CN201647345U - Laminated polymer barrier packaging film - Google Patents
Laminated polymer barrier packaging film Download PDFInfo
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- CN201647345U CN201647345U CN201020179610XU CN201020179610U CN201647345U CN 201647345 U CN201647345 U CN 201647345U CN 201020179610X U CN201020179610X U CN 201020179610XU CN 201020179610 U CN201020179610 U CN 201020179610U CN 201647345 U CN201647345 U CN 201647345U
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Images
Abstract
The utility model discloses a laminated polymer barrier packaging film, which at least comprises a surface layer and at least one laminated barrier composition layer, wherein the surface layer and the laminated barrier composition layer are combined together, each barrier composition layer respectively comprises a plurality of repeating units which are extruded by multiplication layer by layer, and each repeating unit respectively comprises at least one individual layer which is provided with a corresponding polymer composition, wherein at least one polymer composition comprises the components of the barrier polymer.
Description
Technical field
The utility model relates to a kind of isolation laminated polymer packaging film.
Background technology
Along with the raising of people's living standard, particularly the demand of barrier packaging material is increasing to packing, and therefore polymeric packaging material has also obtained develop rapidly.Yet poly-mer generally derives from non-renewable raw materials such as oil, uses polymeric material all to have caused huge burden for the energy and environment in a large number.Novel, High Performance, the development research of separating polymer packing have cheaply become competitively hot of research and development of various countries.
Multi-layer co-extruded combination process is widely used with its special advantages in the world as a kind of job operation of composite plastic film.It is found that the number of plies is many more, the Combination property of material is good more.Use multi-layer co-extruded, co-extrusion technology more than 7 layers particularly, the resin of desired properties can be made film with less thickness, barrier material is divided into several thin layers and has also realized better barrier property, can reduce the use of polymeric material widely, the cost of reduction material reduces the influence to the energy and environment simultaneously; The phenomenon of curling that multi-layer co-extruded reasonable utilization and can avoiding produces because of rete is blocked up.
These co-extrusions no matter be coextrusion blow or coextrusion casting, all have great limitation at present.Because the co-extrusion number of plies is high more, 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.
And the multi-layer co-extruded plastics laminated film blow moulding equipment of China mostly is two to three-layer co-extruded rotating head form at present, and is backward in technique.The production of the composite plastic film of having relatively high expectations for adaptation, some enterprises have introduced five to seven-layer coextruded plastic laminated film blow moulding equipment, but still can not meet the need of market, in a large number dependence on import, make its cost high, suppressed the development of the multi-layer co-extruded plastics laminated film of China.
The utility model content
The utility model provides a kind of isolation laminated polymer packaging film, and it has overcome the existing deficiency of background technology multilayer polymer film material.
The technical scheme that is adopted that the utility model solves its technical matters is:
A kind of isolation laminated polymer packaging film, it is characterized in that: it comprises that at least one superficial layer and at least one lamination intercept composite bed, this superficial layer and lamination intercept composite bed and are laminated together, all contain a plurality of repetitives that adopt layer multiplication mode to extrude in this each obstruct composite bed, this each repetitive all comprises at least one to have pairing poly-mer composition and has at least a poly-mer to form the individual layer that contains a kind of separating polymer composition.
Among one preferred embodiment: it also comprises at least one laminated barrier individual layer that intercepts composite bed in lamination.
Among one preferred embodiment: it also comprises the laminated second barrier composite bed that intercepts composite bed in lamination of at least one non-layer multiplication coextrusion.
Among one preferred embodiment: it also comprises at least one laminated in the barrier individual layer of lamination obstruct composite bed, also is provided with at least one tack coat or/and at least one interlayer between described various barrier composite beds, individual layer and the superficial layer.
Among one preferred embodiment: it also comprises the barrier individual layer that at least one laminated lamination intercepts composite bed, the filler of filled polymer within this individual layer.
Among one preferred embodiment: it also comprises the second barrier composite bed of the laminated lamination obstruct composite bed of at least one non-layer multiplication coextrusion, the filler of filled polymer within this second barrier is compound.
Among one preferred embodiment: it also comprises at least one laminated barrier individual layer that intercepts composite bed in lamination, also be provided with at least one tack coat between described various barrier composite bed, individual layer and the superficial layer or/and at least one interlayer, the filler of filled polymer within this tack coat or the interlayer.
Among one preferred embodiment: the thickness of obstruct composite bed that this repetitive comprises the layer multiplication coextrusion of body layer one by one at least is not more than 2000 microns.
Among one preferred embodiment: the filler of filled polymer within this individual layer.
Among one preferred embodiment: the filler of filled polymer within this superficial layer.
The technical program is compared with background technology, and it has following advantage:
1, the applicant adopt dexterously at least one comprise at least one poly-mer form and have wherein that a barrier forms at least by cut apart-the compound barrier layer of the stacked again layer multiplication multilayer extruding technology preparation that converges and at least one in the surfaces externally and internally layer prepare isolation laminated polymer packaging membraneous material.
2, adopt layer multiplication multilayer extruding technology to prepare the laminated material that contains many layers or have the layer of oriented material effectively, this laminate film material have following advantage: a, by select at least one poly-mer that includes at least a separating polymer composition in the composite bed that layer multiplication extrude form and composite bed in the number of plies amount of repetitive, just can prepare rich and varied compound barrier layer; B, form and the selection of the arrangement of individual layer, can design the compound barrier layer structure that effective protection separating polymer is formed easily by poly-mer; C, when comprising two separating polymers in the repetitive of compound barrier layer and form, a plurality of barrier individual layer are double team mutually, cooperatively interacts, barrier property can be better; D, contain that two poly-mers are formed but the composite bed and other barrier individual layer or the composite bed that wherein have at least two individual layer, can further enrich structure, performance, price and the purposes of compound barrier layer assembly again by what select to introduce other layers multiplication co-extrusion.
3, multi-layer co-extruded more adjustable more flexibly than tradition at aspects such as the quantity of layer and the thickness of individual layer by the separating polymer packing film material of layer multiplication co-extrusion, number of plies amount can increase greatly, and layer thickness can reduce greatly.
4, 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.
5, by should be multi-layer co-extruded, 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 number of plies increase thickness reduces.
6, 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 saved cost again.
7, the increase of the number of plies and bed thickness reduce also to produce more crooked little molecular migration passage, improved barrier; 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.
8, multi-layer co-extruded the making of layer multiplication reaches better barrier with still less barrier material, therefore has excellent more performance and price advantage.
9, at least one in the introducing surfaces externally and internally layer improves safety, leak tightness, impressionability, durability etc.
10, in packing of the present utility model, 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 present other polymer packaging membraneous material and have remarkable advantage.
Description of drawings
The utility model is described in further detail below in conjunction with drawings and Examples.
Fig. 1 is three kinds of preferred overall structure of isolation laminated polymer packaging film of the present utility model.
Formed and repetitive is a kind of preferred version scheme drawing that double-ply intercepts lamination layer structure comprising of extruding by two poly-mers for doubling in isolation laminated polymer packaging film of the present utility model middle level for Fig. 2.
Formed and repetitive is a kind of preferred version scheme drawing of three layers obstruct lamination layer structure comprising of extruding by two poly-mers for doubling in isolation laminated polymer packaging film of the present utility model middle level for Fig. 3.
Fig. 4 comprises for what preparation was extruded in a layer multiplication that comprises in the isolation laminated polymer packaging film of the present utility model that three poly-mers are formed and repetitive is two kinds of preferred version scheme drawings of five layers obstruct lamination layer structure.
The specific embodiment
Below in conjunction with drawings and Examples the utility model is further set forth.
The stacked packing film of barrier of the present utility model comprises at least one at least one obstruct composite bed assembly and the surfaces externally and internally layer assembly.Wherein: intercept the composite bed assembly and comprise at least one the obstruct composite bed that adopts the coextrusion of layer multiplication mode and the barrier individual layer or the composite bed of optionally one or more additive method preparation.Fig. 1 has provided preferred three kinds of membrane structures of the present utility model.Film among Fig. 1 a comprises one and intercepts composite bed assembly 12 and inside and outside two superficial layer assemblies 13 and 11; Film among Fig. 1 b comprises one and intercepts composite bed assembly 22 and an outer surface layer assembly 21; Film among Fig. 1 c comprises one and intercepts composite bed assembly 31 and an interior surface layers assembly 32.Just enumerated three concrete Application Examples above, but and as limit.Here definition is an inside face near the surface of packed article (content), another opposing to the surface then be outside face.In order to reach the well laminated of each component layer, can optionally introduce the tack coat assembly.At some in particular cases, can also introduce the interlayer assembly by selectivity correct position in film.According to the utility model, 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, wherein: certain assembly with many (compound) layer may have been given play to 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.In the utility model, except intercepting the composite bed assembly, other assemblies preferably only comprise one (compound) layer or do not contain many (compound) layer of tack coat.The composite bed here (composite layer) represents that these layers itself are to be made of the individual layer more than, and one of the conduct that one of assembly (component unit) expression comprises one (compound) layer or many (compound) layer has the element layer of specific function (for example obstruct).
In the utility model, contain a plurality of repetitives in the obstruct composite bed that described at least one employing layer multiplication mode is extruded, this repetitive comprises at least one individual layer, each individual layer all is made up of corresponding polymers, and wherein at least one individual layer corresponding polymers includes at least a separating polymer composition in forming.The separating polymer composition here refers to have the poly-mer of good gas barrier.In the utility model, when the repetitive in the obstruct composite bed that described layer multiplication extruded contains more than one individual layer, different 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 form identical but thickness difference or 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.
Poly-mer is formed and is comprised one or more component of polymer and optional other non-polymer compositions.The poly-mer composition that includes the separating polymer composition is called separating polymer and forms, and pairing individual layer then is called the barrier individual layer; Otherwise, then be called non-separating polymer and form and non-barrier individual layer.According to the utility model, the constituent during two poly-mers are formed promptly is considered as poly-mer inequality and forms not simultaneously, and for example nylon 6 and nanoclay filled nylon-6 are that poly-mer inequality is formed.
In the utility model, when the repetitive in the obstruct composite bed that described layer multiplication extruded only contained one by one the body layer, in fact this obstruct composite bed can be considered an individual layer.In addition, when the repetitive in the obstruct composite bed that described layer multiplication extruded contains more than body layer one by one, form when identical when the pairing poly-mer of adjacent individual layer, those individual layer can be considered and are equal to body layer one by one.
Repetitive in the preferred described obstruct composite bed of the utility model comprises at least two and corresponds respectively to the individual layer that at least two different poly-mers are formed, promptly comprise at least two different individual layer, and each individual layer is corresponding to one at least two different poly-mers compositions.
For the ease of understanding, the obstruct composite bed that described at least one layer multiplication extruded describes for example here.
At first, when only comprising obstruct composite bed that the multiplication of layer extrude in the examples of implementation and only comprising body layer one by one or during a plurality of individual layer of forming corresponding to same polymer according to the repetitive of this composite bed of the utility model, then this composite bed can be considered as being contained closing layer by layer that same polymer forms and being formed by a plurality of in theory.When interface layer disappeared, in fact this composite bed should be single layer structure.This composite bed by the preparation of layer multiplication method can be considered as composite bed in the utility model, generally extrude functions such as to cause film (filler) orientation because of layer multiplication method.This will be clear that in specific embodiment more.
When only comprising two individual layer and its in the repetitive and correspond respectively to two different poly-mers and form, according to the utility model, the structure of repetitive can be as shown in Figure 2.Wherein two individual layer are respectively with 111 and 112 expressions, and then repetitive can 111/112 expression.Wherein, for the ease of clear each repetitive of distinguishing of inspector, the subscript difference of the individual layer of each repetitive, for example 111 ', 112 ' or 111 ", 112 ".For example two different poly-mers are formed respectively to form A and to form B and represent, wherein have at least among A and the B and include at least a separating polymer composition in the composition, then when individual layer 111 and 112 corresponds respectively to composition A and B or B and A, two different poly-mers are formed in repetitive with two kinds of different forms arrangements, i.e. A/B and B/A.In the utility model, upward to the outside face towards packing film, downward direction is towards the inside face of packing film, promptly near the surface of content among the right of stepped construction and the figure among the left side of definition layer stack structure (arrangement) and the figure.Then because the difference of individual layer arrangement position may produce different usefulness by the obstruct composite bed that above-mentioned repetitive constitutes.
In addition according to the utility model, repetitive in the obstruct composite bed of this layer multiplication coextrusion can comprise at least three individual layer and only comprise two different poly-mers and form, for example respectively to form A and to form B and represent, wherein have at least a composition to comprise at least a separating polymer composition among A and the B, then has one by one the body layer at least in these three individual layer at least corresponding to forming A, have one by one the body layer at least corresponding to forming B, having at least two individual layer cooresponding is identical composition A or B.For example the repetitive of described composite bed only comprises three individual layer (as shown in Figure 3), respectively with 121,122,123 expressions, and with 121/122/123 expression repetitive, then wherein can form A (for example individual layer 122) corresponding to poly-mer by body layer one by one, two individual layer are formed B (for example individual layer 121 and 123) corresponding to poly-mer; Perhaps form B (for example individual layer 112) by body layer one by one corresponding to poly-mer, two individual layer are formed A (for example individual layer 121 and 123) corresponding to poly-mer; And other corresponding combinations etc.; In like manner, for the ease of clear each repetitive of distinguishing of inspector, the subscript difference of the individual layer of each repetitive, for example 121 ', 122 ', 123 ' or 121 ", 122 ", 123 ".These two different poly-mer compositions can be with A/B/A in repetitive, B/A/B, and A/A/B, four kinds of forms of B/B/A are arranged.Form when identical when adjacent individual layer corresponding polymers in the repetitive, those individual layer can be considered body layer one by one, thus in the utility model preceding two kinds in preferred above-mentioned four kinds of spread patterns.Because have in the stepped construction of the different above-mentioned repetitives of position two diverse locations corresponding to the individual layer of same composition A or the individual layer corresponding to same composition B of two diverse locations.Two thickness corresponding to the individual layer of same composition A can be inequality, and two thickness corresponding to the individual layer of same composition B also can be inequality.The thickness of the individual layer of forming corresponding to same polymer by the design diverse location can be prepared the composite bed membraneous material of different structure and function.But unless otherwise indicated, above-mentioned example structure, for example A/B/A and B/A/B only represent that the pairing poly-mer of individual layer of diverse location is formed, and do not comprise the thickness differential information of the individual layer of the diverse location that corresponding same polymer forms.Repetitive contains more than three individual layer and only to comprise situation and above-mentioned example that two poly-mers form similar, and those skilled in the art can understand easily, just repeat no more here.
In the utility model, for convenience's sake for forming, for example form A or B sometimes corresponding to a certain poly-mer, individual layer (perhaps individual layer), also be referred to as individual layer (perhaps individual layer) A or B.Like this, the permutation and combination that the structure of repetitive and composite bed and film just can directly be formed with its corresponding polymers in the utility model is represented.For example represent a repetitive with A/B/A, then only comprise two different poly-mers in this repetitive and form A and B that wherein two individual layer are corresponding to forming A, the body layer is corresponding to forming B one by one, and three individual layer are arranged with the A/B/A form.The obstruct composite bed that comprises the layer multiplication coextrusion of three individual layer repetitive A/B/A can be with (A/B/A)
nExpression, the number of times that the multiple of subscript n presentation layer multiplication or repetitive repeat; Comprising an obstruct composite bed and the single layer membrane structure of barrier corresponding to poly-mer composition C that comprises the layer multiplication coextrusion of three individual layer repetitive A/B/A can be with (A/B/A)
n/ C represents; The obstruct composite bed or the film that comprise the obstruct composite bed of the obstruct composite bed of a layer multiplication coextrusion that comprises three individual layer repetitive A/B/A and the layer multiplication coextrusion that comprises two individual layer repetitive C/D can be with (A/B/A)
n/ (C/D)
mExpression, wherein subscript m and subscript n are similar.The expression of other structures similarly.
When the repetitive in the obstruct composite bed of described layer multiplication coextrusion comprised more than three individual layer and comprises more than two poly-mers compositions, situation was also similar with above-mentioned example.Describe for the ease of more clearly understanding the utility model, get here to comprise five individual layer and comprise the example that three different poly-mers form.Suppose that three different poly-mers are formed respectively and represent to form A, B and C, then the combined situation of five individual layer corresponding polymers compositions has two A, two B and a C, two A, B and two C, A, two B and two C, three A, B and a C, A, three B and a C, A, a B and a C.Above-mentioned in theory each combination can have 120 kinds of arrangements, and forms that to have a composition among A, B and the C at least be that separating polymer is formed, so the repeat unit structure here is very abundant.When the composition of adjacent individual layer was identical, those individual layer can be equal to body layer one by one, so many here arrangement architectures are equal to but as previously mentioned.Fig. 4 has described the preferred structure of two kinds of repetitives of the present utility model.Five individual layer of the repetitive among Fig. 4 a can be for example two barrier layer A, a non-barrier layer B and two non-barrier layer C, with the C/A/B/A/C structural arrangement; Or for example barrier layer A, two non-barrier layer B and two non-barrier layer C, with the C/B/A/B/C structural arrangement; But the utility model is not limited thereto.The layer of five repetitives among Fig. 4 b can be for example barrier layer A, a barrier layer B and three barrier layer C, and with the C/B/C/A/C structural arrangement, but the utility model is not limited thereto.
In the barrier film of the present utility model except comprising the compound barrier layer that at least one layer multiplication extrude, can also comprise the barrier composite bed of one or more barrier individual layer or other non-layer multiplication method preparations, this has further enriched the design of packing again.The barrier composite bed of non-layer times method preparation can have and is similar to layer structure of the barrier composite bed of multiplication method preparation.
When the barrier composite bed, the barrier individual layer that except having the compound barrier layer that at least one layer multiplication extrude, also have other in the barrier film of the present utility model, during perhaps non-barrier composite bed, can optionally introduce one deck or multilayer interlayer and tack coat between these composite beds and/or the individual layer.Effects such as interlayer can play generally that resistance is wet, resistance light, hyperchromic, support; Tack coat can play close-burning effect between the different layers such as improving composite bed, individual layer, interlayer.
The component of polymer that can be used for barrier of the present utility model mainly refers to have the component of polymer of higher gas (oxygen) barrier, those separating polymer compositions include but not limited to ethylene-vinyl alcohol copolymer (EVOH), polyvinyl alcohol (PVA), polyamide (nylon 6, nylon 66, nylon 10, nylon 11, nylon 4-6, nylon 6-10, nylon 6-12, nylon 12, amorphous nylon, and MXD6 nylon etc.), polyacrylinitrile (PAN), polyvinylidene chloride (PVDC), polyethylene terephthalate (PET), PEN (PEN), polyvinylchloride (PVC), Kynoar (PVDF), high density polyethylene (HDPE) (HDPE), polypropylene (PP), polyimide (PEI), polypropylene imines (PAI), polyetheretherketone (PEEK), polyethylene oxide (PEO), liquid crystal polymer, ionomer based on ethene, the copolymer of ethene and beta-unsaturated esters, acrylonitrile and methacrylic acid copolymer, polyurethane engineering plastics, and their copolymer, condensation product, affixture, resultant of reaction and modifier 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.In the utility model, separating polymer can comprise more than a kind of above-mentioned component of polymer in forming, can be so that with above-mentioned separating polymer mixture of ingredients.The compositions such as one or more non-(low) separating polymer compositions, filler, additive, auxiliary agent that can also comprise other during separating polymer is formed.
Non-(low) separating polymer composition during barrier is formed generally plays enhancing, toughness reinforcing, promote bonding, effects such as cost-cutting, 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, unsaturated polyester (UP), biological polyester, polyethers, polyurethane, polysiloxane, the polystyrene Polymer, the 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, 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, the polyacrylic acid resinoid, polyethers polyurethane, polyesters polyurethane, polyolefins polyurethane, polyacrylic polyurethane, polycarbonate-based polyurethane, polydimethyl diloxanes (PDMS), polyethylene oxide (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.Can select for use one or more non-(low) separating polymer compositions and one or more separating polymer compositions to be combined into the separating polymer matrix in the utility model as required.
The filler composition that is used for the barrier composition can be various suitable organic and inorganic fillers, include but not limited to cellulose fibre, glass fibre, carbon black, graphite, dolomite, chalk, talcum, mica, calcium carbonate, clay, fly ash, glass powder, diatom earth, silica, zeolite, metal hydroxides, metallic oxide, metal sulfate, metal carbonate, and their modifier and reactant.The 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.In order to reach desirable effect, can select to fill more than a kind of filler composition.
Additive, auxiliary agent during separating polymer is formed mainly comprises as antioxidant, ultraviolet absorbent, heat stabilizer, light stabilizer, antistatic additive, lubricant, plasticizer, anticlogging agent, fire retardant, antiseize agent, inorganic/organic expander, foaming agent, coating material and pigment etc.Detailed additive can be consulted relevant handbook with auxiliary agent information.The technical personnel of plastics and rubber materials can reasonably be selected as required easily.
Non-barrier or low separating polymer are formed, it is the poly-mer composition in non-(low) barrier individual layer in the composite bed, general do not have good gas (oxygen) barrier function, and those are formed pairing non-barrier individual layer and generally play effects such as enhancing, toughness reinforcing, dispersion, bonding, sealing, waterproof, cost-cutting.During forming, those poly-mers comprise compositions such as one or more non-(low) separating polymer compositions and optional suitable filler, additive, auxiliary agent.Compositions such as those non-(low) separating polymer compositions and optional suitable filler, additive, auxiliary agent are consistent with corresponding composition in the above-mentioned barrier composition.At least a in non-(low) the preferred low density polyethylene (LDPE) of separating polymer composition (LDPE), linear low density polyethylene (LLDPE), ethylene-acrylic acid copolymer (EAA) and metallocene PE (mPE) in forming for non-(low) separating polymer in the utility model and the metallocene polypropylene (mPP).
Separating polymer in the barrier composite bed of barrier individual layer and other non-layer multiplication method preparations is formed, and optionally non-(low) separating polymer is formed consistent with corresponding polymer composition in above-mentioned barrier and non-(low) barrier individual layer.
Between composite bed and/or the individual layer, be between composite bed and the composite bed, between composite bed and the individual layer, between individual layer and the individual layer, optionally the poly-mer of one or more interlayer is formed consistent with non-(low) separating polymer composition in the above-mentioned non-barrier individual layer.
Can be used to each composite bed that bonds, the barrier individual layer, cohesiveness component of polymer in the tack coat of interlayer 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 and hydrogenated styrene based thermoplastic resin, and their copolymer, condensation product, affixture, modifier, reaction and modified product etc.Wherein copolymerization, condensation, addition, modification and reaction are consistent with above-mentioned corresponding description.The cooresponding cohesiveness poly-mer of an adhesive agent individual layer (individual layer) is formed can comprise at least a above-mentioned cohesiveness component of polymer, and optional other suitable polymers compositions, and optional compositions such as suitable filler, additive, auxiliary agent.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 tack coat.These cohesiveness component of polymer also can be used as the composition that other poly-mers are formed, as the interpolation blend composition that separating polymer is formed and non-(low) separating polymer is formed, in order in the cohesive force that increases under the situation that does not increase extra adhesive layer between adjacent layer.The bulking agent that those adhesive agents of part can be used as other component of polymer blend uses.
A layer multiplication method that is adopted in the utility model is a kind of feed steam to be cut apart-the stacked again extrusion method that converges operation repeatedly, each cuts apart-and stackedly again converge operation and all be accompanied by cutting apart major ingredient stream, width expansion and high shrinkage to branch's materials flow, and stacked again branch is sent away major ingredient fluid layer quantity and is multiplied, and major ingredient stream individual layer thickness reduces at double.Layer multiplication operation can be by for example Chinese utility application 200820229095.4 and 200820229641.4, and the layer multiplicator described in the Chinese invention patent application 200810072529.9 and other suitable layer multiplying assemblies, as U.S. Pat 3635444, carry out.
Result of study shows, adopts layer multiplication extrusion method can prepare the laminated material that contains many layers effectively.Multi-layer co-extruded more adjustable more flexibly than tradition at aspects such as the quantity of layer and the thickness of individual layer by the barrier composite bed that layer multiplication extruded, 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.In the utility model, form and repetitive comprises the obstruct composite bed of the layer multiplication coextrusion that is no less than two individual layer by two poly-mers selecting at least one preferably to comprise wherein to have at least a separating polymer to form, just can prepare rich and varied laminate film material.Form and wherein comprise the repetitive that at least one separating polymer forms and comprise obstruct composite bed and other barrier individual layer or the composite bed of body layer one by one at least by the poly-mer that contains at least that select to introduce other layers multiplication co-extrusion in addition, can further enrich structure, performance, price and the purposes of laminate film material again.Generally speaking, the barrier packaging film only comprises one and comprises the double compound barrier layer of coextrusion of two each and every one poly-mers are formed and wherein is made up of at least one barrier layer, just can have than the multi-layer co-extruded film of tradition excellent comprehensive performance more.Only adopt two poly-mers to form in the obstruct composite bed of each layer multiplication coextrusion, help reducing the quantity of material, save cost, also for the recovery and reuse of film etc. provide bigger may.
In the utility model, if only comprise the compound barrier layer that a repetitive that comprises two poly-mers compositions and wherein be made up of at least one barrier comprises the layer multiplication coextrusion of at least two individual layer in the barrier packaging film, do not comprise other individual layers or composite bed, then the preparation of compound barrier layer is generally finished by sublevel multiplication coextrusion.In the layer multiplication coextrusion process, at first the feed composition that each poly-mer in the film is formed is extruded materials flow by feeder and other accessory equipments of suitable quantity to the conveying of feed head, each feed steam tegillum in the feed head builds up the composite stream with ad hoc structure, this composite stream is cut apart-stacked again converging in the layer multiplicator in downstream repeatedly, after reaching certain number of plies amount, extrude by suitable extruder head.Composite stream after the feed head is stacked, its certain layer stack structure can be considered as repeat unit structure, also can be considered in some certain layer stack structures comprising many littler repeat unit structures when wherein individual layer quantity is even number.For example the composite stream after the feed head is stacked has the structure of A/B/A/B/A/B/A/B, if wherein each bulk layer thickness is suitable, then can be considered in this structure and is comprising repetition unit A/B/A/B or A/B.Generally only looking the structure of feed head after stacked in the utility model is repetitive.Wherein the feed head can be common multithread road feed head, the combination of diverter and common multithread road feed head, and increase a layer feed head.The feed composition that above-mentioned poly-mer is formed may not be formed identical with individual layer corresponding polymers in the final film, 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.
If comprise the obstruct composite bed of extruding more than one layer multiplication in the barrier packaging film, the composite bed of non-layer multiplication coextrusion and the individual layer etc. that perhaps also comprise other, the preparation of compound barrier layer generally be by with each composite bed or individual layer by one or more be similar to common multithread road feed head similarly the extruder head coextrusion of how divergent road finish.Can also pass through suitable annular extruder head and relevant device, carry out blown film and extrude.The thickness of the obstruct composite bed of a layer multiplication coextrusion preferably is not more than 2000 microns in the utility model, more preferably no more than 500 microns, most preferably between 10 microns to 200 microns.If needs are arranged, can preparing each composite bed or individual layer earlier respectively, to carry out laminated or direct co-extrusion part composite bed or individual layer more laminated with other composite bed or individual layer substep again.Extrude the technical personnel in field at Polymer and can select rational laminating method and necessary processing operation as required for use.Coextrusion or laminated after film can proceed follow-up processing such as unidirectional or biaxial tension.
The laminated of at least one superficial layer that comprises in the utility model and other assemblies also can adopt coetrusion, perhaps the laminated method of substep.Concrete operations and above-mentioned a plurality of composite beds or component layer laminated similar.Finally make lamination packing film material of the present utility model.
Because laminated material of the present utility model is a packaging film, so in the film preparation process, top layer near content in the fitness for purpose film is the layer that is easy to involution, and the material in this top layer of fitness for purpose has chemical inertness to content, liquid component in the content there is high barrier, each composition in the content is had low absorption.The component of polymer that generally can be used for interior surface layers 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, resultant of reaction etc.An interior surface layers can comprise above-mentioned at least a component of polymer and other suitable polymers compositions.
The outer surface layer fitness for purpose is water-fast, withstanding corrosion, easily printing, wear-resisting etc.The component of polymer that generally can be used for outer surface layer can include but not limited to 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, resultant of reaction etc.An outer surface layer can comprise above-mentioned at least a component of polymer and other suitable polymers compositions.
Can contain filler and auxiliary agent and additive equally in the surfaces externally and internally layer, but for interior surface layers, be benchmark with the non-toxic and safe.
The stacked packing film material of barrier of the present utility model can directly use as film, for example preservative film; Perhaps be processed to the containers such as bag, bag of different shape, for example the bag of the bag of pillow shape and other multiaspect builds etc.The personnel of this technical field can design processing as required.Packing are processed in the process of bag, bag etc., need carry out involution to material, its method comprises heat-sealing, bright eruption sealing, hot gas sealing, ultrasonic sealing, high frequency sealing etc.Those packing containers can be 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 film material of the present utility model, the structure of material can be by assembly selection and each assembly particularly the selection of the composite bed 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, packing film comprises the compound barrier layer of being extruded by layer multiplication mode that surfaces externally and internally layer and repetitive only comprise two individual layer.Described compound barrier layer is to be formed by being extruded by layer multiplication mode by repetitive.The corresponding respectively separating polymer of described two individual layer forms A and a non-separating polymer is formed B.In repetitive, a barrier individual layer is formed A corresponding to separating polymer: extrusion grade ethylene-vinyl alcohol copolymer (EVOH), non-barrier individual layer is formed the blend (LDPE+maLDPE) of B:95wt% low density polyethylene (LDPE) and the maleic anhydride modified low density polyethylene (LDPE) of 5wt% corresponding to non-separating polymer, and repeat unit structure is B/A.The outer surface layer poly-mer consists of polypropylene (PP), and the interior surface layers poly-mer consists of low density polyethylene (LDPE) (LDPE).
By two single screw extrusion machines, wherein one connects a bidirectional shunt device, provide the materials flow of fusion to a three-channel feed head, the initial stacked materials flow with repeat unit structure is again by 9 series connected double layers multiplicators of head and the tail, and total number of plies of compound barrier layer is 1024 layers; By a Duo Qi road extruder head, the surfaces externally and internally of extruding with two other extruder closes layer by layer, extrudes the about 100 microns film of thickness at last.Wherein, the surfaces externally and internally layer thickness is all about 20 microns; Each bulk layer thickness of repetitive is close in the film, and individual layer thickness is about 60 nanometers.
Can directly use by this packing film, also can be processed into containers such as suitable bag and bag and use as film.
Embodiment 2
In the present embodiment, only comprise an outer surface layer and the obstruct composite bed that layer multiplication extruded in the packing film material.Wherein repetitive has three individual layer, wherein only contains a barrier composition and a non-barrier and forms.One of them barrier individual layer is formed A corresponding to poly-mer: polyethylene oxide (PEO), two non-barrier individual layer are B/A/B corresponding to poly-mer composition B:97wt% polypropylene and the maleic anhydride modified polyacrylic compound repeat unit structure of 3wt%.The outer surface layer poly-mer consists of the compound of 95wt% polypropylene and 5wt% titanium dioxide.
Increase the materials flow that layer feed head provides fusion by two single screw extrusion machines and one, the initial stacked materials flow with repeat unit structure is again by 8 series connected double layers multiplicators, and total number of plies of compound barrier layer is 768 layers; By a clothes hanger type Duo Qi road extruder head, laminated at last with the outer surface layer that the another one extruder is extruded, extrude the about 100 microns film of thickness.About 50 microns of the thickness of compound barrier layer, each bulk layer thickness of repetitive is close in the film, and individual layer thickness is about 65 nanometers.
Embodiment 3
In the present embodiment, comprise an interior surface layers and the obstruct composite bed that layer multiplication extruded in the packing film, the repetitive that wherein intercepts composite bed comprises two individual layer, and wherein two individual layer are formed corresponding to same barrier.A separating polymer is formed A: the nylon 6 that nanoclay is filled builds up repetitive with the A/A Structural layer.The interior surface layers poly-mer consists of ethylene acrylic acid co polymer (EAA).
This packing film material adopts a coetrusion preparation.Wherein intercept composite bed by a dual channel feed head, 3 quadruple-layer multiplicators and 2 double layers multiplicators, the number of plies reaches 512 layers; Composite bed and interior surface layers are extruded into the film that thickness is about 100 microns by a bifid road extruder head, and wherein composite bed is about 50 microns, about 50 microns of interior surface layers.In these examples of implementation, the obstruct composite bed is actual to can be considered an individual layer, but owing to there being a layer multiplicative process in the course of processing, so still be described as composite bed.Wherein the flake nano clay obtains orientation in layer multiplicative process, and its aspect, plane is parallel to thin film planar to a great extent, can improve barrier greatly.
Embodiment 4
In the present embodiment, comprise an outer surface layer in the packing film, two obstruct composite beds that layer multiplication extruded, a tack coat and a barrier individual layer, the integral structure of membraneous material are outer surface layer/composite bed I/ composite bed II/ tack coat/individual layer.Wherein intercept composite bed I repetitive and have three individual layer, it is the compound of polyethylene terephthalate (PET) and nylon 66 nylon that the cooresponding separating polymer of barrier individual layer is formed A, it is ethylene-acrylic acid copolymer (EAA) that two cooresponding separating polymers of non-barrier individual layer are formed B, and the stepped construction of three individual layer is B/A/B.Intercept among the composite bed II, the cooresponding separating polymer of barrier individual layer is formed C: polyvinylchloride (PVC) and an amount of plasticizer and heat stabilizer, another barrier individual layer is formed D corresponding to non-separating polymer: polyacrylinitrile (PAN) and the additive that reduces fusing point in right amount build up repetitive with the C/D Structural layer.It is ethylene-vinyl acetate copolymer (EVA) that the poly-mer of tack coat is formed C; It is the polypropylene (BOPP) of biaxial tension that barrier individual layer corresponding polymers is formed D.Outer surface layer is a metallocene PE.
Outer surface layer/composite bed is by once extruding preparation.Increase the composite bed I materials flow that layer feed head provides fusion by two single screw extrusion machines and one, its structure is B/A/B/B/A/B/B/A/B; The initial stacked materials flow that is tentatively increased layer is again by 3 series connected quadruple-layer multiplicators, and the individuality of compound barrier layer I adds up to 576 layers layer by layer; In addition, provide the composite bed II materials flow of fusion by two extruders and common feed head, its structure is C/D; Reach 128 layers by 4 total numbers of plies of series connected quadruple-layer multiplicator individual layer; Then,, be pressed into the film of suitable thickness at last by the roller machine to extruding two obstruct composite beds on the bidirectional stretching polypropylene film that is coated with tack coat by extruding by a Duo Qi road extruder head with constant cross-sectional area.The thickness of two barrier composite beds is all about 50 microns in the film, and each bulk layer thickness of repetitive is close.About 20 microns of interior surface layers thickness.
Embodiment 5
In the present embodiment, the packing film material comprises an outer surface layer and the barrier composite bed that layer multiplication extruded.Intercept and comprise a barrier composition and a non-barrier composition in the composite bed.It is blown film level polyethylene terephthalate (PET) and PTT (PTN) alloy that the cooresponding separating polymer of one of them barrier individual layer is formed A, it is metallocene linear-low density polyethylene (mLLDPE) that two cooresponding non-separating polymers of non-barrier individual layer are formed B, and repeat unit structure is B/A/B.Outer surface layer is polypropylene (PP).
The preparation of film is undertaken by the method for fractional steps.
At first, increase a layer feed head by one, 3 quadruple-layer multiplicators and a double layers multiplicator, melting charge fluid layer number reaches 384 layers; Fusion materials flow after the layer multiplication is admitted to a suitable annular blown film extruder head, further is extruded into about 50 micron films of thickness by blown film.Obstruct composite bed film after the cutting and polypropylene outer surface layer are passed through the pressing of flame heat method, make final barrier film material.
The above, it only is the utility model preferred embodiment, so can not limit the scope that the utility model is implemented with this, i.e. the equivalence of doing according to the utility model claim and description changes and modifies, and all should still belong in the scope that the utility model patent contains.
Claims (10)
1. isolation laminated polymer packaging film, it is characterized in that: it comprises that at least one superficial layer and at least one lamination intercept composite bed, this superficial layer and lamination intercept composite bed and are laminated together, all contain a plurality of repetitives that adopt layer multiplication mode to extrude in this each obstruct composite bed, this each repetitive all comprises at least one to have pairing poly-mer composition and has at least a poly-mer to form the individual layer that contains a kind of separating polymer composition.
2. isolation laminated polymer packaging film according to claim 1 is characterized in that: it also comprises at least one laminated barrier individual layer that intercepts composite bed in lamination.
3. isolation laminated polymer packaging film according to claim 1 is characterized in that: it also comprises the laminated second barrier composite bed that intercepts composite bed in lamination of at least one non-layer multiplication coextrusion.
4. isolation laminated polymer packaging film according to claim 1, it is characterized in that: it also comprises at least one and laminatedly intercepts the barrier individual layer of composite bed in lamination, also is provided with at least one tack coat or/and at least one interlayer between described various barrier composite beds, individual layer and the superficial layer.
5. isolation laminated polymer packaging film according to claim 1 is characterized in that: it also comprises at least one and laminatedly intercepts the barrier individual layer of composite bed, the filler of filled polymer within this individual layer in lamination.
6. according to the described isolation laminated polymer packaging film of claim 1, it is characterized in that: it also comprises the laminated in the second barrier composite bed of lamination obstruct composite bed, the filler of filled polymer within this second barrier is compound of at least one non-layer multiplication coextrusion.
7. isolation laminated polymer packaging film according to claim 1, it is characterized in that: it also comprises at least one laminated barrier individual layer that intercepts composite bed in lamination, also be provided with at least one tack coat between described various barrier composite bed, individual layer and the superficial layer or/and at least one interlayer, the filler of filled polymer within this tack coat or the interlayer.
8. isolation laminated polymer packaging film according to claim 1 is characterized in that: the thickness of obstruct composite bed that this repetitive comprises the layer multiplication coextrusion of body layer one by one at least is not more than 2000 microns.
9. isolation laminated polymer packaging film according to claim 1 is characterized in that: the filler of filled polymer within this individual layer.
10. isolation laminated polymer packaging film according to claim 1 is characterized in that: the filler of filled polymer within this superficial layer.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201020179610XU CN201647345U (en) | 2010-05-05 | 2010-05-05 | Laminated polymer barrier packaging film |
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| CN201020179610XU CN201647345U (en) | 2010-05-05 | 2010-05-05 | Laminated polymer barrier packaging film |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103813964A (en) * | 2011-09-20 | 2014-05-21 | Cj第一制糖株式会社 | Packaging container |
| CN107662386A (en) * | 2016-07-27 | 2018-02-06 | 海口未来技术研究院 | High-resistant diaphragm for aerostatics and its preparation method and application |
| CN113002100A (en) * | 2021-03-31 | 2021-06-22 | 海南必凯水性新材料有限公司 | High-barrier composite film and preparation method thereof |
-
2010
- 2010-05-05 CN CN201020179610XU patent/CN201647345U/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103813964A (en) * | 2011-09-20 | 2014-05-21 | Cj第一制糖株式会社 | Packaging container |
| CN103813964B (en) * | 2011-09-20 | 2016-09-07 | Cj第一制糖株式会社 | Packing container |
| CN107662386A (en) * | 2016-07-27 | 2018-02-06 | 海口未来技术研究院 | High-resistant diaphragm for aerostatics and its preparation method and application |
| CN113002100A (en) * | 2021-03-31 | 2021-06-22 | 海南必凯水性新材料有限公司 | High-barrier composite film and preparation method thereof |
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