CN101992888B - Laminated material without metal foil for blocking package - Google Patents
Laminated material without metal foil for blocking package Download PDFInfo
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- CN101992888B CN101992888B CN200910168822.XA CN200910168822A CN101992888B CN 101992888 B CN101992888 B CN 101992888B CN 200910168822 A CN200910168822 A CN 200910168822A CN 101992888 B CN101992888 B CN 101992888B
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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 of the metal-foil-free for 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 barrier packaging material has become the focus that various countries competitively develop.
More common barrier packaging material is the rhythmo structure that a class makes by laminated layers of material, and comprise one deck lamination coating for example paper as structural materials ，Qi two sides, with heat sealable plastic layer, cover.In high-barrier Packing Condition, packing comprise one deck choke oxygen barrier material, be generally aluminium foil and be combined on lamination coating by the heat sealable plastics of one deck or adhesive layer, by the one deck or the heat sealable plastics of multilayer that directly contact with content (being the product of packaging), covered again simultaneously.This class mainly comprises that containing the high-barrier packaging material of aluminium foil (Al) 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 PE/ cardboard/Al/PE structure of domestic Quan Lin packaging company exploitation.Although at present domestic spring woods and Tian Longdeng wrapping enterprise also start 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 subject to humidity effect not only.And although many poly-mer barrier materials have high-gas resistance but to humidity sensitive, or general to the insensitive gas barrier property of humidity.Therefore,, in current aseptic packaging, the packing of high barrier are still preponderated with the laminate containing aluminium foil.Yet the fee of material of aluminium foil is high, when application, generally aluminium foil need to be worked into the degree that forms aluminium foil thin slice, processing charges is also high.For aluminium foil, only have when its thickness is greater than more than 25 microns, be only completely sir-tight.And generally to consider the cost of material, the aluminum foil thickness using in packing is substantially 10 microns of left and right, so barrier is had a greatly reduced quality.Aluminium foil has low-down ductility and stretchability in addition, therefore, when being exposed to hale while stretching with flexure stress, is easy to crack, particularly folding the or crooked position with laminated product in packing.Aluminium foil also lacks intensity necessary under high speed pressure processing conditions,, 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, in packing, the existence of aluminium foil also can be disturbed.Use the packing of aluminium foil can not carry out microwave treatment.Therefore, be necessary that exploitation, without the rhythmo structure of aluminium foil, provides the barrier property suitable with aluminium foil, overcome again the shortcoming containing In Aluminium Foil Packing.
In recent years, the company such as Tetrapack Lavalle and U.S.'s International Paper all development and Design comprise substrate layer without aluminium foil rhythmo structure packing.In these structures, as Chinese patent ZL96197841.4, ZL96198157.1 and Chinese patent application 99817009.1,200680031721.2 etc., be wrapped by or the stacking polymer film of the separating polymer of sandwich applies or is laminated on base material inside face, to replacing the laminated packaging material containing aluminium foil.These stacking polymer materials that are layered in 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 packing barrier composite polymer films.So, reach desirable barriering effect and cost advantage, properity and the technology of preparing of the stacking polymer material on base material inside face play conclusive effect.
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 larger performance and price advantage.Yet multilayer film co-extrusion technology, no matter be coextrusion blow or coextrusion casting, has great limitation at present.This is because the co-extrusion number of plies is higher, and 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 the coextrusion casting coextrusion die that compares is simple, 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 the isolation laminated material of a kind of packing without 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 of the metal-foil-free for 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 are combined, this substrate layer assembly can play a supportive role, this compound barrier layer assembly comprise at least one by cutting apart-again prepared by the stacked layer multiplication coextrusion method of converging, the compound barrier layer that contains a plurality of repetitives, this each repetitive at least comprises three kinds of poly-mers and forms, this every kind poly-mer forms can form body layer or more than one individual layer one by one, during those kind of poly-mer forms, only a kind of poly-mer, consisting of is that separating polymer forms, this separating polymer forms can intercept gas.
In a preferred embodiment of the present invention, this substrate layer assembly is selected from least one in paper substrates and Polymers base material.
In a preferred embodiment of the present invention, separating polymer material during this separating polymer forms is at least one is selected from polyvinyl alcohol (PVA), 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 one are selected from nylon 6, 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 forms is at least one is selected from polyvinyl alcohol (PVA), 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 one are selected from 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 one in the compound that forms of the component of polymer of their modifier and resultant of reaction.
In a preferred embodiment of the present invention, this contains at least one and is doubled in the compound barrier layer assembly of the compound barrier layer of coextrusion and also comprised at least one barrier individual layer by layer.
In a preferred embodiment of the present invention, in the compound barrier layer assembly of the compound barrier layer that this contains at least one layer of multiplication coextrusion, also comprise at least one other non-by cutting apart-compound barrier layer that again prepared by the stacked layer multiplication coextrusion converging.
In a preferred embodiment of the present invention, also comprise: can be laminated in the outer layer assembly in substrate layer assembly outside and can be laminated at least one in the interior layer assembly of barrier layer assembly inner side.
In a preferred embodiment of the present invention, also comprise: for the tack coat assembly of each layer in bonding each assembly and assembly.
In a preferred embodiment of the present invention, also comprise: can be laminated between each assembly and within interlayer assembly.
In a preferred embodiment of the present invention, the Charge forming for filled polymer, this Charge slabbing.
Technical scheme of the present invention is compared with background technology: applicant adopts one to comprise at least one and comprise compound barrier layer assembly by the cut apart-compound barrier layer that again prepared by the stacked multi-layer co-extruded technology of layer multiplication of converging that at least three poly-mers form and carry out flexible combination with substrate layer assembly and selectable outer layer assembly, interior layer assembly, interlayer assembly and tack coat assembly dexterously, prepares the isolation laminated packaging material without aluminium foil.Its tool has the following advantages: 1, by select in the composite bed of layer multiplication coextrusion only comprise that at least three poly-mers that a barrier forms form 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 form that comprises, barrier material consumption can be reduced, manufacturing cost can be reduced; 2, at least two non-separating polymers in compound barrier layer form corresponding individual layer can be mutually bonding, mutual double team, cooperatively interact, reach with separating polymer and form better bonding of corresponding 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, when improving barrier property, reduce costs; 5, by selection, introduce obstruct composite bed and other barrier individual layer or the composite bed of other this layer of multiplication co-extrusion, can further enrich again properity, price and the purposes of compound barrier layer assembly.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.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.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 present invention will be further elaborated.
Fig. 1 is the integral structure schematic diagram of using isolation laminated packaging material without In Aluminium Foil Packing of the present invention.
Fig. 2 is integrally-built four kinds of preferred version schematic diagrams of using isolation laminated packaging material without In Aluminium Foil Packing of the present invention.
Fig. 3 be of the present invention without In Aluminium Foil Packing, with the layer multiplication in isolation laminated packaging material, 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. 4 be of the present invention without In Aluminium Foil Packing, with the layer multiplication in isolation laminated packaging material, 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. 5 be of the present invention without In Aluminium Foil Packing, with the layer multiplication in isolation laminated packaging material, 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.
The specific embodiment
Fig. 1 has described the integral structure without aluminium foil isolation laminated packaging material of the present invention.In material, at least comprise a substrate layer assembly 40 and a compound barrier layer assembly 60 of poly-mer.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 substrate layer outside face.Can select to increase a polymer inner layer assembly 80 as required in addition, for directly contact content and sealing.Inside and outside the referring near content with away from content here.In order to improve the laminated intensity between each component layer, can optionally introduce polymer bonding layer assembly, as 30 in Fig. 1,50 and 70.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 than the more excellent performance of certain assembly of single (compound) layer, and between each layer in an assembly that contains multilayer, may need to promote by adhesive agent laminated.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, or does not contain the assembly of many (compound) layer of tack coat.The composite bed here (composite layer) represents that these layers itself are to consist of more than one individual layer or individual layer, and assembly (component unit) represents that one of a conduct that 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.Tack coat assembly can be excluded at first, because there generally can each assembly can be had according to the selection of material to be suitable laminated.Get rid of tack coat assembly can also simplify technique, cost-saving and improve material environmental-protecting performance and can reusing.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.In Fig. 2 a, in this material, only comprise a substrate layer assembly 240 and a compound barrier layer assembly 260.In Fig. 2 b, in this material, only comprise a substrate layer assembly 340, compound barrier layer assembly 360 and an interior layer assembly 380.In Fig. 2 c, in this material, only comprise a substrate layer assembly 440, the interior layer assembly 480 of compound barrier layer assembly 460, one and an outer layer assembly 420.In Fig. 2 d, in this material, only comprise a substrate layer assembly 540, compound barrier layer assembly 560 and an outer layer assembly 520.
According to the present invention, poly-mer forms and comprises 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 that includes separating polymer composition forms and is called separating polymer composition, and corresponding individual layer (or individual layer) is called barrier individual layer (or individual layer); Otherwise, be called non-separating polymer and form and non-barrier individual layer (or individual layer).In the present invention, the poly-mer that can also define except comprising a kind of component of polymer not containing other compositions consists 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 concepts such as the known blend of polymer arts, filling that comprised here.Here defining again one or more component of polymer that comprise in those single polymers and polymer complex is polymeric material, and those polymeric materials are the compound of single polymers composition or multiple polymers composition.For example a poly-mer only comprises linear low density polyethylene (LDPE) in forming and does not comprise other any compositions, and 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 is also polymer complex; The blend of LDPE and HDPE is also polymer complex; The blend of nylon 6 and maleic anhydride modified LDPE can be called separating polymer compound.When constituent during two poly-mers form is different, is considered as not identical poly-mer and forms, the LDPE that for example LDPE and nanoclay are filled be that not identical poly-mer forms, but their central polymeric materials are identical.
According to the present invention, substrate layer can be paper substrates, can be also Polymers base material, for supporting 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.Polymers base material refers to that take poly-mer is the base material of main (base) body to comprise single polymers and polymer complex etc.In the present invention, General Requirements Polymers base material be thickness at more than 100 microns sheet material or sheet material, preferred thickness is between 100 microns to 1000 microns.Can comprise for the preparation of the polymeric matrix of Polymers base material at least one polymers for general use composition, 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, polyamide, unsaturated polyester (UP), biological polyester, polyethers, polyurethane, polystyrene Polymer, 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 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.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.In polymeric matrix, except comprising at least one above-mentioned component of polymer, can also comprise other one or more suitable polymeric material in order to prepare the blended complex of poly-mer.In filled polymer composite, except at least one polymeric material composition, also comprise the various suitable organic and inorganic filler for filled polymer matrix, include but not limited to wood chip, cellulose fibre, glass fibre, carbon black, graphite, dolomite, chalk, talcum, mica, calcium carbonate, clay is (as montmorillonite, 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 polymeric substrate, such as additive, auxiliary agent etc., includes 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.Because substrate layer does not directly contact with content, so Polymers base material can comprise the polymeric material of various suitable recovery, greatly improved the recycling of material, and environmental protection is cost-saving again.Substrate layer assembly can have more than one layer, and the present invention preferably only comprises a layer.
The radical function of polymeric outer layer assembly comprises 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 outer layer assembly preferably comprises at least one 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), 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), 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 substrate layer assembly.Polymeric material in outer layer assembly also can be by one or more suitable graininess organic or Inorganic Fillers Filled, those fillers are consistent with filler available in substrate layer.The poly-mer of the outer layer assembly of the present invention forms preferred Low Density Polyethylene (LDPE), linear low density polyethylene (LLDPE), ethylene-acrylic acid copolymer (EAA) and metallocene PE (mPE) and metallocene polypropylene (mPP), and the single polymers in their modifier and compound.
In the present invention, the composite bed that poly-mer obstruct composite bed assembly comprises one or more layer of multiplication coextrusion and barrier individual layer or the composite bed that optionally prepared by one or more additive method.In the obstruct composite bed of this at least one layer multiplication coextrusion, contain a plurality of repetitives, each repetitive at least comprises three individual layer, each individual layer forms corresponding to a poly-mer, it is mutually different wherein having at least three poly-mers corresponding to individual layer to form, intercept in composite bed and at least containing three different poly-mers, form, but the quantity that poly-mer forms is not more than individual layer quantity.In other words, in the repetitive of the obstruct composite bed of described layer multiplication coextrusion, comprising at least three different poly-mers forms, repetitive at least comprises three individual layer, each individual layer is corresponding to one in described at least three different poly-mers compositions, but the quantity that poly-mer forms is not more than individual layer quantity.In the present invention, during these at least three different poly-mers form, only by one, forming is that the separating polymer that includes at least one separating polymer composition forms, and this separating polymer composition has higher gas (oxygen) obstructing capacity.Poly-mer in barrier individual layer forms and comprises at least one barrier properties for gases component of polymer.In obstruct composite bed prepared by additive method, at least comprise two individual layers, 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, in the situation that individual layer quantity is not too large, can be different between the corresponding poly-mer of those individual layer forms, repetitive comprises how many individual layer and just comprises how many different poly-mers compositions.But generally, the quantity that poly-mer forms is more limited, or for considerations such as costs, preferably the poly-mer of certain some forms.In the middle of the present invention, the quantity that the poly-mer that comprises in preferred repeat units forms is at least three but no more than six.And when individual layer quantity is greater than poly-mer composing quantity, in repetitive, at least two individual layer by some diverse location are formed corresponding to identical poly-mer significantly.Different individual layer can refer to that the poly-mer in those individual layer forms different in the present invention, can refer to those individual layer poly-mers form identical but thickness different or in repetitive position different, but as do not indicate especially Different Individual layer and refer generally to there is the individual layer that different poly-mers form.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 form and repetitive is only the preferred structure of compound barrier layer of the layer multiplication coextrusion of three layers.Here the layer that defines picture top is the layer near substrate layer assembly, and the layer of picture below is the layer near content.Wherein repeat unit structure is with 111/112/113 expression, wherein 111,112,113 individual layer that represents respectively three diverse locations, i.e. first, second, and third individual layer; The subscript of number in the figure is in order to distinguish repetitive in composite bed Zhong position, for example, 111 ' be respectively near first individual layer of repetitive of substrate layer assembly and the first individual layer of the repetitive of close content with 111n.According to the present invention, these three different poly-mers consist of two different non-barriers composition and barriers and form, and represent respectively here to form A, B and C.In Fig. 3, three of the diverse location of repetitive individual layer 111,112,113 poly-mer composition A, B, Cs different from three can have six kinds of corresponding forms, i.e. A/B/C, A/C/B, B/A/C, B/C/A, C/A/B, six kinds of arrangements of C/B/A.Because three compositions are not identical, and lamination layer structure is according to different and different with the individual layer of substrate layer assembly near content, so intercept composite bed, has six kinds of different structures, the spread pattern that each structural correspondence forms in above-mentioned a kind of poly-mer.Sometimes can directly with corresponding poly-mer, form and represent individual layer (or individual layer) for example corresponding to the individual layer 111 that forms A, to be also directly referred to as individual layer A for convenience's sake in the present invention, because the number designation here 111 represents location information.
When repetitive, be four layers but when only comprising three poly-mers and forming, according to the present invention, in four individual layer, can corresponding to non-separating polymer, form A by two, one corresponding to non-barrier composition B and one corresponding to barrier composition C; Also can corresponding to non-barrier, form A by one, two form B and one corresponding to non-barrier and form C corresponding to barrier; Can also corresponding to non-barrier, form A by one, one forms B and two corresponding to non-barrier and forms C corresponding to barrier; Totally three kinds of combinations.If adjacent two layers is same composition, 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 can have 54 kinds of structures.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, certainly the invention is not restricted to this.The repetitive of four layers can also be comprised of four different poly-mers, according to the present invention, can be formed with a barrier and be formed by three different non-barriers, 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.
When repetitive, be five layers but when only comprising three poly-mers and forming, according to the present invention, in five individual layer, can corresponding to non-barrier, form A by two, two form B and one corresponding to barrier composition C corresponding to non-barrier; Can corresponding to non-barrier, form A by two, one forms B and two corresponding to non-barrier and forms C corresponding to barrier; Can corresponding to non-barrier, form A, two by one forms B and two corresponding to non-barrier and forms C corresponding to barrier; Can corresponding to non-barrier, form A by one, one forms B and three corresponding to non-barrier and forms C corresponding to barrier; Can corresponding to non-barrier, form A by one, three non-barriers form B and one and form C corresponding to barrier; Can corresponding to non-barrier, form A by three, one forms B and one corresponding to non-barrier and forms C corresponding to barrier; Totally six kinds of combinations.Every kind of combination has 120 kinds of spread patterns in theory, if but adjacent two layers or three layers are same composition, can be considered in the ordinary course of things and are 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.In Fig. 5 a, repeat unit structure can be A/B/C/B/A for example, and 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.In Fig. 5 b, repeat unit structure can be A/B/A/C/A for example, and 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.The repetitive of five layers can also be comprised of four or five poly-mers, therefore can have more combination and structure.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 carry out rational Choice and design as required.Different poly-mers in preferred repeat units of the present invention form no more than six.
Can find out, in repetitive, comprising more than three different poly-mers forms, and when repetitive has three above individual layer, the structure of those barrier composite beds is very rich and varied, and great facility and freedom can be provided for the design of packing.
In barrier assembly, except the compound barrier layer that comprises layer multiplication coextrusion is when, selection comprises barrier individual layer or composite bed prepared by one or more additive method, can enrich again the design of packing.
Obstruct can be choke, waterproof and anti-wet goods, mainly refers to that choke particularly hinders oxygen here.Therefore separating polymer requires to comprise the component of polymer with higher gas (oxygen) barrier in forming.According to above-mentioned those separating polymers of the definition that poly-mer is formed, form, poly-mer corresponding to barrier individual layer (or individual layer) forms, and can be single separating polymer and separating polymer compound.In those single separating polymers and separating polymer compound, include the separating polymer material forming by one or more separating polymer compositions.In 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 (PE0), Kynoar (PVDF), liquid crystal polyester, the ionomer based on ethene, ethene and beta-unsaturated esters, and one or more in the composition such as their modifier and resultant of reaction.Separating polymer material can also be above-mentioned at least one 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 one the compound in the composition such as their modifier and resultant of reaction.Separating polymer material can also be ethylene-vinyl alcohol copolymer (EVOH) with the polyamide composition such as nylon 6, nylon 66, nylon 10, nylon 6-10, nylon 6-12, nylon 12, amorphous nylon, MXD6 nylon at least one compound, and wherein one or more such as the modifier of those compounds and resultant of reaction.The definition of modifier and resultant of reaction is with similar above.
Non-barrier in barrier composite bed or low separating polymer form, poly-mer corresponding to non-(low) barrier individual layer (or individual layer) forms, general do not have a good gas barrier sexual function, the use of those materials generally play enhancing, toughness reinforcing, dispersion, bonding, the effect such as seal, reduce costs.Component of polymer during those poly-mers form can be 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, Chelate 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), 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), 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.Performance and the good component of polymer of price such as the preferred Low Density Polyethylene of the present invention (LDPE), linear low density polyethylene (LLDPE), ethylene-acrylic acid copolymer (EAA) and metallocene PE (mPE) and metallocene polypropylene (mPP).Suitable non-(low) separating polymer composition also can be used as the optional component of polymer of separating polymer in forming, and mixes use with separating polymer composition, be generally used for play enhancing, toughness reinforcing, promote bonding, the effect such as reduce costs.
Similar in the non-polymer compositions such as the optional granulated filler for barrier composite bed and individual layer poly-mer composition and additive and auxiliary agent and other assemblies.When there is no interior layer assembly, those non-polymer composition General Requirements are nontoxic, harmless, without ill-effect etc.In the present invention, for filling the granulated 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.
Interior layer assembly directly contacts content, and in therefore forming, the material of layer assembly depends on the character of content.At the veteran technical personnel of packaging field, can reasonably select as required.In generally requiring, the material of layer assembly has chemical inertness to content, and the liquid component in content and aqueous vapor are had to high barrier, and each composition in content is had to low absorption.And the material of layer assembly has sealability in generally requiring, heat sealability particularly.So in formation of the present invention, the poly-mer composition of layer assembly preferably forms similar with the outer layer assembly of formation.At least one the suitable component of polymer wherein comprising 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), ethylene-acrylic acid copolymer (EAA), and their modifier and resultant of reaction etc.The definition of modifier and resultant of reaction is with similar above.In the present invention, preferably Low Density Polyethylene (LDPE), linear low density polyethylene (LLDPE), ethylene-acrylic acid copolymer (EAA) and metallocene PE (mPE), and their modifier and resultant of reaction.In the non-polymer compositions such as filler, additive and auxiliary agent in can forming for internal layer component assembly thing and other assemblies, poly-mer composition is similar, but General Requirements is nontoxic, harmless, without ill-effect etc.Interior layer assembly is optional.General when barrier layer assembly in the layer of close content be non-involution or while forming for the thinner involution poly-mer of Thickness Ratio, need selection introducing involution internal layer polymer assembly.In select introducing, during layer assembly, this assembly can comprise one deck or multilayer, is preferably one deck.
The binder polymer composition that can form for the adhesive agent of each layer in bond each component layer or component layer 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 (TP0), 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 of copolymer, condensation product, affixture, modifier, reaction and modified product is with similar above.Tack coat assembly is optional.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 adhesive material also can be used as other poly-mers interpolation blend in forming, and to reach, increase the cohesive force between adjacent layer in the situation that does not increase extra tack coat.Those Binder Compositions of part can be used with separating polymer or non-separating polymer blend or as the bulking agent of blend.
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.The effects such as this class component generally can play that resistance is wet, resistance light, hyperchromic, support, but be non-essential.The component of polymer that can be used for interlayer assembly includes but not limited to polyolefin, polyester, biological polyester, and their modifier and resultant of reaction.The definition of modifier and resultant of reaction is with similar above.In like manner, if while having more than one layer in interlayer assembly, can be directly laminated or laminated by tack coat assembly between each layer.In like manner, the poly-mer in tack coat assembly and interlayer assembly also can comprise the compositions such as suitable filler, additive and auxiliary agent in forming.
The layer multiplication coetrusion adopting in the present invention is a kind of to the cut apart-stacked method of converging operation again of feed steam, each such operation is accompanied by width expansion and the high shrinkage to material stream, and make to expect that fluid layer quantity is multiplied, material stream individual layer thickness reduces at double.Layer multiplication operation is undertaken by layer multiplicator.The layer multiplicator extrusion device with layer multiplication ability can be referring to Chinese utility model patent application 200820229095.4 and 200820229641.4, and Chinese invention patent application 200810072529.9.When layer multiplicator uses with head and the tail series connection, it is 2 that material fluid layer number is added to original multiple
m2* 3
m3* 4
m4* ... * n
mn, wherein exponent m 2, m3, and m4 ..., mn be respectively material stream extrude adopt in direction dual, triple, quadruple ..., the quantity of n double-layer multiplicator.In the present invention, preferably adopt dual and/or quadruple-layer multiplicator to be composed in series from beginning to end a layer multiplication portion, as module and other extrude the needed module of operation for example feeder, measuring pump, confession stub bar, extrude first-class being used in combination.The preferred single screw rod of feeder or double screw extrusion machine in the present invention, and can only have and simply converge stacked function or there is the layer of increasing ability for stub bar.The number of plies amount of converging major ingredient stream providing for stub bar of simply converging stacked function is consistent with feed steam quantity; The number of plies amount of converging major ingredient stream providing for stub bar with layer ability that increase is greater than feed steam quantity; Increase layer and for stub bar, can be equivalent to a certain extent the combination that connects diverter for stub bar upstream common.While extruding, each feed composition is by feeder (with selectable measuring pump), enter for stub bar and obtain converging stacked (and may tentatively be increased layer), feed steam after stacked is used as the first stream of expecting of layer multiplication operation and sends into a layer multiplication portion, cut apart-the stacked layer multiplication operation converging again, the material stream that reaches the specific number of plies after layer multiplication is extruded and is collected or directly and other assembly coextrusion laminatings by suitable extruder head.Material stream after stacked for stub bar is generally considered as a repetitive, sometimes can comprise several repetitives.For example, when two different non-separating polymers form A, B and a separating polymer composition C is extruded by a single screw extrusion machine plasticizing respectively and is transported to a simple stub bar that supplies with three runners by measuring pump, and then converged and be laminated into the three-decker material with A/C/B and flow, this material stream continues constantly cut apart-stacked converging again by layer multiplication portion, and finally material stream is (A/C/B)
k, wherein k, for the number of times that the stream of just expecting is doubled, is 2
m2* 3
m3* 4
34* ... * n
mndoubly, wherein exponent m 2, m3, and m4 ..., mn be respectively material stream extrude adopt in direction dual, triple, quadruple ..., the quantity of n double-layer multiplicator; And increase layer and converge while being laminated into nine layers of structure material stream with A/C/B/A/C/B/A/C/B for stub bar when three above-mentioned feed compositions are passed one, if the individual layer with same polymer composition in this structure is suitable at the thickness of diverse location, the repetitive that this material stream can be considered as the repetitive of nine layers or comprise three three layers.While needing compound barrier layer that more than one layer multiplication extrude in packing, preferably directly that a plurality of compound barrier layers are directly laminated by Duo Qi road extruder head or the similar direct coextrusion of extruder head for stub bar.
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 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.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 layer multiplication coextrusion comprise that three poly-mers in the composite bed that at least three poly-mers form and is wherein only comprised of a barrier form 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 selection, introduce in addition composite bed and other barrier individual layer or the composite bed that at least three poly-mers form and are wherein only comprised of a barrier that comprise of other layer of multiplication coextrusion, can further enrich again properity and the purposes of compound barrier layer assembly.Generally, in barrier assembly, comprise the compound barrier layer of a layer multiplication coextrusion that only comprises three poly-mers compositions and wherein only formed by a barrier, just can there are other without the more excellent Combination property of the packing of aluminium foil.
Except compound barrier layer assembly, in other assemblies that contain a plurality of (compound) layer, also can contain the composite bed of preparing with layer multiplication coextrusion.The preparation of the assembly that in the present invention, whole laminated packaging material and any one contain a plurality of (compound) layer can be completed or first be prepared respectively each individual layer or composite bed to carry out laminated or direct co-extrusion part many (compound) layer laminated step by step with other layer more again by direct coextrusion laminating.In extrusion, the feed composition that poly-mer forms may not with in final material poly-mer composition corresponding to individual layer (or individual layer) identical, 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.The those of skill in the art of packing preparation field, can reasonably design easily as required and select.
When substrate layer module outer surface does not contain outer layer assembly, as shown in Fig. 2 a and 2b, the substrate layer assembly in those materials is generally Polymers base material, and the Polymers base material that preferably can print, and ink is directly printed on base material outside face.When substrate layer is paper substrates, General Requirements base material outside face applies polymeric outer layer (as Fig. 2 c and 2d), for the protection of paper substrates, is not subject to moisture penetration and destruction, increases the resistance to abrasion of base material simultaneously.When base material is paper material, in order to increase cohesiveness, can in treatment process, with corona, flame or ozone pretreatment, activate the outside face of outer field inside face and/or base material.Can be at paper substrates outside face containing printed layers in the material of paper substrates assembly at those, the also outside face of layer assembly or inside face outside, preferably at the outside face of paper substrates.
The containers such as bag, bag, box or case that can be processed to various shapes without aluminium foil barrier packaging material of the present invention, for example the box of the bag of pillow shape, hexahedron and other polyhedrals, rooftop box, with the bag of dumping mouth or box etc.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 to 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 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 of the present invention, the structure of material can be by assembly selection and each assembly particularly the Choice and design of the compound barrier layer 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, the integral structure of packing is skin/substrate layer/barrier layer, and its ectomesoderm is Low Density Polyethylene, and substrate layer is millboard, and barrier layer is for only forming containing three kinds of poly-mers and repetitive is the composite bed that the layer multiplication of five layers extruded.The non-separating polymer composition A wherein intercepting in composite bed is Low Density Polyethylene, and it is the polyvinyl alcohol that maleic anhydride modified Low Density Polyethylene separating polymer forms the melt-processable that C is modification that non-separating polymer forms B.
First (Substance is about 400g/m at approximately 325 ℃, Low Density Polyethylene curtain coating to be coated on to millboard
2) the outside face with printed layers on, coating thickness is about 20 microns.
In coating, be laminated with the obstruct composite bed that on the inside face of millboard of Low Density Polyethylene, coextrusion is extruded by layer multiplication method.The repeat unit structure of composite bed is A/B/C/B/A, and wherein each elementary layer thickness is suitable.By the double layers multiplicator of 8 head and the tail series connection, total number of plies of compound barrier layer is 1280 layers, and individual layer thickness is about 20 nanometers.
By these packing, can form hexahedron brick shape box or rooftop box.
Embodiment 2
In the present embodiment, the integral structure of packing is skin/substrate layer/barrier layer, its ectomesoderm is Low Density Polyethylene (LDPE), and substrate layer is thin paper, and barrier layer assembly is to comprise that three kinds of poly-mers form and repetitive is the composite bed that the layer multiplication of four layers extruded.The non-separating polymer composition A wherein intercepting in composite bed is ethylene acrylic acid co polymer (EAA), it is the blend of 95wt% Low Density Polyethylene and the maleic anhydride modified Low Density Polyethylene of 5wt% that non-separating polymer forms B, and it is the nylon 6 that extrusion grade ethylene-vinyl alcohol copolymer (EVOH) and commodity rank nanoclay are filled that separating polymer forms C.
First (Substance is about 150g/m at approximately 325 ℃, Low Density Polyethylene curtain coating to be coated on to millboard
2) the outside face with printed layers on, coating thickness is about 20 microns.
In coating, be laminated with the obstruct composite bed that on the inside face of thin paper of Low Density Polyethylene, coextrusion is extruded by layer multiplication method.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 the double layers multiplicator of 7 head and the tail series connection, total number of plies of compound barrier layer is 512 layers, and barrier individual layer thickness is about 100 nanometers.
By these packing, can form pillow-like packaging bag etc.
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 millboard, barrier layer assembly is to comprise that three kinds of poly-mers form and repetitive is the composite bed that the layer multiplication of three layers extruded, the LLDPE that internal layer is nanon calcium carbonatefilled.The non-barrier composition A wherein intercepting in composite bed is ethylene-vinyl acetate copolymer (EVA), it is the blend of 95wt% Low Density Polyethylene and the maleic anhydride modified Low Density Polyethylene of 5wt% that non-barrier forms B, and it is the blend of extrusion grade polyvinyl alcohol copolymer (PVA) and MXD6 nylon that separating polymer forms C.
First (Substance is about 320g/m at approximately 350 ℃, linear low density polyethylene curtain coating to be coated on to millboard
2) the outside face with 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 the double layers multiplicator of 8 head and the tail series connection, total number of plies of compound barrier layer is 768 layers, and barrier individual layer thickness is about 30 nanometers.Intercept composite bed and internal layer (approximately 20 microns) containing the LLDPE of 20wt% nano-calcium carbonate by the extruder head coextrusion of Duo Qi road outside surface-coated be laminated with the inside face of the millboard of LLDPE.
By these packing, can form hexahedron brick shape box or rooftop box etc.
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 barrier layer assembly is for forming containing four kinds of poly-mers and repetitive is the composite bed that the layer multiplication of four layers extruded.The non-separating polymer composition A wherein intercepting in composite bed is anhydride modified polypropylene, it is oxidic polyethylene that non-separating polymer forms B, it is metallocene Low Density Polyethylene (mLDPE) that non-separating polymer forms C, and it is polyethylene terephthalate (PET) that separating polymer forms D.
Substrate layer thickness is about 100 microns, containing 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 the quadruple-layer multiplicator of 4 head and the tail series connection, total number of plies of compound barrier layer is 1024 layers, and individual layer thickness is about 35 nanometers.Substrate layer becomes packing with obstruct composite bed by the extruder head coextrusion one-shot forming of Duo Qi road.
By these packing, can form hexahedron brick shape box or rooftop box etc.
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), substrate layer is millboard, barrier layer comprises one and comprises that three kinds of poly-mers form and repetitive is only composite bed and the barrier individual layer that the layer multiplication of three layers extruded, and internal layer is Low Density Polyethylene.
First (Substance is about 400g/m at approximately 325 ℃, Low Density Polyethylene curtain coating to be coated on to millboard
2) the outside face with printed layers on, coating thickness is about 20 microns.
In coating, be laminated with coextrusion barrier layer assembly of millboard inside face and the internal layer of Low Density Polyethylene.It is ethylene-vinyl acetate copolymer (EVA) that non-barrier in the obstruct composite bed of layer multiplication coextrusion forms A, it is the maleic anhydride modified polyacrylic compound of 97wt% polypropylene and 3wt% that non-barrier forms B, it is extrusion grade Vingon that separating polymer forms C, and its repeat unit structure is A/C/B.The poly-mer of barrier individual layer consists of the isotactic polypropylene (iPP+Mt) that montmorillonite is filled so.Internal layer polymer consists of metallocene Low Density Polyethylene (mLDPE), and thickness is about 10 microns.The gross thickness of the obstruct composite bed of layer multiplication is about 30 microns, by 4 quadruple-layer multiplicators, extrudes, and the number of plies reaches 768 layers.Internal layer thickness is about 20 microns.
By these packing, can form hexahedron brick shape box or rooftop box etc.
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 millboard, interlayer is that cast polypropylene (cPP), tack coat are acrylate adhesives, and barrier layer assembly is one and comprises the composite bed that three kinds of poly-mers form and repetitive has the layer multiplication of three layers to extrude.
In the present embodiment, each assembly adopts a minute one-step preparation method, more laminated with substrate layer respectively.First by 3 quadruple-layer multiplicators, prepare the obstruct composite bed of 192 layers, wherein non-separating polymer forms A polymethyl methacrylate (PMMA), non-separating polymer forms B for filling metallocene Low Density Polyethylene for 10wt% nanometer winnofil, it is the compound of PEN (PEN) and nylon 6 (Nylon6) that separating polymer forms C, and repeat unit structure is A/C/B.Approximately 60 microns of the thickness of obstruct composite bed film.Then linear low-density polyethylene film is laminated to millboard outside face under ozonization, then in substrate layer inside face curtain coating, applies polypropylene, then in polypropylene surface, apply acrylate adhesives while laminate barrier composite bed film.
By these packing, can form hexahedron brick shape box or rooftop box etc.
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, barrier layer assembly comprises the obstruct composite bed that two layer multiplications are extruded, one of them comprises, and three kinds of poly-mers form and repetitive is five layers, another one comprises near the composite bed of content that three kinds of poly-mers form and repetitive is three layers, tack coat is vinyl-vinyl acetate copolymer (EVA), internal layer is carbon black filled metallocene linear-low density polyethylene (mLLDPE).
In the present embodiment, each assembly adopts classification coetrusion.First a coextrusion in coating, be laminated with on the inside face of heavy kraft paper plate of LLDPE that coextrusion is outer, substrate layer and first obstruct composite bed of being extruded by layer multiplication method.It is epoxy-functional polypropylene that non-barrier in the first composite bed forms A, it is EU that non-separating polymer forms B, it is polyacrylinitrile (PAN) that separating polymer forms 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 (approximately 20 microns) by 3 quadruple-layer multiplicators, reaches 320 layers.In the recovery polypropylene of substrate layer, also add foaming agent extrusion foaming, the thickness after foaming is about 250 microns.At the above-mentioned laminated material that contains the first composite bed completely before cooling curing, toward other assembly of coextrusion on its inside face, and utilize rolling press pressing.In the second composite bed, non-barrier composition D is epoxy-functional polypropylene, and it is maleic anhydride modified Low Density Polyethylene that non-barrier forms E, and it is nylon 6 that barrier polymer forms F, and repeat unit structure is D/F/E, and three each and every one bulk layer thickness are suitable.Second intercepts composite bed (approximately 30 microns) by 3 quadruple-layer multiplicators and 1 double layers multiplicator, reaches 384 layers.In outer linear low density polyethylene, titanium dioxide loading is 6wt%, for printing and hide the color of expanded polypropylene.In internal layer linear low density polyethylene, the loading of carbon black is 12wt%, for shading.
By these packing, can form hexahedron brick shape box or rooftop box etc.
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 (10)
1. the laminated material 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 are combined, this substrate layer assembly can play a supportive role, this compound barrier layer assembly comprise at least one by cutting apart-again prepared by the stacked layer multiplication coextrusion method of converging, the compound barrier layer that contains a plurality of repetitives, it is characterized in that: this each repetitive at least comprises three kinds of poly-mers and forms, this every kind poly-mer forms can form body layer or more than one individual layer one by one, during those kind of poly-mer forms, only a kind of poly-mer, consisting of is that separating polymer forms, this separating polymer forms 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 one in paper substrates and Polymers 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 forms is at least one is selected from polyvinyl alcohol (PVA), 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) is selected from nylon 6 with at least one, nylon 66, nylon 10, nylon 6-10, nylon 6-12, nylon 12, amorphous nylon, the compound of the polyamide composition 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 forms is at least one is selected from polyvinyl alcohol (PVA), 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 one are selected from ethylene-vinyl alcohol copolymer (EVOH), nylon 6, nylon 66, nylon 10, nylon 6-10, nylon 6-12, nylon 12, amorphous nylon, MXD6 nylon, and the compound that forms of the component of polymer of their modifier and resultant of reaction.
5. a kind of isolation laminated packaging material according to claim 1, is characterized in that: in this compound barrier layer assembly that contains at least one layer of compound barrier layer of multiplication coextrusion, also comprise at least one barrier individual layer.
6. a kind of isolation laminated packaging material according to claim 1, is characterized in that: in the compound barrier layer assembly of the compound barrier layer that this contains at least one layer of multiplication coextrusion, also comprise at least one other non-by cutting apart-compound barrier layer that again prepared by the stacked layer multiplication coextrusion converging.
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 substrate layer assembly outside and can be laminated at least one in the interior layer assembly of barrier layer assembly inner side.
8. a kind of isolation laminated packaging material according to claim 1, is characterized in that: also comprise: for the tack coat assembly of each layer in bonding each assembly and 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 interlayer assembly.
10. a kind of isolation laminated packaging material according to claim 1, is characterized in that: also comprise: the Charge forming for filled polymer, 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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| WO1996005055A1 (en) * | 1994-08-16 | 1996-02-22 | Minnesota Mining And Manufacturing Company | Barrier films |
| JP2000355080A (en) * | 1999-04-12 | 2000-12-26 | Toppan Printing Co Ltd | Composite barrier film and package using the same |
| CN1745197A (en) * | 2002-12-20 | 2006-03-08 | 艾利丹尼森公司 | Composite barrier films and method |
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| WO1996005055A1 (en) * | 1994-08-16 | 1996-02-22 | Minnesota Mining And Manufacturing Company | Barrier films |
| JP2000355080A (en) * | 1999-04-12 | 2000-12-26 | Toppan Printing Co Ltd | Composite barrier film and package using the same |
| CN1745197A (en) * | 2002-12-20 | 2006-03-08 | 艾利丹尼森公司 | Composite barrier films and method |
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| CN101992888A (en) | 2011-03-30 |
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