CN102001486B - Barrier-property lapped polymer film packaging material - Google Patents
Barrier-property lapped polymer film packaging material Download PDFInfo
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- CN102001486B CN102001486B CN200910306300.1A CN200910306300A CN102001486B CN 102001486 B CN102001486 B CN 102001486B CN 200910306300 A CN200910306300 A CN 200910306300A CN 102001486 B CN102001486 B CN 102001486B
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Abstract
The invention discloses a barrier-property lapped polymer film packaging material comprising at least one layer-multiplied and coextruded lapped barrier compound layer. Each barrier compound layer comprises a plurality of repeating units which comprise at least two individual layers; each individual layer corresponds to one of two different polymers; at least one repeating unit of the lapped barrier compound layer at least comprises three individual layers; each of the individual layers corresponds to one of three different polymers; and at least one of the at least three polymers forms at least one barrier-property polymer part which can separate gas.
Description
Technical field
The present invention relates to a kind of stacking polymer thin-film material structure for barrier packaging.
Background technology
Modern society people to the guaranteeing the quality of the products such as food, beverage, cosmetics, medical product, tealeaves, chemical reagent, agricultural chemicals, spices, feed, fresh-keeping, protect local flavor and extend shelf life etc. and require more and more higher.Therefore also increasing, novel, the High Performance of the demand of barrier packaging material, barrier packaging material cheaply, become especially for the development research of the plastic sheeting of barrier flexible packaging the focus that various countries competitively develop.But the most performance of barrier packaging membraneous material of domestic production is lower, be generally applied in the packing of low-end product, and the barrier packaging material of function admirable also needs a large amount of imports.
Multi-layer co-extruded combination process, as a kind of job operation of composite plastic film, is widely used in the world with its unique advantage.It is found that the number of plies is more, the Combination property of material is better.Use multi-layer co-extrudedly, particularly 7 layers of above co-extrusion technology, can make film with minimum thickness by the resin of desired properties, can reduce widely the use of expensive material, to reduce the cost of material; And can avoid the phenomenon of curling that produces because rete is blocked up.Because being divided into several thin layers, barrier material also realized better barrier property.
The multi-layer co-extruded plastics laminated film blow moulding equipment of China mostly is two to three-layer co-extruded rotating head form at present, backward in technique.Production for the higher composite plastic film of to meet the need, some enterprises have introduced five to seven-layer coextruded plastic laminated film blow moulding equipment, but still can not meet the need of market, in a large number dependence on import, make its cost high, suppressed the development of the multi-layer co-extruded plastics laminated film of China.
And these co-extrusions, no matter be coextrusion blow or coextrusion casting, have great limitation at present.Because the co-extrusion number of plies is higher, the construction of co-extrusion die head and operation are just more difficult.The current whole world 9 layers of coextrusion blow manufacturing line of 25 cover of only having an appointment.The die head of coextrusion casting is relatively simpler than the die head of coextrusion blow, but will build the die head that the number of plies is high still has very large difficulty.So, the number of plies of coextruded film is just very limited, causes coextruded film performance cannot continue to improve.
Summary of the invention
The invention provides a kind of barrier-property lapped polymer film packaging material, it has overcome the existing deficiency of background technology multilayer polymer film material.
The technical solution adopted for the present invention to solve the technical problems is:
A kind of barrier-property lapped polymer film packaging material, it is characterized in that: it comprises that the lamination of at least one layer of multiplication coextrusion intercepts composite bed, this each obstruct composite bed all contains a plurality of repetitives, this repetitive comprises at least two individual layer, and each individual layer is corresponding to one at least two different poly-mers compositions; Wherein the repetitive of at least one this lamination obstruct composite bed at least comprises three individual layer, this each individual layer is corresponding to one at least three different poly-mers compositions, and, during these at least three poly-mers form, have at least a composition to include at least one separating polymer composition, this separating polymer composition can intercept gas.
In one preferred embodiment, in membraneous material, also comprise barrier individual layer or/and the barrier composite bed of non-layer multiplication coextrusion.
In one preferred embodiment, in membraneous material, also comprise at least one deck tack coat of being present between described various composite bed and individual layer or/and one deck interlayer at least.
In one preferred embodiment, the thickness that this comprises that at least one repetitive and repetitive comprise that at least three different poly-mers form and wherein at least one is the obstruct composite bed of the layer multiplication coextrusion that forms of barrier is not more than 900 microns.
In one preferred embodiment, this at least one barrier properties for gases component of polymer is selected from ethylene-vinyl alcohol copolymer (EVOH), polyvinyl alcohol (PVA), polyamide (PA), polyacrylinitrile (PAN), polyvinylidene chloride (PVDC), polyethylene terephthalate (PET), PEN (PEN), polyvinylchloride (PVC), polyoxyethylene (PEO), Kynoar (PVDF), high density polyethylene (HDPE) (HDPE), polypropylene (PP), polyimide (PEI), PPI (PAI), polyetheretherketone (PEEK), liquid crystal polymer, ionomer based on ethene, the copolymer of ethene and beta-unsaturated esters, one or more in acrylonitrile and methacrylic acid copolymer or polyurethane engineering plastics, or be selected from the copolymer of above-mentioned one or more, condensation product, affixture, resultant of reaction or modifier.
In one preferred embodiment, this at least one non-pneumatic separating polymer composition is selected from one or more in polyolefin Polymer, acrylic resin, vinyl cyanide resin, polyester, unsaturated polyester (UP), biological polyester, polyethers, polyurethane, polysiloxane, polystyrene Polymer, vinyl chloride Polymer, polysulfide, epoxy resin or phenol resin, or is selected from copolymer, condensation product, affixture, resultant of reaction or the modifier of above-mentioned one or more.
In one preferred embodiment, also comprise the filler for filled polymer.
In one preferred embodiment, also comprise polymer builder.
In one preferred embodiment, also comprise polymeric additive.
The technical program is compared with background technology, and its tool has the following advantages: applicant adopt dexterously at least one comprise at least three poly-mers form and wherein have that a barrier forms at least by cutting apart-a compound barrier layer that again prepared by the stacked multi-layer co-extruded technology of layer multiplication of converging prepares barrier-property lapped polymer film packaging material.Adopt the multi-layer co-extruded technology of layer multiplication effectively to prepare the laminated material that contains many layers.This laminate film material tool has the following advantages: 1, by least three poly-mers selecting at least one in the composite bed of layer multiplication coextrusion to include at least one separating polymer composition in forming, form and composite bed in the number of plies amount of repetitive, just can prepare the rich and varied compound barrier layer that comprises at least three poly-mers compositions; 2, in the repetitive of compound barrier layer, comprise more than two when property poly-mer forms, a plurality of barrier individual layer are double team mutually, cooperatively interacts, and barrier property is better, and material usage can be still less, and cost is lower; 3, by selection, introduce containing at least two poly-mers compositions but wherein thering is composite bed and other barrier individual layer or the composite bed that is no less than a barrier composition of other layer of multiplication co-extrusion, can further enrich again properity, price and the purposes of compound barrier layer assembly.Separating polymer film packing material by layer multiplication co-extrusion is multi-layer co-extruded more adjustable more flexibly than tradition at aspects such as the quantity of layer and the thickness of individual layer, and number of plies amount can increase greatly, and layer thickness can reduce greatly.This is multi-layer co-extruded forms with the mutual double team of sandwich form different poly-mers, has improved the overall mechanical strength of multilayer material.Multi-layer co-extruded by this, more crisp material barrier material particularly originally, can be well and non-brittle material coextrusion, and when the number of plies increases thickness and reduces, the fragility of layer material can weaken greatly.Multilayer material demonstrates excellent lear energy, anti-pin hole.More when the number of plies, hour, due to the interface layer application force greatly increasing, make also can have the binding power of relative raising at general each bad layer of multi-layer co-extruded middle cohesiveness to bed thickness, thereby can omit the use of adhesive agent, simplifies technique and saves again cost.The reducing of the increase of the number of plies and bed thickness also produces more crooked little molecular migration passage, improved barrier.Simultaneously, due to the increase of the number of plies and reducing of bed thickness, barrier material is placed in restricted clearance, can show the special crystal property, microscopic pattern etc. that contribute to improve barrier.Layer multiplication be multi-layer co-extruded to be made to reach better barrier with barrier material still less, therefore has more excellent performance and price advantage.In packing of the present invention, the structure of material can be by assembly selection and each assembly particularly the Choice and design of layer multiplication composite bed unit construction carry out Choice and design, therefore there is very various properity and price, can meet packing requirements widely, with therefore at present other compare and there is remarkable advantage without aluminium foil laminated packaging material.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the invention will be further described.
Fig. 1 be layer multiplication of comprising in isolation laminated film packing material of the present invention extrude preparation comprise that three poly-mers form and repetitive is a kind of preferred version schematic diagram of the obstruct lamination layer structure of three layers.
Fig. 2 be layer multiplication of comprising in isolation laminated film packing material of the present invention extrude preparation comprise that three poly-mers form and repetitive is a kind of preferred version schematic diagram of the obstruct lamination layer structure of four layers.
Fig. 3 be layer multiplication of comprising in isolation laminated film packing material of the present invention extrude preparation comprise that three poly-mers form and repetitive is two kinds of preferred version schematic diagrams of the obstruct lamination layer structure of five layers.
Fig. 4 be layer multiplication of comprising in isolation laminated film packing material of the present invention extrude preparation comprise that three poly-mers form and repetitive be the obstruct composite bed of three layers and layer multiplication extrude preparation comprise that two poly-mers form and repetitive is a kind of preferred version schematic diagram of the obstruct composite bed of three layers.
The specific embodiment
Below in conjunction with drawings and Examples, the present invention will be further elaborated.
Barrier individual layer or composite bed prepared by the obstruct composite bed that the stacked packing film of barrier of the present invention comprises at least one layer of multiplication coextrusion and optionally one or more additive method.In the obstruct composite bed of this at least one layer multiplication coextrusion, contain a plurality of repetitives, this repetitive comprises at least two individual layer, each individual layer is all comprised of corresponding poly-mer, and wherein at least two poly-mers corresponding to individual layer form different; Wherein the repetitive at least one this at least one obstruct composite bed at least comprises three individual layer, during this each individual layer forms corresponding at least three different poly-mers one, and these at least three different poly-mers have at least in forming and in a composition, include at least one separating polymer composition.The separating polymer composition here refers to have the poly-mer of good gas barrier.Different individual layer can refer to that the poly-mer in those individual layer forms different in the present invention, can refer to that those individual layer poly-mers form identical but thickness difference or position are different, but refer generally to there is the individual layer that different poly-mers form as do not indicated especially Different Individual layer.For example a repetitive comprises five individual layer, wherein by two individual layer, corresponding to identical poly-mer, forms A, and two individual layer form B corresponding to identical poly-mer, and body layer forms C corresponding to poly-mer one by one; With corresponding poly-mer, form while representing individual layer, in this repetitive, comprise two individual layer A, two individual layer B and one by one body layer C, five individual layer for example A/B/C/B/A Structural layer build up repetitive.The left side of definition layer stack structure is towards the outside face of packing film, and the right is towards the inside face of packing film, near the surface of content.Because in the stepped construction of the above-mentioned repetitive of difference of position by two diverse locations corresponding to poly-mer, form the individual layer of A and two diverse locations corresponding to poly-mer, form the individual layer of B.The thickness of the individual layer corresponding to poly-mer composition A of two diverse locations can be not identical, and the thickness of the individual layer corresponding to poly-mer composition B of two diverse locations can be not identical yet.In the present invention, if do not need to particularly point out, different individual layer refers generally to the individual layer forming corresponding to different poly-mers.Poly-mer forms and comprises one or more component of polymer and optional other non-polymer compositions.The poly-mer that includes separating polymer composition forms and is called separating polymer composition, and corresponding individual layer is called barrier individual layer; Otherwise, be called non-separating polymer and form and non-barrier individual layer.According to the present invention, when constituent during two kinds of poly-mers form is different, is considered as not identical poly-mer and forms, for example nylon 6 and nanoclay filled nylon-6 be not identical poly-mer composition.
Fig. 1 has described a preferred version of barrier packaging laminate film material of the present invention.In this preferred version, film 1 includes the three-layer unit 10 of a plurality of repetition of plural number.These three layers of repetitives 10 consist of with 111/112/113 stepped construction the individual layer 111,112 of three diverse locations and 113; The multiplicity of repetitive is not less than 2, is preferably greater than 10, more preferably greater than 50; Wherein, for the ease of clear each repetitive of distinguishing of reader, the subscript of the individual layer of each repetitive is different, for example 111 ', 111 ', 113 ' or 111 ", 111 ", 113 ".According to the present invention, those individual layer form corresponding to three different poly-mers, for example the individual layer of 111 positions is corresponding to forming A, the individual layer of 112 positions is corresponding to forming B, the individual layer of 113 positions is corresponding to forming C, wherein has at least and in a composition, includes at least one separating polymer composition.
According to the above-mentioned definition to repetition elementary layer stack structure, the outside face that in figure, the surface of upward direction is packing film, in figure, the surface of downward direction is inside face, is generally used for direct contact packed article.This definition is also applicable to structures all in the present invention and schematic diagram.According to the present invention, the individual layer that includes at least one separating polymer composition can be arranged in any position of repetitive.So a kind of, there are three combinations that correspond respectively to the individual layer of different poly-mers compositions and can have 6 kinds of arrangements, and this preferred version has 3 kinds of individual layer combinations, three kinds of situations that comprise one, two and three barrier individual layer, the repetitive of this preferred version can have 18 kinds of structures.For the preferred version described in Fig. 1, if only there is a barrier individual layer in three individual layer, general preferred this barrier individual layer is between two non-barrier individual layer.
The repetitive that comprises three different poly-mers compositions also can have four or four above individual layer.In the present invention, described at least one at least comprises and in the repetitive that three different poly-mers form, at least comprises a separating polymer and form.When repetitive is four individual layer structures, four individual layer that comprise three poly-mers compositions at least can have following combination: when comprising a barrier composition: a barrier individual layer A, a non-barrier individual layer B and two non-barrier individual layer C; Two barrier individual layer A, a non-barrier individual layer B and a non-barrier individual layer C; When comprising two barriers compositions: a barrier individual layer A, a barrier individual layer B and two non-barrier individual layer C; Two barrier individual layer A, a barrier individual layer B and a non-barrier individual layer C; When comprising three barriers compositions: two barrier individual layer A, a barrier individual layer B and a barrier individual layer C.In theory, every kind of combination can have 24 kinds of arrangement architectures, but when the composition of adjacent two individual layer is identical, and those adjacent layer can be considered as body layer one by one.Fig. 2 has described the repetitive preferred structure of a kind of four individual layer that comprise three poly-mers compositions of the present invention, wherein individual layer 121 forms B corresponding to non-barrier, individual layer 123 forms A corresponding to barrier, individual layer 122 and 124 forms C corresponding to identical non-barrier, and the structure of repetitive is B/C/A/C.The repeat unit structure of four individual layer that comprise three poly-mers compositions certainly of the present invention is not limited to this, and those skilled in the art person can easily understand other Rational structure.
Fig. 3 has described two kinds of repetitives of the present invention to be five layers but only to comprise the preferred structure of the compound barrier layer of the layer multiplication coextrusion that three poly-mers form.Because comprise five individual layer of three kinds of poly-mers compositions, than four above-mentioned individual layer, have more combination, five layers of repetitive that comprise three kinds of poly-mers compositions so of the present invention are not limited to two kinds of structures shown in Fig. 3.Five individual layer of the repetitive in Fig. 3 a can be for example two barrier layer A, a non-barrier layer B and two non-barrier layer C, with C/A/B/A/C structural arrangement; Or for example barrier layer A, two non-barrier layer B and two non-barrier layer C, with C/B/A/B/C structural arrangement; But the invention is not restricted to this.The layer of five repetitives in Fig. 5 b can be for example barrier layer A, a barrier layer B and three barrier layer C, with C/B/C/A/C structural arrangement, but the invention is not restricted to this.
According to above example, can find out the repetitive forming only comprising three poly-mers, by three poly-mers being formed and the selection of the individual layer quantity that repetitive comprises just can be arranged out diversified repeat unit structure by composite design.According to the present invention, the repetitive in the compound barrier layer of layer multiplication coextrusion can be by forming more than three poly-mers and more than five individual layer, so repetitive can have very various structure.The veteran personnel of this technical field can carry out rational Choice and design as required.Poly-mer in the present invention in preferred repeat units forms no more than five, and no more than five individual layer.
In barrier film of the present invention, except at least comprising one, at least comprise three different poly-mers and form and wherein have at least the compound barrier layer of the layer multiplication coextrusion that includes at least one separating polymer composition in a composition, can also optionally comprise one or more other at least comprise the composite bed that repetitive that two different poly-mers form is at least the layer multiplication coextrusion of two individual layer, as shown in Figure 4.Can find out, the structure of those optional composite beds is more rich and varied, both can have described gas barrier function, can be also not have described gas barrier function, and poly-mer does not comprise separating polymer composition in forming.The composite bed of selecting suitable extra layer multiplication to extrude, can provide for the design of packing film great facility and freedom.
In barrier film of the present invention, except the compound barrier layer that comprises layer multiplication coextrusion, can also comprise barrier composite bed prepared by one or more barrier individual layer or other non-layer multiplication methods, this has further enriched again the design of packing.Barrier composite bed prepared by non-layer times method can have the structure that is similar to barrier composite bed prepared by layer multiplication method.
In barrier film of the present invention, except thering is one, at least comprise three different poly-mers and form and wherein have the compound barrier layer of the layer multiplication coextrusion that includes at least one separating polymer composition in a composition other barrier composite bed, barrier individual layer in addition at least, or during non-barrier composite bed, between these composite beds and/or individual layer, can optionally introduce one deck or multilayer interlayer and tack coat.The effects such as interlayer generally can play that resistance is wet, resistance light, hyperchromic, support; Tack coat can play close-burning effect between different layers such as improving composite bed, individual layer, interlayer.
Can for separating polymer of the present invention, mainly refer to have the poly-mer of higher gas (oxygen) barrier, those separating polymer compositions include but not limited to ethylene-vinyl alcohol copolymer (EVOH), polyvinyl alcohol (PVA), polyamide (nylon 6, nylon 66, nylon 10, nylon 11, nylon 4-6, nylon 6-10, nylon 6-12, nylon 12, amorphous nylon, and MXD6 nylon etc.), polyacrylinitrile (PAN), polyvinylidene chloride (PVDC), polyethylene terephthalate (PET), PEN (PEN), polyvinylchloride (PVC), polyoxyethylene (PEO), Kynoar (PVDF), high density polyethylene (HDPE) (HDPE), polypropylene (PP), polyimide (PEI), PPI (PAI), polyetheretherketone (PEEK), liquid crystal polymer, ionomer based on ethene, the copolymer of ethene and beta-unsaturated esters, acrylonitrile and methacrylic acid copolymer, one or more in polyurethane engineering plastics, and their copolymer, condensation product, affixture, resultant of reaction and modifier etc.Wherein copolymerization, condensation, addition are that field of polymer technology technical personnel is known; Reaction can be various suitable chemical reactions; modification can be the modification that various suitable chemistry or physical method carry out; these reactions and this property include but not limited to grafting, oxidation, ozonidation, crosslinked, hydrolysis, halogenation, acidifying, acidylate, esterification, amination, alkylation etc., and simultaneous reactions and modification are applicable to above-mentioned component of polymer itself and their monomer, presoma and prepolymer etc.In the present invention, separating polymer can comprise more than a kind of above-mentioned component of polymer in forming, can be so that with the compound of above-mentioned separating polymer composition.The compositions such as one or more non-(low) separating polymer compositions, filler, additive, auxiliary agent that can also comprise other during separating polymer forms.
Non-(low) separating polymer composition during barrier forms generally plays enhancing, toughness reinforcing, promote bonding, the effect such as reduce costs, those component of polymer can be natural or synthetic thermoplastic base resin or the thermosetting resins of any appropriate, can be linear, cladodification shape, starlike or cross-linked polymer, include but not limited to polyolefin Polymer, acrylic resin, Chelate resin, polyester, unsaturated polyester (UP), biological polyester, polyethers, polyurethane, polysiloxane, polystyrene Polymer, vinyl chloride Polymer, polysulfide, epoxy resin, one or more in phenol resin, and their copolymer, condensation product, affixture, resultant of reaction and modifier etc.The object lesson of suitable non-(low) separating polymer composition includes but not limited to high density polyethylene (HDPE) (HDPE), medium density polyethylene (MDPE), Low Density Polyethylene (LDPE), linear low density polyethylene (LLDPE), Low Density Polyethylene (VLDPE) very, ultra-low density polyethylene (ULDPE), metallocene PE (mPE), cyclic olefin copolymer (COC), isotactic polypropylene (iPP), syndiotactic polypropylene (sPP), metallocene polypropylene (mPP), ethene-alpha olefin copolymer, ethylene-vinyl acetate copolymer (EVA), ethylene-methacrylic acid copolymer (EMA), ethylene-acrylic acid copolymer (EAA), anhydride modified polyethylene, the polyolefin of acid modification, epoxy-functional polyethylene, oxidic polyethylene, haloflex, the ethylene methacrylic acid copolymer of metal neutralization, anhydride modified polypropylene, epoxy-functional polypropylene, polyacrylic acid, polybutene, polyisobutene, poly-butadiene, polyisoprene, polyprene, ethylene-propylene copolymer, ethylene-propylene-diene copolymer (EPDM), polystyrene (PS), acrylic nitrile-butadiene-alkene-styrol copolymer (ABS), acrylonitritrile-styrene resin (AS), butadiene-styrene copolymer, polyformaldehyde, polymethyl methacrylate (PMMA), polyether polyurethane, polyesters polyurethane, polyolefins polyurethane, polyacrylic polyurethane, polycarbonate-based polyurethane, polydimethyl diloxanes (PDMS), polypropyleneoxide (PPO), PEP-101, PolyTHF, polycarbonate (PC), poly-ε-acid esters in oneself, poly(lactic acid) (PLA), one or more in polyhydroxyalkanoate (PHA), and their copolymer, condensation product, affixture, reaction and modified product etc.In the present invention, can select as required one or more non-(low) separating polymer compositions and one or more separating polymer compositions to be combined into separating polymer matrix.
The filler composition forming for barrier can be various suitable organic and inorganic fillers, include but not limited to one or more in cellulose fibre, glass fibre, carbon black, graphite, dolomite, chalk, talcum, mica, calcium carbonate, clay, fly ash, glass powder, diatom earth, silica, zeolite, metal hydroxides, metallic oxide, metal sulfate, metal carbonate and their modifier and reactant.In the present invention, for filling the filler of separating polymer, preferably there is the flaky inorganic filler of certain diameter Thickness Ratio (aspect ratio), as graphite, clay, talcum, mica, calcium carbonate, dolomite, chalk etc.Fill separating polymer and can greatly reduce material cost, because the price of general separating polymer is to determine packing price principal element.Fill the flaky inorganic filler of major diameter Thickness Ratio, can also produce the little molecular migration passage of curved elongated, improve the barrier property of material.In order to reach desirable effect, can select to fill more than a kind of filler composition.
Additive, auxiliary agent during separating polymer forms mainly comprise as antioxidant, ultraviolet absorbent, heat stabilizer, light stabilizer, antistatic additive, lubricant, plasticizer, anticlogging agent, fire retardant, antiseize agent, inorganic/organic expander, foaming agent, coating material and pigment etc.Detailed additive and auxiliary agent information can be consulted relevant handbook.The technical personnel of plastics and rubber materials, can reasonably select as required easily.
Non-barrier or low separating polymer form, it is the poly-mer composition in non-(low) barrier individual layer in composite bed, general do not have good gas (oxygen) barrier function, those form corresponding non-barrier individual layer generally play enhancing, toughness reinforcing, dispersion, bonding, the effect such as seal, reduce costs.Those poly-mers form compositions such as comprising one or more non-(low) separating polymer compositions and optional suitable filler, additive, auxiliary agent.Those non-(low) separating polymer compositions, and the composition such as optional suitable filler, additive, auxiliary agent composition is consistent accordingly in forming with above-mentioned barrier.Non-(low) the preferred Low Density Polyethylene of separating polymer composition (LDPE), linear low density polyethylene (LLDPE), ethylene-acrylic acid copolymer (EAA) and metallocene PE (mPE) in forming for non-(low) separating polymer in the present invention and at least one in metallocene polypropylene (mPP).
Separating polymer in barrier composite bed prepared by non-layer of multiplication method of barrier individual layer and other forms and non-separating polymer forms consistent with corresponding poly-mer composition in above-mentioned barrier and non-(low) barrier individual layer.
Between composite bed and/or individual layer, be between composite bed and composite bed, between composite bed and individual layer, between individual layer and individual layer, the poly-mer of optional one deck or multilayer interlayer forms consistent with non-(low) separating polymer composition in above-mentioned non-barrier individual layer.
Can be for each composite bed that bonds, barrier individual layer, the binder polymer composition of interlayer includes but not limited to anhydride modified polyethylene, the polyolefin of acid modification, epoxy-functional polyethylene, oxidic polyethylene, ethylene-vinyl acetate copolymer (EVA), the ethylene methacrylic acid copolymer of metal neutralization, ethylene acrylic acid co polymer (EAA), ethylene methacrylic acid copolymer (EMA), anhydride modified polypropylene, epoxy-functional polypropylene, metallocene PE (mPE), polyacrylic acid, polyester, polyurethane, ionomer, styrene series thermoplastic elastomer (SBC), vinyl chloride thermoplastic base resin (TPVC), ethylene series thermoplastic base resin (TPO), nitrile based thermoplastic resin, polyamide-based thermoplastic base resin (TPAE), one or more in fluorine based thermoplastic resin and hydrogenated styrene based thermoplastic resin, and their copolymer, condensation product, affixture, modifier, reaction and modified product etc.Wherein copolymerization, condensation, addition, modification and reaction are consistent with above-mentioned corresponding description.The cohesiveness poly-mer that adhesive layer is corresponding forms can comprise at least above-mentioned a kind of cohesiveness component of polymer, and optional other suitable component of polymer, and the composition such as optional suitable filler, additive, auxiliary agent.Consider the factor such as preparation technology, price, environmental protection, toxicity, recycling of packing, preferred anhydrides improved polyalkene of the present invention and ethylene-vinyl acetate copolymer (EVA) when choice for use adhesive agent.These binder polymer compositions also can be used as the composition that other poly-mers form, as the interpolation blend composition that separating polymer forms and non-(low) separating polymer forms, in order to increase the cohesive force between adjacent layer in the situation that not increasing extra adhesive layer.The bulking agent that those adhesive agents of part can be used as other component of polymer blend is used.
The layer multiplication method adopting in the present invention is a kind of to the cut apart repeatedly-stacked coextrusion method of converging operation again of feed steam, each cuts apart-and stackedly again converge operation and be accompanied by cutting apart major ingredient stream, width expansion and high shrinkage to branch's material stream, and within stacked minute, send away major ingredient fluid layer quantity again and be multiplied, major ingredient stream individual layer thickness reduces at double.Layer multiplication operation can be by for example Chinese utility model patent application 200820229095.4 and 200820229641.4, and the layer multiplicator described in Chinese invention patent application 200810072529.9 and other suitable layer multiplying assemblies, as US Patent No. 3635444, carry out.
Result of study shows, adopts the multi-layer co-extruded method of layer multiplication can effectively prepare the laminated material that contains many layers.Barrier composite bed by layer multiplication coextrusion is multi-layer co-extruded more adjustable more flexibly than tradition at aspects such as the quantity of layer and the thickness of individual layer, and number of plies amount can increase greatly, and layer thickness can reduce greatly.This is multi-layer co-extruded forms with the mutual double team of sandwich form different poly-mers, has improved the overall mechanical strength of multilayer material.Multi-layer co-extruded by this, unmanageable more crisp material barrier material particularly originally, also can be well and non-brittle material coextrusion, and when the number of plies increases thickness and reduces, the fragility of layer material can reduce greatly.Multilayer material demonstrates excellent lear energy, anti-pin hole.More when the number of plies, hour, due to the interface layer application force greatly increasing, make also can have the binding power of relative raising at general each bad layer of multi-layer co-extruded middle cohesiveness to bed thickness, thereby can omit the use of adhesive agent, simplifies technique and also saves cost.The reducing of the increase of the number of plies and bed thickness also produces more crooked little molecular migration passage, improved barrier.Simultaneously, due to the increase of the number of plies and reducing of bed thickness, barrier material is placed in restricted clearance, can show the crystal property, microscopic pattern etc. that contribute to improve barrier.This is multi-layer co-extruded, makes to reach better barrier with barrier material still less, therefore has more excellent performance and price advantage.In the present invention, by select at least one composite bed of layer multiplication coextrusion comprise that at least three poly-mers that at least one separating polymer forms form and composite bed in the individual layer quantity of repetitive, just can prepare the rich and varied compound barrier layer that comprises at least three poly-mers compositions.By selection, introduce containing at least two poly-mers compositions but wherein thering is composite bed and other barrier individual layer or the composite bed that any amount barrier forms of other layer of multiplication co-extrusion in addition, can further enrich again properity, price and the purposes of compound barrier layer assembly.Generally, barrier packaging film only comprises the compound barrier layer of a layer multiplication coextrusion that comprises at least three poly-mers compositions and be wherein comprised of at least one barrier, just can have than the more excellent Combination property of the multi-layer co-extruded film of tradition.
In the present invention, if only comprise the compound barrier layer of a layer multiplication coextrusion that comprises at least three poly-mers compositions and wherein formed by least one barrier in barrier packaging film, do not comprise other individual layers or composite bed, the preparation of film generally completes by a sublevel multiplication coextrusion.In layer multiplication coextrusion process, first the feed composition each poly-mer in film being formed carries extruded stock to flow by feeder and other accessory equipments of suitable quantity to confession stub bar, each feed steam is building up the composite stream with specific repeat unit structure for tegillum in stub bar, this composite stream cut apart in multiplicator repeatedly at the layer in downstream-stacked converging again, reach after certain number of plies amount, by suitable extruder head, extrude.Wherein for stub bar can be common multiple flow passages for stub bar, diverter and the combination for stub bar of common multiple flow passages, and increase layer and supply stub bar.The feed composition that above-mentioned poly-mer forms may not form identical with corresponding poly-mer, in feed composition, can comprise poly-mer form in the monomer, presoma, prepolymer etc. of each composition, can also comprise the composition that various suitable solvents, diluent, dispersing agent etc. finally can be removed.
If in barrier packaging film except comprising a compound barrier layer that comprises the layer multiplication coextrusion that at least three poly-mers form and be wherein comprised of at least one barrier, also comprise the composite bed of other layer multiplication coextrusion, other the composite bed of non-layer multiplication coextrusion and individual layer etc., the preparation of film is generally to complete for the similar Duo Qi of stub bar road extruder head coextrusion by each composite bed or individual layer are similar to common multiple flow passages by one or more.If necessary, can first preparing respectively each composite bed or individual layer, to carry out laminated or direct co-extrusion part composite bed or individual layer laminated with other composite bed or individual layer substep more again.At Polymer, extrude the technical personnel in field and can select as required rational laminating method and necessary treatment process.
Because laminated material of the present invention is packaging film, so in film preparation process, top layer near content in General Requirements film is the layer that is easy to involution, and the material in this superficial layer of General Requirements has chemical inertness to content, liquid component in content is had to high barrier, each composition in content is had to low absorption.The component of polymer that generally can be used for superficial layer can include but not limited to high density polyethylene (HDPE) (HDPE), Low Density Polyethylene (LDPE), linear low density polyethylene (LLDPE), Low Density Polyethylene (VLDPE) very, metallocene PE (mPE), cyclic olefin copolymer (COC), isotactic polypropylene (iPP), syndiotactic polypropylene (sPP), biaxial stretch-formed polypropylene (BOPP), cast polypropylene (CPP), metallocene polypropylene (mPP), ethene-alpha olefin copolymer, ethylene-vinyl acetate copolymer (EVA), ethylene-methacrylic acid copolymer (EMA), one or more in ethylene-acrylic acid copolymer (EAA), and their modifier, resultant of reaction etc.
At least one in the stacked packing film material of barrier of the present invention comprise that at least three poly-mers form and thickness that wherein at least one is the obstruct composite bed of the layer multiplication coextrusion that forms of barrier is preferably not more than 900 microns, more preferably no more than 500 microns, most preferably between 10 microns to 200 microns.
The stacked packing film material of barrier of the present invention can directly be used as film, for example preservative film; Or be processed to the containers such as bag, bag of various shapes, such as the bag of pillow shape and the bag of other polyhedrals etc.The personnel of this technical field can design processing as required.Packing are processed in the process of bag, bag etc., need to carry out involution to material, its method comprises heat-sealing, bright eruption sealing, hot gas sealing, ultrasonic sealing, high frequency sealing etc.Those packing containers can be for splendid attire fluid product for example fresh milk, dairy products, soya-bean milk, beverage, fruit juice, wine, seasonings and other food, and agricultural chemicals, Medicines, chemical, biopreparate, ink etc.Can also be for packing solid product, food and other products such as cheese, bean curd, chocolate.In packing film material of the present invention, the structure of material can be by assembly selection and each assembly particularly the Choice and design of the composite bed unit construction of layer multiplication coextrusion carry out Choice and design, therefore there is very various properity and price, can meet packing requirements widely.
In the present embodiment, packing film only comprises layer compound barrier layer that multiplication is extruded that a repetitive only comprises three individual layer, wherein only a separating polymer, consists of.In repetitive, the separating polymer of body layer correspondence composition A is extrusion grade ethylene-vinyl alcohol copolymer (EVOH) one by one, the non-separating polymer composition B of body layer correspondence is the blend (LDPE+maLDPE) of 95wt% Low Density Polyethylene and the maleic anhydride modified Low Density Polyethylene of 5wt% one by one, the non-separating polymer composition C of body layer correspondence is ethylene-acrylic acid copolymer (EAA) one by one, and repeat unit structure is B/A/C.
By three single screw extrusion machines, to a three-channel stub bar that supplies, provide the material of melting to flow, have the initial stacked material stream of repeat unit structure again by the double layers multiplicators of 8 head and the tail series connection, total number of plies of compound barrier layer is 768 layers; Finally, by the extruder head of a clothes hanger type, extrude the film of approximately 100 microns of thickness.In film, each bulk layer thickness of repetitive is close, and barrier individual layer thickness is about 130 nanometers.
By this packing film, can directly as film, be used, also can be processed into the containers such as suitable bag and bag and use.
Embodiment 2
In the present embodiment, only comprise the obstruct composite bed that a layer multiplication is extruded in packing film material, wherein repetitive has four individual layer, but only comprise three poly-mers, forms wherein only containing a barrier composition.It is the nylon 6 that 5wt% nanoclay is filled that poly-mer corresponding to one of them barrier individual layer forms A, it is the maleic anhydride modified polyacrylic compound of 97wt% polypropylene and 3wt% that two poly-mers corresponding to non-barrier individual layer form B, it is metallocene Low Density Polyethylene that a poly-mer corresponding to non-barrier individual layer forms C, and repeat unit structure is C/B/A/B.
By three single screw extrusion machines and a bidirectional shunt device, to a four-way, for stub bar, provide the material of melting to flow, have the initial stacked material stream of repeat unit structure again by the double layers multiplicator of 7 series connection, total number of plies of compound barrier layer is 512 layers; Finally, by the extruder head of a clothes hanger type, extrude the film of approximately 200 microns of thickness.In film, each bulk layer thickness of repetitive is close, and barrier individual layer thickness is about 400 nanometers.
Embodiment 3
In the present embodiment, only comprise the obstruct composite bed that a layer multiplication is extruded in packing film, wherein repetitive has five individual layer, but only comprise three poly-mers, forms and wherein only containing a barrier, forms.In five individual layer, it is Vingon (PVDC) that a separating polymer corresponding to barrier individual layer forms A, it is polyesters polyurethane that two non-separating polymers corresponding to non-barrier individual layer form B, it is biological polyester PHBV (PHBV) that two non-separating polymers corresponding to non-barrier individual layer form C, with C/B/A/B/C Structural layer, builds up repetitive.
By three single screw extrusion machines and two bidirectional shunt devices, to a Five-channel, for stub bar, provide the material of melting to flow, have the initial stacked material stream of repeat unit structure again by the double layers multiplicator of 7 series connection, total number of plies of compound barrier layer is 640 layers; Finally, by the extruder head of a clothes hanger type, extrude the film of approximately 120 microns of thickness.In film, each bulk layer thickness of repetitive is close, and barrier individual layer thickness is about 180 nanometers.
Embodiment 4
In the present embodiment, only comprise the obstruct composite bed that a layer multiplication is extruded in packing film, wherein repetitive has four individual layer, corresponds respectively to four poly-mers and forms and wherein containing two barriers, form.The separating polymer that barrier individual layer A is corresponding consists of the compound of polyethylene terephthalate (PET) and MXD6 nylon, the separating polymer that barrier individual layer B is corresponding consists of polyvinylchloride (PVC) and appropriate plasticizer, non-separating polymer corresponding to non-barrier individual layer C consists of ethylene-acrylic acid copolymer (EAA), non-separating polymer corresponding to non-barrier individual layer D consists of acrylic nitrile-butadiene-alkene-styrol copolymer (ABS), and the stepped construction of four individual layer is D/A/B/C.
By four single screw extrusion machines and an increasing layer, for stub bar, provide the material of melting to flow, its structure is D/A/B/C/D/A/B/C/D/A/B/C; By the preliminary initial stacked material stream that increases layer, again by the quadruple-layer multiplicator of 3 series connection, total number of plies of compound barrier layer is 768 layers; Finally, by an extruder head with constant cross-sectional area, extrude the film of approximately 230 microns of thickness.In film, each bulk layer thickness of repetitive is close, and individual layer thickness is about 300 nanometers.
Embodiment 5
In the present embodiment, packing film material comprises obstruct composite bed and the barrier individual layer that the multiplication of layer extruded, and intercepts between composite bed and individual layer and is connected with a tack coat, and the integral structure of membraneous material is composite bed/tack coat/individual layer.Wherein intercept composite bed comprise three poly-mers form wherein two for barrier and repetitive be three layers, it is polyvinyl alcohol (PVA) that a separating polymer corresponding to barrier individual layer forms A, it is polyacrylinitrile (PAN) that a separating polymer corresponding to barrier individual layer forms B, it is oxidic polyethylene that a non-separating polymer corresponding to non-barrier individual layer forms C, and repeat unit structure is C/A/B; The poly-mer that barrier individual layer is corresponding consists of PEN (PEN); The poly-mer of tack coat consists of ethylene-vinyl acetate copolymer (EVA).
By three single screw extrusion machines and a common multiple flow passages, for stub bar, provide the compound coating layer of melting to flow, have the initial stacked material stream of repeat unit structure again by quadruple-layer multiplicator and a double layers multiplicator of 4 series connection, total number of plies of compound barrier layer is 1536 layers; The barrier individual layer material stream that last and other two extruders is carried and bonding layered material stream pass through Yi Gesanqi road extruder head, extrude the film of approximately 100 microns of thickness.In film, the thickness of barrier composite bed is about 80 microns, and each bulk layer thickness of its repetitive is close, and individual layer thickness is about 50 nanometers.
Embodiment 6
In the present embodiment, packing film material comprises the barrier composite bed that two layer multiplications are extruded, and the repetitive of one of them barrier composite bed I is three layers, corresponds respectively to three poly-mers and forms, and one of them is barrier composition; The repetitive of another one barrier composite bed II is only two-layer, corresponding to a barrier, forms and a non-barrier composition; The integral structure of film is composite bed I/ composite bed II.In composite bed I, it is the nylon 66 that shell mica is filled that a separating polymer corresponding to barrier individual layer forms A, it is the metallocene linear-low density polyethylene (mLLDPE) that titanium dioxide is filled that a non-separating polymer corresponding to non-barrier individual layer forms B, and it is carbon black filled maleic anhydride modified polypropylene that a non-separating polymer corresponding to non-barrier individual layer forms C; In composite bed II, it is polyoxyethylene (PEO) that separating polymer corresponding to barrier individual layer forms D, and it is polyether polyurethane that non-separating polymer corresponding to non-barrier individual layer forms E.
This packing film material adopts a coetrusion preparation.Wherein intercept composite bed I and supply stub bar by three runners, 3 quadruple-layer multiplicators and 1 double layers multiplicator, the number of plies reaches 384 layers; Intercept composite bed II and supply stub bar by a dual channel, 5 quadruple-layer multiplicators, the number of plies reaches 2048 layers; Two composite beds, by a bifid road extruder head, are extruded into the film that thickness is about 150 microns, and wherein composite bed I is approximately 50 microns, approximately 100 microns of composite bed II.
The above, be only preferred embodiment of the present invention, therefore can not limit scope of the invention process with this, the equivalence of doing according to the present patent application the scope of the claims and description changes and modifies, and all should still remain within the scope of the patent.
Claims (15)
1. a barrier-property lapped polymer film packaging material, it is characterized in that: it comprises that the lamination of at least one layer of multiplication coextrusion intercepts composite bed, this each obstruct composite bed all contains a plurality of repetitives, this repetitive comprises at least two individual layer, and each individual layer is corresponding to one at least two different poly-mers compositions; Wherein the repetitive of at least one this lamination obstruct composite bed at least comprises three individual layer, this each individual layer is corresponding to one at least three different poly-mers compositions, and, during these at least three poly-mers form, have at least a composition to include at least one separating polymer composition, this separating polymer composition can intercept gas; This layer of multiplication coextrusion is a kind of to the cut apart repeatedly-stacked coextrusion method of converging operation again of feed steam.
2. barrier-property lapped polymer film packaging material according to claim 1, is characterized in that: in membraneous material, also comprise barrier individual layer or/and the barrier composite bed of non-layer multiplication coextrusion.
3. barrier-property lapped polymer film packaging material according to claim 2, is characterized in that: in membraneous material, also comprise at least one deck tack coat of being present between described various composite bed and individual layer or/and one deck interlayer at least.
4. barrier-property lapped polymer film packaging material according to claim 1, is characterized in that: the thickness that this comprises that at least one repetitive and repetitive comprise that at least three different poly-mers form and wherein at least one is the obstruct composite bed of the layer multiplication coextrusion that forms of barrier is not more than 900 microns.
5. according to the barrier-property lapped polymer film packaging material described in claim 1 or 2 or 3 or 4, it is characterized in that: this at least one barrier properties for gases component of polymer is selected from ethylene-vinyl alcohol copolymer (EVOH), polyvinyl alcohol (PVA), polyamide (PA), polyacrylinitrile (PAN), polyvinylidene chloride (PVDC), polyethylene terephthalate (PET), PEN (PEN), polyvinylchloride (PVC), polyoxyethylene (PEO), Kynoar (PVDF), high density polyethylene (HDPE) (HDPE), polypropylene (PP), polyimide (PEI), PPI (PAI), polyetheretherketone (PEEK), liquid crystal polymer, ionomer based on ethene, the copolymer of ethene and beta-unsaturated esters, one or more in acrylonitrile and methacrylic acid copolymer or polyurethane engineering plastics, or be selected from the copolymer of above-mentioned one or more, condensation product, affixture, resultant of reaction or modifier.
6. according to the barrier-property lapped polymer film packaging material described in claim 1 or 2 or 3 or 4, it is characterized in that: this at least one non-pneumatic separating polymer composition is selected from one or more in polyolefin Polymer, acrylic resin, vinyl cyanide resin, polyester, unsaturated polyester (UP), biological polyester, polyethers, polyurethane, polysiloxane, polystyrene Polymer, vinyl chloride Polymer, polysulfide, epoxy resin or phenol resin, or be selected from copolymer, condensation product, affixture, resultant of reaction or the modifier of above-mentioned one or more.
7. according to the barrier-property lapped polymer film packaging material described in claim 1 or 2 or 3 or 4, it is characterized in that: also comprise the filler for filled polymer.
8. according to the barrier-property lapped polymer film packaging material described in claim 1 or 2 or 3 or 4, it is characterized in that: also comprise polymer builder.
9. according to the barrier-property lapped polymer film packaging material described in claim 1 or 2 or 3 or 4, it is characterized in that: also comprise polymeric additive.
10. barrier-property lapped polymer film packaging material according to claim 1, is characterized in that:
Packing film only comprises layer compound barrier layer that multiplication is extruded that a repetitive only comprises three individual layer, wherein only a separating polymer, consists of.
11. barrier-property lapped polymer film packaging materials according to claim 1, is characterized in that:
In packing film material, only comprise the obstruct composite bed that a layer multiplication is extruded, wherein repetitive has four individual layer, but only comprise three poly-mers, forms wherein only containing a barrier composition.
12. barrier-property lapped polymer film packaging materials according to claim 1, is characterized in that:
In packing film, only comprise the obstruct composite bed that a layer multiplication is extruded, wherein repetitive has five individual layer, but only comprise three poly-mers, forms and wherein only containing a barrier, forms.
13. barrier-property lapped polymer film packaging materials according to claim 1, is characterized in that:
In packing film, only comprise the obstruct composite bed that a layer multiplication is extruded, wherein repetitive has four individual layer, corresponds respectively to four poly-mers and forms and wherein containing two barriers, form.
14. barrier-property lapped polymer film packaging materials according to claim 1, is characterized in that:
Packing film material comprises obstruct composite bed and the barrier individual layer that a layer multiplication is extruded, intercept between composite bed and individual layer and be connected with a tack coat, the integral structure of membraneous material is composite bed/tack coat/individual layer, wherein intercept composite bed comprise three poly-mers form wherein two for barrier and repetitive be three layers.
15. barrier-property lapped polymer film packaging materials according to claim 1, is characterized in that:
Packing film material comprises the barrier composite bed that two layer multiplications are extruded, and the repetitive of one of them barrier composite bed I is three layers, corresponds respectively to three poly-mers and forms, and one of them is barrier composition; The repetitive of another one barrier composite bed II is only two-layer, corresponding to a barrier, forms and a non-barrier composition; The integral structure of film is composite bed I/ composite bed II.
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Effective date of registration: 20180720 Address after: 363000 block D, 15 floor, Garden Mansion, Yanan North Road, Zhangzhou, Fujian. Patentee after: Weng Wengui Address before: 361000 801, 803, 805, block D, Jianye Road, Xiamen torch high tech Zone (Xiangan) Industrial Zone, Xiamen, Fujian Patentee before: XIAMEN SINOPEG BIOTECH Co.,Ltd. |
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| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20181112 Address after: 361000 1, building five, five Qishan North Road, 770 Huli District, Xiamen, Fujian. Patentee after: Xiamen iron cloth Mstar Technology Ltd. Address before: 363000 block D, 15 floor, Garden Mansion, Yanan North Road, Zhangzhou, Fujian. Patentee before: Weng Wengui |
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| TR01 | Transfer of patent right | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 361000 1, building five, five Qishan North Road, 770 Huli District, Xiamen, Fujian. Patentee after: Xiamen Tiance Material Technology Co.,Ltd. Address before: 361000 1, building five, five Qishan North Road, 770 Huli District, Xiamen, Fujian. Patentee before: Xiamen iron cloth Mstar Technology Ltd. |
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| CP01 | Change in the name or title of a patent holder | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140115 |