrous ion, quaternary ammonium cation is with quaternary phosphine cation and composition thereof, and wherein said electrolyte solubility in water under 25 ℃ is 1g/100g water at least.
31. the oxygen-scavenging compositions of claim 25, wherein said molysite are iron ammonium sulfate.
32. the oxygen-scavenging compositions of claim 25, described composition also comprise other polymer of the polymer that is different from component A, described other polymer are selected from the polymer that has less than 5 aliphatic carbon-to-carbon double bond/100 comonomer units.
33. a laminated material, described laminated material comprises:
A. ground floor, described ground floor comprises:
1. has polymer less than 5 aliphatic carbon-to-carbon double bond/100 comonomer units;
2. oxidable metal; With
3. be selected from compound with the cationic molysite of ferrous ammonium and composition thereof, wherein said molysite solubility in water under 25 ℃ is 1g/100g water at least; With
B. at least one deck other the layer.
34. the laminated material of claim 33, other layers of wherein said one deck at least comprise thermoplastic polymer.
35. the laminated material of claim 34, the thermoplastic polymer of wherein said other layers of one deck at least is selected from polypropylene, polyethylene and ethylene-vinyl alcohol.
36. single thin film, described single thin film comprises and at least aly has less than polymer, the oxidable metal of 5 aliphatic carbon-to-carbon double bond/100 comonomer units and be selected from compound with the cationic molysite of ferrous ammonium and composition thereof, and wherein said molysite solubility in water under 25 ℃ is 1g/100g water at least.
37. goods, described goods comprise at least a component that has less than polymer, the oxidable metal of 5 aliphatic carbon-to-carbon double bond/100 comonomer units and be selected from compound with the cationic molysite of ferrous ammonium and composition thereof, and wherein said molysite solubility in water under 25 ℃ is 1g/100g water at least.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US79174906P | 2006-04-13 | 2006-04-13 | |
| US60/791,749 | 2006-04-13 | ||
| US11/728,506 | 2007-03-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101415343A true CN101415343A (en) | 2009-04-22 |
Family
ID=40595552
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007800121945A Pending CN101415343A (en) | 2006-04-13 | 2007-04-13 | Composition for controlling exposure to oxygen |
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| Country | Link |
|---|---|
| CN (1) | CN101415343A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101803786A (en) * | 2010-04-09 | 2010-08-18 | 王力 | Dual-effect anti-staling agent and preparation method thereof |
| CN113166464A (en) * | 2018-12-07 | 2021-07-23 | Sabic环球技术有限责任公司 | Polyolefin compositions with improved oxygen scavenging capacity |
-
2007
- 2007-04-13 CN CNA2007800121945A patent/CN101415343A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101803786A (en) * | 2010-04-09 | 2010-08-18 | 王力 | Dual-effect anti-staling agent and preparation method thereof |
| CN101803786B (en) * | 2010-04-09 | 2013-07-17 | 王力 | Dual-effect anti-staling agent and preparation method thereof |
| CN113166464A (en) * | 2018-12-07 | 2021-07-23 | Sabic环球技术有限责任公司 | Polyolefin compositions with improved oxygen scavenging capacity |
| CN113166464B (en) * | 2018-12-07 | 2023-09-12 | Sabic环球技术有限责任公司 | Polyolefin compositions with improved oxygen scavenging capability |
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