CN101992888A - Laminated material without metal foil for blocking package - Google Patents
Laminated material without metal foil for blocking package Download PDFInfo
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- CN101992888A CN101992888A CN200910168822XA CN200910168822A CN101992888A CN 101992888 A CN101992888 A CN 101992888A CN 200910168822X A CN200910168822X A CN 200910168822XA CN 200910168822 A CN200910168822 A CN 200910168822A CN 101992888 A CN101992888 A CN 101992888A
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Links
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Images
Abstract
The invention discloses a laminated material without metal foil for a blocking package. The material at least comprises a substrate layer assembly and a composite blocking layer assembly, wherein the substrate layer assembly and the composite blocking layer assembly are laminated together; the substrate layer assembly has the effect of supporting; and the composite blocking layer assembly comprises at least one composite blocking layer which is prepared through a partition-laminated confluence layer multiplication and coextrusion method and comprises a plurality of repeated units. The material is characterized in that each repeated unit at least comprises three polymer constitutes, and each polymer constitute can form an individual layer or more than one individual layer; and only one of the polymer constitutes is a blocking polymer constitute which can block gas.
Description
Technical field
The present invention relates to a kind of laminated material that is used for the metal-foil-free of barrier packaging.
Background technology
In modern society's life, more and more higher to the requirement fresh-keeping, that guarantee the quality, protect local flavor and prolongation shelf life function of various food, medical product and articles for daily use etc., so the barrier packaging material has become competitively hot of research and development of various countries.
More common barrier packaging material is the rhythmo structure that a class makes by laminated layers of material, and for example paper is as structural materials to comprise one deck lamination coating, and its two sides covers with heat sealable plastic layer.In the high-barrier Packing Condition, packing comprise one deck choke oxygen barrier material, be generally aluminium foil and be combined on the lamination coating by heat sealable plastics of one deck or adhesive layer, simultaneously again by directly and content (being the product of packaging) contacted one deck or the heat sealable plastics of multilayer cover.The high-barrier packaging material that this class contains aluminium foil (Al) comprises that mainly the structure of the Tetrapack company exploitation of Sweden is the laminated material of PE/ cardboard/tack coat/Al/PE/PE, the structure of Switzerland SIG company development and Design is the laminated material of PE/ white board/PE/Al/ tack coat/PE, and the material of the PE/ cardboard/Al/PE structure of domestic spring woods packaging company exploitation.Though wrapping enterprises such as at present domestic spring woods and day dragon also begin to grow up, the market share of Chinese Enterprise is still very little.
Metal aluminum foil has inherent advantages as high barrier material, and it is choke but also be not subjected to humidity effect not only.Though and many poly-mer barrier materials then have high gas barrier property but to humidity sensitive, and are perhaps general to the insensitive gas barrier property of humidity.Therefore, in the present aseptic packaging, the packing of high barrier are still preponderated with the laminate that contains aluminium foil.Yet the fee of material height of aluminium foil generally need be worked into the degree that forms the aluminium foil thin slice to aluminium foil when using, processing charges is also high.For aluminium foil, have only to be only sir-tight fully greater than time more than 25 microns when its thickness.And to consider the cost of material generally speaking, the aluminum foil thickness that uses in the packing is substantially about 10 microns, so barrier is had a greatly reduced quality.Aluminium foil has low-down ductility and stretchability in addition, therefore, is easy to crack when stretching with flexure stress when being exposed to hale, particularly at the folding or crooked position of packaging laminated product.Aluminium foil also lacks necessary strength under the high speed pressure processing conditions, promptly in line, packing box moulding and packing box assigning process, lacks the ability that forms the comprehensive desired anti-stress cracking of low permeability structure.In addition, the use of aluminium foil also has the harmful effect of environment aspect.During metal detection, the existence of aluminium foil also can be disturbed in the packing.Use the packing of aluminium foil can not carry out microwave treatment.Therefore, be necessary to develop the rhythmo structure of no aluminium foil, provide and the cooresponding barrier property of aluminium foil, overcome the shortcoming that contains In Aluminium Foil Packing again.
In recent years, company such as Tetrapack Lavalle and U.S.'s International Paper all comprises the no aluminium foil rhythmo structure packing of substrate layer in development and Design.In these structures, as Chinese patent ZL96197841.4, ZL96198157.1 and Chinese patent application 99817009.1,200680031721.2 etc., coated or the stacking polymer film of the separating polymer of sandwich applies or is laminated on the base material inside face, in the hope of replacing containing the laminated packaging material of aluminium foil.These stacking polymer materials that are layered in the base material inside face can adopt compound, the solvent-free method preparation such as compound of dry type, are similar to common multi-layer co-extruded packaging barrier composite polymer films.So, reach desirable barriering effect and cost advantage, the structure of the stacking polymer material on the base material inside face, performance and technology of preparing decisive role.
The R and D of multi-layer co-extruded composite polymer films also obtain significant progress in recent years.And multi-layer co-extruded film is compared with conventional films and is had bigger performance and price advantage.Yet the multilayer film co-extrusion technology no matter be coextrusion blow or coextrusion casting, all has great limitation at present.This is because the co-extrusion number of plies is high more, and the construction of co-extrusion die head and operation are just difficult more.The present whole world 9 layers of coextrusion blow manufacturing line of 25 covers of only having an appointment.The die head of the coextrusion casting coextrusion die that compares is simple, but will build the high die head of the number of plies still has very big difficulty.So, the number of plies of coextruded film is just very limited, causes the coextruded film performance can't continue to improve.
Summary of the invention
The invention provides a kind of isolation laminated material of packaging that does not have aluminium foil, it has overcome the existing deficiency of background technology laminated material.
The technical solution adopted for the present invention to solve the technical problems is:
A kind of laminated material that is used for the metal-foil-free of barrier packaging, which comprises at least a substrate layer assembly and a compound barrier layer assembly, this substrate layer assembly and compound barrier layer component layer lump together, this substrate layer assembly can play a supportive role, this compound barrier layer assembly comprises at least one by cutting apart-the stacked again layer multiplication coextrusion method preparation that converges, the compound barrier layer that contains a plurality of repetitives, this each repetitive comprises three kinds of poly-mers at least and forms, this every kind poly-mer is formed can both form body layer one by one or more than one individual layer, only being made up of a kind of poly-mer during those kinds poly-mer is formed is that separating polymer is formed, and this separating polymer is formed can intercept gas.
In a preferred embodiment of the present invention, this substrate layer assembly is selected from least a in paper substrates and the polymer-matrix base material.
In a preferred embodiment of the present invention, separating polymer material during this separating polymer is formed is at least a polyvinyl alcohol (PVA) that is selected from, polyacrylinitrile (PAN), polyimide (PI), polymethylpentene (PMP), polyvinylidene chloride (PVDC), polyethylene terephthalate (PET), PEN (PEN), polyvinylchloride (PVC), polymerization oxidation ethene (PEO), Kynoar (PVDF), high density polyethylene (HDPE) (HDPE), polypropylene (PP), liquid crystal polyester, ionomer based on ethene, acrylonitrile copolymer, the copolymer of ethene and beta-unsaturated esters, ethylene-vinyl alcohol copolymer (EVOH) and at least a nylon 6 that is selected from, nylon 66, nylon 10, nylon 6-10, nylon 6-12, nylon 12, amorphous nylon, and the compound of MXD6 nylon, and their modifier and resultant of reaction.
In a preferred embodiment of the present invention, separating polymer material during this separating polymer is formed is at least a polyvinyl alcohol (PVA) that is selected from, polyacrylinitrile (PAN), polyimide (PI), polymethylpentene (PMP), polyvinylidene chloride (PVDC), polyethylene terephthalate (PET), PEN (PEN), polyvinylchloride (PVC), polymerization oxidation ethene (PEO), Kynoar (PVDF), liquid crystal polyester, ionomer based on ethene, acrylonitrile copolymer, the copolymer of ethene and beta-unsaturated esters, and the component of polymer of their modifier and resultant of reaction and at least a ethylene-vinyl alcohol copolymer (EVOH) that is selected from, nylon 6, nylon 66, nylon 10, nylon 6-10, nylon 6-12, nylon 12, amorphous nylon, MXD6 nylon, and at least a in the compound that component of polymer constituted of their modifier and resultant of reaction.
In a preferred embodiment of the present invention, this contains at least one compound barrier layer assembly by the compound barrier layer of layer multiplication coextrusion and also comprises at least one barrier individual layer.
In a preferred embodiment of the present invention, this contain also comprise in the compound barrier layer assembly of compound barrier layer of at least one layer multiplication coextrusion at least one other non-by cutting apart-the compound barrier layer of the stacked again layer multiplication coextrusion preparation that converges.
In a preferred embodiment of the present invention, also comprise: can be laminated in the outer layer assembly in the substrate layer assembly outside and can be laminated in the interior layer assembly of barrier layer assembly inboard at least one.
In a preferred embodiment of the present invention, also comprise: the tack coat assembly that is used for each layer in bonding each assembly and the assembly.
In a preferred embodiment of the present invention, also comprise: can be laminated between each assembly and within the interlayer assembly.
In a preferred embodiment of the present invention, be used for the Charge that filled polymer is formed, this Charge slabbing.
Technical scheme of the present invention is compared with background technology: the applicant adopt dexterously one comprise that at least one comprises that at least three poly-mers form by cut apart-the compound barrier layer assembly of the compound barrier layer of the stacked more multi-layer co-extruded technology preparation of layer multiplication that converges carries out flexible combination with substrate layer assembly and selectable outer layer assembly, interior layer assembly, interlayer assembly and tack coat assembly, prepares the isolation laminated packaging material of no aluminium foil.It has following advantage: 1, by in the composite bed of selecting layer multiplication coextrusion only comprise that at least three poly-mers that a barrier forms are formed and composite bed in the number of plies amount of repetitive, just can prepare the rich and varied compound barrier layer that at least three poly-mers are formed that comprises, the barrier material consumption can be reduced, manufacturing cost can be reduced; 2, at least two non-separating polymers in the compound barrier layer form pairing individual layer can be bonding mutually, mutual double team, cooperatively interact, reach with separating polymer and form better bonding of pairing individual layer, guarantee the complete of barrier individual layer, improve the mechanical strength that intercepts composite bed, promote to intercept the smooth of composite bed; 3, by the selection of the separating polymer composition during separating polymer is formed, can conveniently process and improve barrier property; 4, select to introduce laminal filter, cost-cutting when improving barrier property; 5, by selecting to introduce obstruct composite bed and other barrier individual layer or the composite bed of other this layer multiplication co-extrusions, can further enrich structure, performance, price and the purposes of compound barrier layer assembly again.Barrier packaging 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.These multi-layer co-extruded feasible different poly-mers are formed with the mutual double team of sandwich form, have improved the overall mechanical strength of multilayer material.Multi-layer co-extruded by this, originally more crisp material is barrier material particularly, can be well and non-brittle material coextrusion, and the fragility of layer material can weaken greatly when the number of plies increases thickness and reduces.Multilayer material demonstrates excellent lear energy, anti-pin hole.The increase of the number of plies and bed thickness reduce also to produce more crooked little molecular migration passage, improved barrier.Simultaneously because the increase of the number of plies and reducing of bed thickness, barrier material is placed in the restricted clearance, can show the special crystal property that helps to improve barrier, microscopic pattern etc.Layer multiplication be multi-layer co-extruded to be made and reaches better barrier with still less barrier material, therefore has excellent more performance and price advantage.In packing of the present invention, the structure of material can be by assembly selection and each assembly particularly the selection of layer multiplication composite bed unit construction and design are selected and are designed, therefore have very various structure, performance and price, can satisfy packing requirements widely, compare with therefore at present other no aluminium foil laminated packaging material and have remarkable advantage.
Description of drawings
The present invention will be further elaborated below in conjunction with drawings and Examples.
Fig. 1 is the integral structure scheme drawing of no In Aluminium Foil Packing of the present invention with isolation laminated packaging material.
Fig. 2 is the integrally-built four kind preferred version scheme drawings of no In Aluminium Foil Packing of the present invention with isolation laminated packaging material.
Fig. 3 for no In Aluminium Foil Packing of the present invention with the layer multiplication in the isolation laminated packaging material extrude preparation comprise three poly-mers compositions and repetitive is a kind of preferred version scheme drawing of three layers obstruct lamination layer structure.
Fig. 4 for no In Aluminium Foil Packing of the present invention with the layer multiplication in the isolation laminated packaging material extrude preparation comprise three poly-mers compositions and repetitive is a kind of preferred version scheme drawing of four layers obstruct lamination layer structure.
Fig. 5 for no In Aluminium Foil Packing of the present invention with the layer multiplication in the isolation laminated packaging material extrude preparation comprise three poly-mers compositions and repetitive is two kinds of preferred version scheme drawings of five layers obstruct lamination layer structure.
The specific embodiment
Fig. 1 has described the integral structure of no aluminium foil isolation laminated packaging material of the present invention.At least comprise a substrate layer assembly 40 and the compound barrier layer assembly 60 of poly-mer in the material.In embodiments of the invention, except substrate layer assembly 40 and the compound barrier layer assembly 60 of poly-mer, other component layer is non-essential.The material character that depends on substrate layer optionally increases a polymeric outer layer assembly 20 at the substrate layer outside face.In addition can be as required, selecting increases a polymer inner layer assembly 80, is used for direct contact content and sealing.Inside and outside the referring to here near content with away from content.In order to improve the laminated intensity between each component layer, can optionally introduce the polymer bonding layer assembly, as 30,50 and 70 in 1.According to the present invention, each assembly can comprise one or more (compound) layer, and the laminated of each layer can directly or by tack coat (assembly) be undertaken in each assembly.Reason is that certain assembly with many (compound) layer may be brought into play the performance more excellent more than certain assembly of single (compound) layer, and may need to promote by adhesive agent laminated between each layer in assembly that contains multilayer.Can also be laminated between those assemblies other the interlayer assembly that comprises one or more layer.The present invention preferably only comprises the assembly of one (compound) layer, does not perhaps contain the assembly of many (compound) layer of tack coat.The composite bed here (composite layer) represents that these layers itself are to be made of individual layer or individual layer more than one, and one of the conduct that one of assembly (component unit) expression comprises one deck or multilayer has the element layer of specific function (for example supporting).
According to the present invention, outer layer assembly, interior layer assembly, interlayer assembly and tack coat assembly are optional components, therefore except the described laminated material integral structure of Fig. 1, also have other multiple preferred versions.The tack coat assembly can be excluded at first, because it is suitable laminated to make that generally speaking each assembly can have according to the selection of material.But get rid of environmental-protecting performance and reuse that the tack coat assembly can also be simplified technology, save cost and improve material.Fig. 2 has described several preferred versions that do not contain the material monolithic structure of tack coat assembly of the present invention, but the invention is not restricted to this.Among Fig. 2 a, only comprise a substrate layer assembly 240 and a compound barrier layer assembly 260 in this material.Among Fig. 2 b, only comprise layer assembly 380 in a substrate layer assembly 340, the compound barrier layer assembly 360 and in this material.Among Fig. 2 c, only comprise a layer assembly 480 and an outer layer assembly 420 in the compound barrier layer assembly of a substrate layer assembly 440,460, in this material.Among Fig. 2 d, only comprise a substrate layer assembly 540, a compound barrier layer assembly 560 and an outer layer assembly 520 in this material.
According to the present invention, poly-mer is formed and is comprised one or more component of polymer and optional other non-polymer compositions, includes but not limited to polymeric additive, auxiliary agent, filler etc.The poly-mer composition that includes the separating polymer composition is called separating polymer and forms, and pairing individual layer (perhaps individual layer) then is called barrier individual layer (perhaps individual layer); Otherwise, then be called non-separating polymer and form and non-barrier individual layer (perhaps individual layer).In the present invention, can also define the poly-mer that except comprising a kind of component of polymer, does not contain other compositions and consist of single polymers, and the poly-mer that also comprises other one or more poly-mers or non-polymer composition except comprising a kind of component of polymer consists of polymer complex.So compound notions such as the known blend of polymer arts, filling that comprised here.Here defining one or more component of polymer that comprise in those single polymers and the polymer complex again is polymeric material, and promptly those polymeric materials are single polymers composition or multiple polymers mixture of ingredients.Only comprise linear low density polyethylene (LDPE) during for example a poly-mer is formed and do not comprise other any compositions, then this composition is called single polymers; The LDPE that nanoclay is filled can be described as filled polymer composite; Being added with ageing-resistant LDPE also is polymer complex; The blend of LDPE and HDPE also is a polymer complex; The blend of nylon 6 and maleic anhydride modified LDPE can be called the separating polymer compound.Constituent during two poly-mers are formed promptly is considered as poly-mer inequality and forms not simultaneously, and for example the LDPE of LDPE and nanoclay filling is that poly-mer inequality is formed, but the polymeric material in the middle of their is identical.
According to the present invention, substrate layer can be a paper substrates, can be the polymer-matrix base material also, is used to support packing of the present invention.Paper substrates can be selected from lamination paper, clay coated paper, fluting board, synthetic paper, craft paper, sulfide paper, multilayer gluing cardboard of bleached paper, non-bleached paper, non-bleaching and bleached paper etc.The present invention preferably has the bleached paper of proper strength and thickness and craft paper as paper substrates.The polymer-matrix base material is meant based on the base material of poly-mer (base) body, comprises single polymers and polymer complex etc.In the present invention, fitness for purpose polymer-matrix base material be thickness at sheet material more than 100 microns or sheet material, preferred thickness is between 100 microns to 1000 microns.The polymeric matrix that can be used to prepare the polymer-matrix base material comprises at least a polymers for general use composition, those component of polymer can be the natural or synthetic thermoplastic base resin or the thermosetting resins of any appropriate, can be linear, the cladodification shape, starlike or cross-linked polymer, include but not limited to the polyolefin Polymer, acrylic resin, the acrylic resin, polyester, polyamide, unsaturated polyester (UP), biological polyester, polyethers, polyurethane, the polystyrene Polymer, the vinyl chloride Polymer, polysulfide, epoxy resin, phenol resin, and their copolymer, condensation product, affixture, modifier and resultant of reaction etc.Wherein copolymerization, condensation, addition are that the 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 reaction and modification simultaneously is applicable to above-mentioned component of polymer itself and their monomer, presoma and prepolymer etc.The example of preferred suitable polymers for general use composition includes but not limited to by polyethylene (PE), polypropylene (PP), polyvinylchloride (PVC), polystyrene (PS), polycarbonate (PC), biological polyester, ABS, polyformaldehyde, polymethyl methacrylate (PMMA), and their copolymer, condensation product, affixture, resultant of reaction and modifier etc.Except comprising above-mentioned at least a component of polymer, can also comprise the blended complex of other one or more suitable polymers materials in the polymeric matrix in order to the preparation poly-mer.Except at least a polymeric material composition, also comprise the various suitable organic and inorganic filler that is used for the filled polymer matrix in the filled polymer composite, include but not limited to wood chip, cellulose fibre, glass fibre, carbon black, graphite, dolomite, chalk, talcum, mica, calcium carbonate, clay (if you would take off stone, kaolin etc.), fly ash, glass powder, diatom earth, silica, silicon dioxide, zeolite, metal hydroxides, metallic oxide is (as calcium oxide, titanium dioxide etc.), metal sulfate, metal carbonate, and their modifier and compound, can also be various suitable lines, net, cloth etc.The non-polymer composition that can also comprise other in the polymeric substrate, for example additive, auxiliary agent etc. include but not limited to the known compositions in polymeric material field such as antioxidant, ultraviolet absorbent, antistatic additive, lubricant, anticlogging agent, inorganic/organic expander, foaming agent, coating material and pigment.Since substrate layer not with the content direct contact, so the polymer-matrix base material can comprise the polymeric material of various suitable recovery, the utilization again that has improved material greatly, cost is saved in environmental protection again.The substrate layer assembly can have more than a layer, and the present invention preferably only comprises a layer.
The radical function of polymeric outer layer assembly comprises the protection substrate layer, improves printing, improves leak tightness and improves barrier, particularly liquid and aqueous vapor barrier etc.In the present invention, the polymeric material in the outer layer assembly preferably comprises at least a polyolefin polymers composition, as polyethylene, polypropylene, vinyl copolymer etc.These component of polymer can include but not limited to high density polyethylene (HDPE) (HDPE), medium density polyethylene (MLPE), low density polyethylene (LDPE) (LDPE), linear low density polyethylene (LLDPE), low density polyethylene (LDPE) (VLDPE) very, ultra-low density polyethylene (ULDPE), 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), ethylene-acrylic acid copolymer (EAA), and their resultant of reaction and modifier etc.The definition of resultant of reaction and modifier is consistent with corresponding definition in the substrate layer assembly.Polymeric material in the outer layer assembly also can be by the organic or Inorganic Fillers Filled of one or more suitable graininess, and filler available in those fillers and the substrate layer is consistent.The poly-mer of the outer layer assembly of the present invention is formed preferred low density polyethylene (LDPE) (LDPE), linear low density polyethylene (LLDPE), ethylene-acrylic acid copolymer (EAA) and metallocene PE (mPE) and metallocene polypropylene (mPP), and single polymers in their modifier and compound.
In the present invention, poly-mer intercepts barrier individual layer or the composite bed that the composite bed assembly comprises the composite bed of one or more layer multiplication coextrusion and optionally one or more additive method preparation.Contain a plurality of repetitives in the obstruct composite bed of this at least one layer multiplication coextrusion, each repetitive comprises three individual layer at least, each individual layer is formed corresponding to a poly-mer, it is mutually different wherein having at least three individual layer corresponding polymers to form, promptly intercept and contain three different poly-mers in the composite bed at least and form, but the quantity that poly-mer is formed is not more than individual layer quantity.In other words, comprising at least three different poly-mers in the repetitive of the obstruct composite bed of described layer multiplication coextrusion forms, repetitive comprises three individual layer at least, each individual layer is corresponding to one in described at least three different poly-mers compositions, but the quantity that poly-mer is formed is not more than individual layer quantity.Among the present invention, only forming by one during these at least three different poly-mers are formed is that the separating polymer that includes at least a separating polymer composition is formed, and this separating polymer composition has higher gas (oxygen) obstructing capacity.Poly-mer in the barrier individual layer is formed and is comprised at least a barrier properties for gases component of polymer.At least comprise two individual layers in the obstruct composite bed of additive method preparation, wherein at least one barrier individual layer; This composite bed can have a structure that is similar to the obstruct composite bed that layer multiplication extrude.
In the present invention, each individual layer in the repetitive of the composite bed of layer multiplication coextrusion is corresponding to one at least three different poly-mers compositions.In theory, under the not too big situation of individual layer quantity, the pairing poly-mer of those individual layer can be different between forming, and promptly what individual layer repetitive comprises and just comprise what different poly-mers compositions.But generally speaking, the quantity that poly-mer is formed is more limited, and perhaps for considerations such as costs, preferably the poly-mer of certain some is formed.In the middle of the present invention, the quantity that the poly-mer that comprises in the preferred repeat units is formed is at least three but no more than six.And, will form corresponding to identical poly-mer by at least two individual layer of some diverse location in the repetitive significantly when individual layer quantity during greater than the poly-mer composing quantity.Different in the present invention individual layer can refer to that the poly-mer composition in those individual layer is different, can refer to that those individual layer poly-mers are formed identical but thickness different or in repetitive the position difference, but as indicate especially then that the Different Individual layer refers generally to have the individual layer that different poly-mers are formed.Below by the description to some preferred versions, the structure that can make layer multiplication coextrusion of the present invention intercept composite bed is more clear.
Fig. 3 has described and has of the present inventionly a kind ofly only comprised that three poly-mers are formed and repetitive only is the preferred structure of compound barrier layer of three layers layer multiplication coextrusion.Here the layer that defines the picture top is the layer near the substrate layer assembly, and the layer of picture below is the layer near content.Wherein repeat unit structure is with 111/112/113 expression, 111,112,113 individual layer of representing three diverse locations respectively wherein, i.e. first, second and the 3rd individual layer; The subscript of number in the figure is in order to distinguish the position of repetitive in composite bed, for example 111 ' and 111n be respectively near first individual layer of the repetitive of substrate layer assembly and near first individual layer of the repetitive of content.According to the present invention, these three different poly-mers consist of two different non-barriers composition and barriers to be formed, and represents to form A, B and C respectively here.Three of the diverse location of repetitive individual layer 111,112,113 poly-mer composition A, B, Cs different with three can have six kinds of corresponding forms, i.e. A/B/C, A/C/B, B/A/C, B/C/A, six kinds of arrangements of C/A/B, C/B/A among Fig. 3.Because three compositions are inequality, and lamination layer structure has six kinds of different structures according to different and different near the individual layer of content and substrate layer assembly so intercept composite bed, the spread pattern that each structure is formed corresponding to above-mentioned a kind of poly-mer.Sometimes can directly form expression individual layer (perhaps individual layer) for convenience's sake in the present invention, for example also directly be referred to as individual layer A, because the 111 expression location informations of the number designation here corresponding to the individual layer 111 of forming A with corresponding polymers.
Be four layers when repetitive but when only comprising three poly-mers and forming,, can form A corresponding to non-separating polymer by two in four individual layer according to the present invention, one corresponding to non-barrier composition B and one corresponding to barrier composition C; Also can form A corresponding to non-barrier, form B and one corresponding to non-barrier for two and form C corresponding to barrier by one; Can also form A corresponding to non-barrier by one, form B and two corresponding to non-barrier for one and form C corresponding to barrier; Totally three kinds of combinations.If adjacent two layers is a same composition, then can be considered in the ordinary course of things and be equal to three layers of repeat unit structure.Therefore every kind of above-mentioned combination in fact all has 18 kinds of arrangements, makes four layers of repetitive that comprise three poly-mers compositions that 54 kinds of structures can be arranged.Fig. 4 has described a kind of repetitive of the present invention to be four layers but only to comprise the preferred structure of the compound barrier layer of the layer multiplication coextrusion that three kinds of poly-mers form, its repeat unit structure can be B/A/C/A for example, the individual layer 121,122,123 and 124 that is diverse location corresponds respectively to poly-mer composition B, A, C and A, the invention is not restricted to this certainly.Four layers repetitive can also be made up of four different poly-mers, then can be made up of with a barrier three different non-barriers according to the present invention and form, and repetitive can have 24 kinds of structures.The repetitive that comprises four different poly-mers compositions also can have more than four individual layer,, structure can be more various.
Be five layers when repetitive but when only comprising three poly-mers and forming,, can form A corresponding to non-barrier by two in five individual layer, form B and one corresponding to barrier composition C corresponding to non-barrier for two according to the present invention; Can form A corresponding to non-barrier by two, form B and two corresponding to non-barrier for one and form C corresponding to barrier; Can form A, two corresponding to non-barrier by one forms B and two corresponding to non-barrier and forms C corresponding to barrier; Can form A corresponding to non-barrier by one, form B and three corresponding to non-barrier for one and form C corresponding to barrier; Can form A corresponding to non-barrier by one, three non-barriers are formed B and one and are formed C corresponding to barrier; Can form A corresponding to non-barrier by three, form B and one corresponding to non-barrier for one and form C corresponding to barrier; Totally six kinds of combinations.Every kind of combination all has 120 kinds of spread patterns in theory, if but adjacent two layers or three layers are same composition, then can be considered in the ordinary course of things to be equal to four layers or three layers of repeat unit structure.Fig. 5 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 kinds of poly-mers form, but the invention is not restricted to this.Repeat unit structure can be A/B/C/B/A for example among Fig. 5 a, and promptly the individual layer 131,132,133,134 and 135 of diverse location corresponds respectively to poly-mer and forms A, B, C, B and A, but the invention is not restricted to this.Repeat unit structure can be A/B/A/C/A for example among Fig. 5 b, and promptly the individual layer 141,142,143,144 and 145 of diverse location corresponds respectively to poly-mer and forms A, B, A, C and A, but the invention is not restricted to this.Five layers repetitive can also be made up of four or five poly-mers, therefore more combination and structure can be arranged.The repetitive that comprises five poly-mers compositions also can have more than five individual layer, and structure can be more various.
According to the present invention, the repetitive in the compound barrier layer of layer multiplication coextrusion can be by forming more than six poly-mers and more than six layers, so repetitive can have very various structure.The veteran technical personnel in this field can reasonably be selected and design as required.Different poly-mers in the preferred repeat units of the present invention are formed no more than six.
As can be seen, when comprising different poly-mers compositions more than three in the repetitive, and when repetitive had three above individual layer, the structure of those barrier composite beds was very rich and varied, and great facility and freedom can be provided for the design of packing.
When in the barrier assembly except the compound barrier layer that comprises layer multiplication coextrusion when, select to comprise barrier individual layer or the composite bed that one or more additive method prepares, can enrich the design of packing again.
Obstruct can be choke, waterproof and anti-wet goods, refers to mainly that here choke particularly hinders oxygen.Therefore require to comprise component of polymer during separating polymer is formed with higher gas (oxygen) barrier.Form according to above-mentioned those separating polymers of definition that poly-mer is formed, promptly barrier individual layer (perhaps individual layer) corresponding polymers is formed, and can be single separating polymer and separating polymer compound.Include the separating polymer material that constitutes by one or more separating polymer compositions in those single separating polymers and the separating polymer compound.Among the present invention, those separating polymer materials can be the copolymers of polyvinyl alcohol (PVA), polyacrylinitrile (PAN), acrylonitrile copolymer, polyimide (PI), polymethylpentene (PMP), polyvinylidene chloride (PVDC), polyethylene terephthalate (PET), PEN (PEN), polyvinylchloride (PVC), polymerization oxidation ethene (PEO), Kynoar (PVDF), liquid crystal polyester, the ionomer based on ethene, ethene and beta-unsaturated esters, and in the compositions such as their modifier and resultant of reaction one or more.The separating polymer material can also be above-mentioned at least a separating polymer composition and ethylene-vinyl alcohol copolymer (EVOH), nylon 6, nylon 66, nylon 10, nylon 6-10, nylon 6-12, nylon 12, amorphous nylon, MXD6 nylon, and at least a compound in the compositions such as their modifier and resultant of reaction.The separating polymer material can also be ethylene-vinyl alcohol copolymer (EVOH) with polyamide compositions such as nylon 6, nylon 66, nylon 10, nylon 6-10, nylon 6-12, nylon 12, amorphous nylon, MXD6 nylon at least a compound, and wherein one or more such as the modifier of those compounds and resultant of reaction.The definition and the preamble of modifier and resultant of reaction are similar.
Non-barrier in the barrier composite bed or low separating polymer are formed, promptly non-(low) barrier individual layer (perhaps individual layer) corresponding polymers is formed, general do not have a good gas barrier sexual function, and effects such as enhancing, toughness reinforcing, dispersion, bonding, sealing, cost-cutting are generally played in the use of those materials.Component of polymer during those poly-mers are formed can be the natural or synthetic thermoplastic base resin or the thermosetting resin of any appropriate, can be linearity, cladodification shape, starlike or cross-linked polymer, include but not limited to polyolefin Polymer, acrylic resin, acrylic resin, polyester, unsaturated polyester (UP), biological polyester, polyethers, polyurethane, polysiloxane, polystyrene Polymer, vinyl chloride Polymer, polysulfide, epoxy resin, 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) (LDPE), linear low density polyethylene (LLDPE), low density polyethylene (LDPE) (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, the epoxy-functional polyethylene, oxidic polyethylene, haloflex, the ethylene methacrylic acid copolymer of metal neutralization, anhydride modified polypropylene, the 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), polyethers polyurethane, polyesters polyurethane, polyolefins polyurethane, polyacrylic polyurethane, polycarbonate-based polyurethane, polydimethyl diloxanes (PDMS), polyoxyethylene (PEO), polypropyleneoxide (PPO), PEP-101, PolyTHF, polycarbonate (PC), poly-ε-acid esters in oneself, poly(lactic acid) (PLA), polyhydroxyalkanoate (PHA), and their copolymer, condensation product, affixture, reaction and modified product etc.The preferred low density polyethylene (LDPE) of the present invention (LDPE), linear low density polyethylene (LLDPE), ethylene-acrylic acid copolymer (EAA) and metallocene PE (mPE) and metallocene polypropylene performance and the good component of polymer of price such as (mPP).Suitable non-(low) separating polymer composition also can be used as the optional component of polymer in the separating polymer composition, mixes use with the separating polymer composition, generally is used to play enhancing, toughness reinforcing, effects such as promotion is bonding, cost-cutting.
Optionally be used in non-polymer composition such as granulated filler that barrier composite bed and individual layer poly-mer form and additive and auxiliary agent and other assemblies similar.In not having during layer assembly, those non-polymer composition fitness for purposes are nontoxic, harmless, no ill-effect etc.The granulated filler that is used to fill separating polymer among the present invention preferably has the flaky inorganic filler of certain diameter thickness than (aspect ratio), as graphite, clay, talcum, mica, calcium carbonate, dolomite, chalk etc.Fill separating polymer and can reduce material cost greatly, because the price of general separating polymer is a decision 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.
Interior layer assembly direct contact content, the material of layer assembly depends on the character of content in therefore constituting.Can reasonably select as required at the veteran technical personnel of packaging field.The material of layer assembly has chemical inertness to content in requiring generally speaking, and liquid component in the content and aqueous vapor are had high barrier, and each composition in the content is had low absorption.And the material of layer assembly has sealability in requiring generally speaking, particularly heat sealability.So the poly-mer composition of layer assembly is preferably formed similar with the outer assembly of formation in the formation of the present invention.At least a suitable polymers composition that wherein comprises can include but not limited to high density polyethylene (HDPE) (HDPE), low density polyethylene (LDPE) (LDPE), linear low density polyethylene (LLDPE), low density polyethylene (LDPE) (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), ethylene-acrylic acid copolymer (EAA), and their modifier and resultant of reaction etc.The definition and the preamble of modifier and resultant of reaction are similar.Among the present invention, preferred low density polyethylene (LDPE) (LDPE), linear low density polyethylene (LLDPE), ethylene-acrylic acid copolymer (EAA) and metallocene PE (mPE), and their modifier and resultant of reaction.It is similar to be used in non-polymer compositions such as filler, additive and auxiliary agent that internal layer component assembly thing forms and other assemblies poly-mer composition, but fitness for purpose is nontoxic, harmless, no ill-effect etc.Interior layer assembly is optional.General when in the barrier layer assembly the layer of close content be non-involution or when forming for the relatively thinner involution poly-mer of thickness, need selection introducing involution internal layer polymer assembly.During layer assembly, this assembly can comprise one deck or multilayer, is preferably one deck in select introducing.
The binder polymer composition that the adhesive agent of each layer is formed in each component layer or the component layer that can be used to bond includes but not limited to anhydride modified polyethylene, the polyolefin of acid modification, the 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, the 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), fluorine based thermoplastic resin, polyvinyl chloride thermoplastic base resin (CPE) and hydrogenated styrene based thermoplastic resin, and their copolymer, condensation product, affixture, modifier, reaction and modified product etc.The definition and the preamble of copolymer, condensation product, affixture, modifier, reaction and modified product are similar.The tack coat assembly is optional.Consider the preparation technology, price, environmental protection, toxicity of packing, factor such as utilization again, preferred anhydrides improved polyalkene of the present invention and ethylene-vinyl acetate copolymer (EVA) when selecting to use adhesive agent.These adhesive material also can be used as the interpolation blend in other poly-mers compositions, to reach the cohesive force that increases under the situation that does not increase extra tack coat between adjacent layer.Those adhesive agent compositions of part can use with separating polymer or non-separating polymer blend or as the bulking agent of blend.
The interlayer assembly refers generally to be laminated in some polymer assemblies between the assemblies such as skin, substrate layer, compound barrier layer and internal layer.Effects such as this class component can play generally that resistance is wet, resistance light, hyperchromic, support, but be non-essential.The component of polymer that can be used for the interlayer assembly includes but not limited to polyolefin, polyester, biological polyester, and their modifier and resultant of reaction.The definition and the preamble of modifier and resultant of reaction are similar.In like manner, if when having in the interlayer assembly more than a layer, can be directly laminated or laminated between each layer by the tack coat assembly.In like manner, the poly-mer in tack coat assembly and the interlayer assembly also can comprise compositions such as appropriate filler, additive and auxiliary agent in forming.
A layer multiplication coetrusion that is adopted among the present invention is a kind of feed steam to be cut apart-the stacked again method of operating of converging, each such operation all is accompanied by width expansion and the high shrinkage to materials flow, and materials flow number of plies amount is multiplied, and materials flow individual layer thickness reduces at double.Layer multiplication operation is undertaken by layer multiplicator.Layer multiplicator extrusion device with layer multiplication ability can be referring to Chinese utility application 200820229095.4 and 200820229641.4, and Chinese invention patent application 200810072529.9.When layer multiplicator used with the head and the tail series connection, it was 2 that the materials flow number of plies is added to original multiple
M2* 3
M3* 4
M4* ... * n
Mn, wherein exponent m 2, m3, and m4 ..., mn be respectively dual, triple, the quadruple extruding on the direction to be adopted in materials flow ..., the quantity of n double-layer multiplicator.Preferably among the present invention adopt dual and/or the quadruple-layer multiplicator is composed in series a layer multiplication portion from beginning to end, as module and other extrude operate needed module for example feeder, measuring pump, feed head, extrude first-class being used in combination.Preferred single screw rod of feeder or double screw extrusion machine among the present invention, and the feed head can only have and simply converges stacked function or have layer ability that increase.It is consistent with feed steam quantity simply to converge the number of plies amount of converging major ingredient stream that the feed head of stacked function provides; Has the number of plies amount of converging major ingredient stream that the feed head that increases layer ability provides greater than feed steam quantity; Increase layer feed head and can be equivalent to the combination that connects diverter in common feed head upstream to a certain extent.When extruding, each feed composition is by feeder (with selectable measuring pump), enter the feed head and obtain converging stacked (and may tentatively be increased layer), feed steam after stacked is used as the initial materials flow of layer multiplication operation and sends into a layer multiplication portion, cut apart-the stacked again layer multiplication operation that converges, the materials flow that reaches the specific number of plies after the layer multiplication is extruded by suitable extruder head and is collected or directly and other assembly coextrusion laminatings.Materials flow after process feed head is stacked generally is considered as a repetitive, can comprise several repetitives sometimes.For example forming A, B and separating polymer when two different non-separating polymers forms C and is extruded by a single screw extrusion machine plasticizing respectively and be transported to a simple feed head with three runners by measuring pump, and then be laminated into three-decker materials flow by being converged with A/C/B, this materials flow continues constantly to be cut apart-stacked again converging by layer multiplication portion, and last materials flow is (A/C/B)
k, wherein k is the number of times that initial materials flow is doubled, and is 2
M2* 3
M3* 4
M4* ... * n
MnDoubly, wherein exponent m 2, m3, and m4 ..., mn be respectively dual, triple, the quadruple extruding on the direction to be adopted in materials flow ..., the quantity of n double-layer multiplicator; And converged when being laminated into nine layers of structure materials flow with A/C/B/A/C/B/A/C/B when above-mentioned three feed compositions increase layer feed head by one, if the individual layer with same polymer composition in this structure is suitable at the thickness of diverse location, then this materials flow can be considered as one nine layers repetitive or comprise three three layers repetitive.In the time need doubling the compound barrier layer of extruding more than one layer in the packing, preferred directly that a plurality of compound barrier layers are directly laminated by the direct coextrusion of extruder head of how divergent road extruder head or similar feed head.
Result of study shows, adopts the multi-layer co-extruded method of layer multiplication can prepare the laminated material that contains many layers effectively.Barrier packaging material 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.These multi-layer co-extruded feasible different poly-mers are formed with the mutual double team of sandwich form, have 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 the fragility of layer material can reduce greatly when the number of plies increases thickness and reduces.Multilayer material demonstrates excellent lear energy, anti-pin hole.More when the number of plies, bed thickness hour because the interface layer application force that increases greatly, makes in general multi-layer co-extruded each bad layer of cohesiveness that the binding power of relative raising also can be arranged, thus the use that can omit adhesive agent, and simplification technology is also saved cost.The increase of the number of plies and bed thickness reduce also to produce more crooked little molecular migration passage, improved barrier.Simultaneously because the increase of the number of plies and reducing of bed thickness, barrier material is placed in the restricted clearance, can show the crystal property that helps to improve barrier, microscopic pattern etc.This is multi-layer co-extruded, makes to reach better barrier with still less barrier material, therefore has excellent more performance and price advantage.Form by three poly-mers in the composite bed that comprises that at least three poly-mers are formed and wherein only forms by a barrier of selecting layer multiplication coextrusion in the present invention and composite bed in the individual layer quantity of repetitive, just can prepare the rich and varied compound barrier layer that only comprises two kinds of poly-mers compositions.By selecting to introduce composite bed and other barrier individual layer or the composite bed that at least three poly-mers are formed and wherein only are made up of a barrier that comprise of other layers multiplication coextrusion, can further enrich structure, performance and the purposes of compound barrier layer assembly again in addition.Generally speaking, comprise one in the barrier assembly and only comprise the double compound barrier layer of coextrusion of three poly-mers are formed and wherein only is made up of a barrier layer, the packing that just can have other no aluminium foils are the excellent comprehensive performance more.
Except compound barrier layer assembly, other contain the composite bed that also can contain in the assembly of a plurality of (compound) layer with layer multiplication coextrusion preparation.In the present invention, whole laminated packaging material and any one preparation that contains the assembly of a plurality of (compound) layer can be finished or prepares earlier each individual layer or composite bed respectively to carry out laminated or direct co-extrusion part many (compound) layer more laminated step by step with other layer again by direct coextrusion laminating.In the extrusion, the feed composition that poly-mer is formed may not be formed identical with individual layer (perhaps individual layer) corresponding polymers in the final material, can comprise in the feed composition 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.The those of skill in the art of packing preparation field can reasonably design and select as required easily.
During layer assembly, shown in Fig. 2 a and 2b, the substrate layer assembly in those materials is not generally the polymer-matrix base material, and the polymer-matrix base material that preferably can print outside the substrate layer module outer surface does not contain, and printing ink directly is printed on the base material outside face.When substrate layer was paper substrates, fitness for purpose base material outside face applied polymeric outer layer (as Fig. 2 c and 2d), is used to protect paper substrates not to be subjected to moisture penetration and destruction, increases the resistance to abrasion of base material simultaneously.When base material is paper material,, can in treatment process, activate the outside face of outer field inside face and/or base material with corona, flame or ozone pretreatment in order to increase cohesiveness.Containing in the material of paper substrates assembly printed layers at those can be at the paper substrates outside face, and the also outside face of layer assembly or inside face outside are preferably at the outside face of paper substrates.
No aluminium foil barrier packaging material of the present invention can be processed to the containers such as bag, bag, box or case of different shape, for example the bag of the box of the bag of pillow shape, hexahedron and other multiaspect builds, rooftop box, band dumping mouth or box or the like.The those of skill in the art in this field can design processing as required.Packing are processed in the process of bag, bag or box etc., need carry out involution to material, its method comprises heat-sealing, bright eruption sealing, hot gas sealing, ultrasonic sealing, high frequency sealing etc.This packing container can be used 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, printing ink etc.Can also be used to pack solid product, for example food and other products such as cheese, bean curd, chocolate.In packing of the present invention, the structure of material can be by assembly selection and each assembly particularly the selection of the compound barrier layer unit construction of layer multiplication coextrusion and design are selected and are designed, therefore have very various structure, performance and price, can satisfy packing requirements widely.
Embodiment 1
In the present embodiment, the integral structure of packing is skin/substrate layer/barrier layer, and its ectomesoderm is a low density polyethylene (LDPE), and substrate layer is a millboard, and barrier layer is for only containing three kinds of poly-mers and form and repetitive being the composite bed that five layers layer multiplication extruded.The non-separating polymer composition A that wherein intercepts in the composite bed is a low density polyethylene (LDPE), and it is that maleic anhydride modified low density polyethylene (LDPE) separating polymer composition C is the polyvinyl alcohol of the melt-processable of modification that non-separating polymer is formed B.
(Substance is about 400g/m at first under about 325 ℃ the low density polyethylene (LDPE) curtain coating to be coated on millboard
2) the outside face that has printed layers on, coating thickness is about 20 microns.
Be laminated with the obstruct composite bed that coextrusion is extruded by layer multiplication method on the inside face of millboard of low density polyethylene (LDPE) in coating.The repeat unit structure of composite bed is A/B/C/B/A, and wherein each elementary layer thickness is suitable.By 8 series connected double layers multiplicators of head and the tail, total number of plies of compound barrier layer is 1280 layers, and individual layer thickness is about 20 nanometers.
Can form hexahedron brick shape box or rooftop box by these packing.
Embodiment 2
In the present embodiment, the integral structure of packing is skin/substrate layer/barrier layer, its ectomesoderm is low density polyethylene (LDPE) (LDPE), and substrate layer is a thin paper, and the barrier layer assembly is to comprise that three kinds of poly-mers are formed and repetitive is the composite bed that four layers layer multiplication extruded.The non-separating polymer composition A that wherein intercepts in the composite bed is ethylene acrylic acid co polymer (EAA), it is the blend of 95wt% low density polyethylene (LDPE) and the maleic anhydride modified low density polyethylene (LDPE) of 5wt% that non-separating polymer is formed B, and it is the nylon 6 that extrusion grade ethylene-vinyl alcohol copolymer (EVOH) and commodity rank nanoclay are filled that separating polymer is formed C.
(Substance is about 150g/m at first under about 325 ℃ the low density polyethylene (LDPE) curtain coating to be coated on millboard
2) the outside face that has printed layers on, coating thickness is about 20 microns.
Be laminated with the obstruct composite bed that coextrusion is extruded by layer multiplication method on the inside face of thin paper of low density polyethylene (LDPE) in coating.The gross thickness that intercepts composite bed is about 50 microns.The repeat unit structure of composite bed is A/B/C/B, and wherein each elementary layer thickness is suitable, and non-barrier layer A is near substrate layer.By 7 series connected double layers multiplicators of head and the tail, total number of plies of compound barrier layer is 512 layers, and barrier individual layer thickness is about 100 nanometers.
Can form pillow-like packaging bag etc. by these packing.
Embodiment 3
In the present embodiment, the integral structure of packing is skin/substrate layer/barrier layer/internal layer, its ectomesoderm is linear low density polyethylene (LLDPE), substrate layer is a millboard, the barrier layer assembly is to comprise that three kinds of poly-mers are formed and repetitive is the composite bed that three layers layer multiplication extruded, and internal layer is the LLDPE that nano-calcium carbonate is filled.The non-barrier composition A that wherein intercepts in the composite bed is ethylene-vinyl acetate copolymer (EVA), it is the blend of 95wt% low density polyethylene (LDPE) and the maleic anhydride modified low density polyethylene (LDPE) of 5wt% that non-barrier is formed B, and it is the blend of extrusion grade polyvinyl alcohol copolymer (PVA) and MXD6 nylon that separating polymer is formed C.
(Substance is about 320g/m at first under about 350 ℃ the linear low density polyethylene curtain coating to be coated on millboard
2) the outside face that has printed layers on, coating thickness is about 20 microns.
The gross thickness of the obstruct composite bed of layer multiplication coextrusion is about 25 microns, and wherein repeat unit structure is A/C/B, and three each and every one bulk layer thickness are suitable.By 8 series connected double layers multiplicators of head and the tail, total number of plies of compound barrier layer is 768 layers, and barrier individual layer thickness is about 30 nanometers.Intercept LLDPE that composite bed and internal layer (about 20 microns) contain the 20wt% nano-calcium carbonate by the extruder head coextrusion of how divergent road at the folded inside face that the millboard of LLDPE is arranged of outside face coating layer.
Can form hexahedron brick shape box or rooftop box etc. by these packing.
Embodiment 4
In the present embodiment, the integral structure of packing is substrate layer/barrier layer, and wherein substrate layer is calcium carbonate-filled polypropylene, and the barrier layer assembly is to contain that four kinds of poly-mers are formed and repetitive is the composite bed that four layers layer multiplication extruded.The non-separating polymer composition A that wherein intercepts in the composite bed is anhydride modified polypropylene, it is oxidic polyethylene that non-separating polymer is formed B, it is metallocene low density polyethylene (LDPE) (mLDPE) that non-separating polymer is formed C, and it is polyethylene terephthalate (PET) that separating polymer is formed D.
Substrate layer thickness is about 100 microns, contains about 40wt% winnofil.The gross thickness that intercepts composite bed is about 40 microns.Wherein repeat unit structure is A/D/B/C, and four each and every one bulk layer thickness are suitable.By 4 series connected quadruple-layer multiplicators of head and the tail, total number of plies of compound barrier layer is 1024 layers, and individual layer thickness is about 35 nanometers.Substrate layer becomes packing with the obstruct composite bed by the extruder head coextrusion one-shot forming of how divergent road.
Can form hexahedron brick shape box or rooftop box etc. by these packing.
Embodiment 5
In the present embodiment, the integral structure of packing is skin/substrate layer/barrier layer/internal layer, its ectomesoderm is low density polyethylene (LDPE) (LDPE), substrate layer is a millboard, barrier layer comprises one and comprises that three kinds of poly-mers are formed and repetitive only is composite bed and barrier individual layer that three layers layer multiplication extruded, and internal layer is a low density polyethylene (LDPE).
(Substance is about 400g/m at first under about 325 ℃ the low density polyethylene (LDPE) curtain coating to be coated on millboard
2) the outside face that has printed layers on, coating thickness is about 20 microns.
Be laminated with the millboard inside face coextrusion barrier layer assembly and the internal layer of low density polyethylene (LDPE) in coating.It is ethylene-vinyl acetate copolymer (EVA) that non-barrier in the obstruct composite bed of layer multiplication coextrusion is formed A, it is the maleic anhydride modified polyacrylic compound of 97wt% polypropylene and 3wt% that non-barrier is formed B, it is the extrusion grade Vingon that separating polymer is formed C, and its repeat unit structure is A/C/B.The single layer poly-mer of barrier consists of the isotactic polypropylene (iPP+Mt) of montmorillonite filling so.Internal layer polymer consists of metallocene low density polyethylene (LDPE) (mLDPE), and thickness is about 10 microns.The gross thickness of the obstruct composite bed of layer multiplication is about 30 microns, extrudes by 4 quadruple-layer multiplicators, and the number of plies reaches 768 layers.Interior layer thickness is about 20 microns.
Can form hexahedron brick shape box or rooftop box etc. by these packing.
Embodiment 6
In the present embodiment, the integral structure of packing is skin/substrate layer/interlayer/tack coat/barrier layer, its ectomesoderm is linear low density polyethylene (LLDPE), substrate layer is a millboard, interlayer is that cast polypropylene (cPP), tack coat are acrylate adhesives, and the barrier layer assembly is one and comprises the composite bed that three kinds of poly-mers are formed and repetitive has three layers layer multiplication to extrude.
In the present embodiment, each assembly adopts and divides one-step preparation method, and is laminated with substrate layer respectively again.At first prepare 192 layers obstruct composite bed by 3 quadruple-layer multiplicators, wherein non-separating polymer is formed A polymethyl methacrylate (PMMA), non-separating polymer is formed B for filling the metallocene low density polyethylene (LDPE) for 10wt% nanometer winnofil, it is the compound of PEN (PEN) and nylon 6 (Nylon6) that separating polymer is formed C, and repeat unit structure is A/C/B.About 60 microns of the thickness of obstruct composite bed film.Under ozonization, linear low-density polyethylene film is laminated to the millboard outside face then, then applies polypropylene, apply acrylate adhesives and while laminate barrier composite bed film in polypropylene surface then in substrate layer inside face curtain coating.
Can form hexahedron brick shape box or rooftop box etc. by these packing.
Embodiment 7
In the present embodiment, the integral structure of packing is skin/substrate layer/barrier layer/tack coat/internal layer, its ectomesoderm is the metallocene linear-low density polyethylene (mLLDPE) that titanium dioxide is filled, substrate layer is for reclaiming polypropylene, the barrier layer assembly comprises the obstruct composite bed that two layer multiplications are extruded, one of them comprises, and three kinds of poly-mers are formed and repetitive is five layers, the composite bed of the close content of another one comprises three kinds of poly-mers compositions and repetitive is three layers, tack coat is vinyl-vinyl acetate copolymer (EVA), and internal layer is carbon black filled metallocene linear-low density polyethylene (mLLDPE).
In the present embodiment, each assembly adopts the classification coetrusion.At first a coextrusion is laminated with coextrusion skin, substrate layer and first obstruct composite bed of being extruded by layer multiplication method on the inside face of heavy kraft paper plate of LLDPE in coating.It is the epoxy-functional polypropylene that non-barrier in first composite bed is formed A, and it is EU that non-separating polymer is formed B, and it is polyacrylinitrile (PAN) that separating polymer is formed C, and repeat unit structure is A/C/B/C/A, and five each and every one bulk layer thickness are suitable.First intercepts composite bed (about 20 microns) by 3 quadruple-layer multiplicators, reaches 320 layers.Also add the foaming agent extrusion foaming in the recovery polypropylene of substrate layer, the thickness after the foaming is about 250 microns.At the above-mentioned laminated material that contains first composite bed fully before the cooling curing, other assembly of coextrusion on its inside face, and utilize the rolling press pressing.Non-barrier composition D is the epoxy-functional polypropylene in second composite bed, and it is maleic anhydride modified low density polyethylene (LDPE) that non-barrier is formed E, and it is nylon 6 that barrier polymer is formed F, and repeat unit structure is D/F/E, and three each and every one bulk layer thickness are suitable.Second intercepts composite bed (about 30 microns) by 3 quadruple-layer multiplicators and 1 double layers multiplicator, reaches 384 layers.The titanium dioxide loading is 6wt% in the outer linear low density polyethylene, is used to print and hide the color of expanded polypropylene.The loading of carbon black is 12wt% in the internal layer linear low density polyethylene, is used for shading.
Can form hexahedron brick shape box or rooftop box etc. by these packing.
The above, only for preferred embodiment of the present invention, so can not limit scope of the invention process with this, i.e. the equivalence of doing according to the present patent application claim and description changes and modification, all should still belong in the scope that patent of the present invention contains.
Claims (10)
1. laminated material that is used for the metal-foil-free of barrier packaging, which comprises at least a substrate layer assembly and a compound barrier layer assembly, this substrate layer assembly and compound barrier layer component layer lump together, this substrate layer assembly can play a supportive role, this compound barrier layer assembly comprises at least one by cutting apart-the stacked again layer multiplication coextrusion method preparation that converges, the compound barrier layer that contains a plurality of repetitives, it is characterized in that: this each repetitive comprises three kinds of poly-mers at least and forms, this every kind poly-mer is formed can both form body layer one by one or more than one individual layer, only being made up of a kind of poly-mer during those kinds poly-mer is formed is that separating polymer is formed, and this separating polymer is formed can intercept gas.
2. a kind of isolation laminated packaging material according to claim 1 is characterized in that: this substrate layer assembly is selected from least a in paper substrates and the polymer-matrix base material.
3. a kind of isolation laminated packaging material according to claim 1, it is characterized in that: the separating polymer material during this separating polymer is formed is at least a polyvinyl alcohol (PVA) that is selected from, polyacrylinitrile (PAN), polyimide (PI), polymethylpentene (PMP), polyvinylidene chloride (PVDC), polyethylene terephthalate (PET), PEN (PEN), polyvinylchloride (PVC), polymerization oxidation ethene (PEO), Kynoar (PVDF), liquid crystal polyester, ionomer based on ethene, acrylonitrile copolymer, the copolymer of ethene and beta-unsaturated esters, ethylene-vinyl alcohol copolymer (EVOH) and at least a nylon 6 that is selected from, nylon 66, nylon 10, nylon 6-10, nylon 6-12, nylon 12, amorphous nylon, the polyamide mixture of ingredients of MXD6 nylon, and their modifier and resultant of reaction.
4. a kind of isolation laminated packaging material according to claim 1, it is characterized in that: the separating polymer material during this separating polymer is formed is at least a polyvinyl alcohol (PVA) that is selected from, polyacrylinitrile (PAN), polyimide (PI), polymethylpentene (PMP), polyvinylidene chloride (PVDC), polyethylene terephthalate (PET), PEN (PEN), polyvinylchloride (PVC), polymerization oxidation ethene (PEO), Kynoar (PVDF), liquid crystal polyester, ionomer based on ethene, acrylonitrile copolymer, the copolymer of ethene and beta-unsaturated esters, and the component of polymer of their modifier and resultant of reaction and at least a ethylene-vinyl alcohol copolymer (EVOH) that is selected from, nylon 6, nylon 66, nylon 10, nylon 6-10, nylon 6-12, nylon 12, amorphous nylon, MXD6 nylon, and the compound that component of polymer constituted of their modifier and resultant of reaction.
5. a kind of isolation laminated packaging material according to claim 1 is characterized in that: this contains in the compound barrier layer assembly of the compound barrier layer of at least one layer multiplication coextrusion and also comprises at least one barrier individual layer.
6. a kind of isolation laminated packaging material according to claim 1 is characterized in that: this contain also comprise in the compound barrier layer assembly of compound barrier layer of at least one layer multiplication coextrusion at least one other non-by cutting apart-the compound barrier layer of the stacked again layer multiplication coextrusion preparation that converges.
7. a kind of isolation laminated packaging material according to claim 1 is characterized in that: also comprise: can be laminated in the outer layer assembly in the substrate layer assembly outside and can be laminated in the interior layer assembly of barrier layer assembly inboard at least one.
8. a kind of isolation laminated packaging material according to claim 1 is characterized in that: also comprise: the tack coat assembly that is used for each layer in bonding each assembly and the assembly.
9. a kind of isolation laminated packaging material according to claim 1 is characterized in that: also comprise: can be laminated between each assembly and within the interlayer assembly.
10. a kind of isolation laminated packaging material according to claim 1 is characterized in that: also comprise: be used for the Charge that filled polymer is formed, this Charge slabbing.
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| CN115612377B (en) * | 2022-11-23 | 2023-11-21 | 昆明理工大学 | Application of composite coating in green-skin walnut preservation |
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