CN102555379A - Highly obstructed multilayer coextrusion thermal shrink film - Google Patents
Highly obstructed multilayer coextrusion thermal shrink film Download PDFInfo
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Abstract
The invention discloses a highly obstructed multilayer coextrusion thermal shrink film which comprises a heat sealing layer, an outer surface layer, an obstruction layer and a bonding layer, wherein the heat sealing layer, the outer surface layer and the obstruction layer are contacted with a packaged object, and the bonding layer connects the outer surface layer, the heat sealing layer and the obstruction layer; the heat sealing layer comprises polyolefin resin; the outer surface layer comprises polyethylene with middle density and the like; the obstruction layer comprises at least one layer of one out of ethylene-vinyl alcohol copolymer or polyamide or the mixture of the two; and the structure of the multilayer coextrusion thermal shrink film has 5-9 layers. The highly obstructed multilayer coextrusion thermal shrink film has good oxygen obstruction performance and higher tensile strength, and even objects sensitive to air cannot suffer from the risk that the color is changed or even aged or the food flavor is changed due to entrance of oxygen after being stored for a longer time. Furthermore, the structure of the outer layer can improve the optical property, the mechanical property, the surface printing capability and the stretching capability, and resist high temperature sealing and burning.
Description
Technical field
The present invention relates to the constituent structure of plastic sheeting, be specifically related to a kind of multi-layer co-extruded heat-shrinkable film of high-barrier.
Background technology
The packing of commodity for the storage of commodity, guarantee the quality, beautify and have important function.Shrink film has good bandwagon effect, and trade mark, icon, packed article are high-visible, beautiful and clean; Shrink closely light; Also have excellent toughness and deflection simultaneously, excellent package integrity properties can be provided in transportation and handling procedure, the shrinkage tensions of utilizing its high shrinkage to produce can be wrapped the one group of article that will pack; Be highly suitable for the assembly package of many article, especially excellent to the packing effect of special-shaped article.At the market initial stage, because the heat-shrinkable film price is higher, domestic except the high enterprise of packing instructions is used, market capacity is not very big.In recent years along with the raising of environmental consciousness; A lot of countries have forbidden or have limited the use of toxic packaging product; Though the domestic use that does not have clear and definite laws and regulations to forbid or limit poisonous packaging material; But receive the guiding and the regulation and control of international market, domestic a lot of enterprises have stopped the use of poisonous plastic flexible packaging material, then use high-grade environment-friendly type heat shrink films material.
Shrink film adopts polyvinyl chloride (PVC) or polyvinylidene chloride (PVDC) to do barrier layer mostly at present; But PVC, PVDC belong to thermosensitive polymer; Very responsive to high temperature, so processing is relatively more difficult, and contain the chlorion monomer; To plasticizing extrude and die head, machinery corrosivity very strong, bigger to the destruction of ozone layer simultaneously.
The disclosed EP1034076B1 of EUROPEAN PATENT OFFICE has discussed a kind of packaging film, but is called the thermal contraction thermoplastic multilayered film, and it has the heat-resisting skin of being processed by nylon (PA).Yet these 5 layers of structures; Do not have any vistanex (PO) layer as steam being isolated in outside screen layer; And lack outer PO layer and will cause extra high outside curling test; Follow with steam screen layer that highly weakens and the intensity that highly weakens, because ethylene-vinyl alcohol copolymer (EVOH) and PA all are exposed to moisture and do not receive any protection.
A kind of multilayer heat shrinkable film is disclosed in the International Patent Application WO 00/32393; Said heat shrink films has the skin of being made up of thermoplastic polymer's mixture; This skin has high melt point with respect to internal layer, has the generation that dystectic skin can prevent to burn phenomenon.The multilayer heat shrinkable film of preparation has excellent heat seal scope, and internal layer and skin all do not need crosslinked.But such packaging film lacks necessary transparency, glossiness, can't satisfy the require degree of various products to film.
Publication number is the multilayered packaging film that discloses the obstruct oxygen of a kind of U.S. Cryovac company application among the CN1216499A; Barrier layer employing evoh layer that uses in this technology and aramid layer and two extexines, two adhesive linkage structures; Though do not adopt the PVDC resin; Adopt the EVOH resin to do barrier layer, but adopt the method for complicated crosslinking with radiation and chemical crosslinking to realize the production of high shrinking film in the process.The multilayer coextruding pyrocondensation film and the production method thereof that the purpose of this invention is to provide a kind of high-barrier, it adopts multi-layer co-extruded film-blowing process to replace complicated " double bubble process ", " three bubble methods " to realize high shrinking film production.
Summary of the invention
The objective of the invention is to overcome the defective that exists in the prior art; A kind of multi-layer co-extruded heat-shrinkable film that adopts the high-barrier of multi-layer co-extruded film-blowing process production is provided; This film has good oxygen barrier property and higher draw tensile strength; Even to the responsive especially article of air in addition when the long storage after date, not have fully that occurrence of color changes and even risk aging or the change food flavor because oxygen gets into yet.And layer structure also can improve optical property, mechanical property, surface printing ability, stretch capability, high temperature resistant envelope and scald.
For realizing above-mentioned purpose, technical scheme of the present invention is the multi-layer co-extruded heat-shrinkable film of a kind of high-barrier of design, it is characterized in that said film comprises hot sealing layer, extexine, barrier layer and is connected the tack coat of said extexine, hot sealing layer and barrier layer.
Wherein optimized technical scheme is, said hot sealing layer comprises vistanex, its molecular weight 50,000～200,000, melt index 0.3～10g/10min.
Further optimized technical scheme is; Said hot sealing layer comprises low density polyethylene (LDPE), medium density polyethylene; Any one or its any mixture in the Ionomer of high density polyethylene (HDPE), LLDPE, metallocene PE, polypropylene, vinylacetate-ethylene copolymer, methacrylic acid-ethylene copolymer, ethylene-butyl acrylate copolymer, acid modification, said polyolefinic fusing point is 85～96 ℃.
Further optimized technical scheme also has, and the shared weight percent content of medium density polyethylene is 5wt%～35wt% in said hot sealing layer.
Optimized technical scheme also has, and said barrier layer comprises a kind of by in ethylene-vinyl alcohol copolymer or the polyamide of one deck at least, or its mixture.
Further optimized technical scheme also has, and the weight percent content of ethene is 20%～38% in said barrier layer.
Optimized technical scheme also has; Said extexine comprises medium density polyethylene; Any one or its any mixture in the Ionomer of high density polyethylene (HDPE), LLDPE, metallocene PE, polypropylene, vinylacetate-ethylene copolymer, methacrylic acid-ethylene copolymer, acid modification, the fusing point of said extexine is 85 ℃～125 ℃.
Optimized technical scheme also has, and said tack coat comprises vinylacetate-ethylene copolymer or maleic anhydride modified ethene polymers, and the density of said vinylacetate-ethylene copolymer is 0.93～0.94g/cm
3, the shared weight percentage of vinylacetate-ethylene copolymer is 5%～25% in said multi-layer co-extruded heat-shrinkable film.
Optimized technical scheme also has, and the structure of said multilayer coextruding pyrocondensation film is the 5-9 layer.
Optimized technical scheme also has, and in said hot sealing layer, extexine and barrier layer, is added with at least a in slipping agent, antitack agent, antistatic additive and the color masterbatch.
Advantage of the present invention and beneficial effect are: the multi-layer co-extruded heat-shrinkable film film of this high-barrier has good oxygen barrier property and higher draw tensile strength; Even to the responsive especially article of air in addition when the long storage after date, not have fully that occurrence of color changes and even risk aging or the change food flavor because oxygen gets into yet.And layer structure also can improve optical property, mechanical property, surface printing ability, stretch capability, high temperature resistant envelope and scald.
Description of drawings
Fig. 1 is 5 layers a structural representation in the multi-layer co-extruded heat-shrinkable film of high-barrier of the present invention;
Fig. 2 is 7 layers a structural representation in the multi-layer co-extruded heat-shrinkable film of high-barrier of the present invention;
Fig. 3 is 9 layers a structural representation in the multi-layer co-extruded heat-shrinkable film of high-barrier of the present invention.
The specific embodiment
Below in conjunction with accompanying drawing and embodiment, specific embodiments of the invention further describes.Following examples only are used for technical scheme of the present invention more clearly is described, and can not limit protection scope of the present invention with this.
The present invention is a kind of multi-layer co-extruded heat-shrinkable film of high-barrier, and this film comprises hot sealing layer, extexine, barrier layer and is connected the tack coat of said extexine, hot sealing layer and barrier layer.
In the present invention, said hot sealing layer comprises vistanex, its molecular weight 50,000～200,000, melt index 0.3～10g/10min.PO has advantageously realized needed steam screen layer, and can influence the sealability of internal layer, promptly possibly can realize high heat-sealing strength under the heat-sealing temperature minimum.Said hot sealing layer comprises low density polyethylene (LDPE), medium density polyethylene; Any one or its any mixture in the Ionomer of high density polyethylene (HDPE), LLDPE, metallocene PE, polypropylene, vinylacetate-ethylene copolymer, methacrylic acid-ethylene copolymer, ethylene-butyl acrylate copolymer, acid modification, said polyolefinic fusing point is 85～96 ℃.The shared weight percent content of medium density polyethylene is 5wt%～35wt% in said hot sealing layer.The weight content of medium density polyethylene can also be 1wt%～50wt%, more preferably 10wt%～20wt%.
Embodiment preferred also has in the present invention, and said barrier layer comprises a kind of by in ethylene-vinyl alcohol copolymer or the polyamide of one deck at least, or its mixture.The weight percent content of ethene is 20%～38% in said barrier layer.
Embodiment preferred also has in the present invention; Said extexine comprises medium density polyethylene; Any one or its any mixture in the Ionomer of high density polyethylene (HDPE), LLDPE, metallocene PE, polypropylene, vinylacetate-ethylene copolymer, methacrylic acid-ethylene copolymer, acid modification, the fusing point of said extexine is 85 ℃～125 ℃.This top layer has the advantages that wearability is good, smooth, processability is good.
Embodiment preferred also has in the present invention, and said tack coat (Tie) comprises vinylacetate-ethylene copolymer or maleic anhydride modified ethene polymers, and the density of said vinylacetate-ethylene copolymer is 0.93～0.94g/cm
3, the shared weight percentage of vinylacetate-ethylene copolymer is 5%～25% in said multi-layer co-extruded heat-shrinkable film.
Embodiment preferred also has in the present invention, and the structure of said multilayer coextruding pyrocondensation film is the 5-9 layer.Five-layer structure wherein, that is, each layer material is from top to bottom: PO/Tie/EVOH/Tie/PO; Or seven-layer structure, that is, each layer material is PO/Tie/PA/EVOH/PA/Tie/PO from top to bottom; Or nine layers of structure, that is, each layer material is PET/Tie/PO/Tie/PA/EVOH/PA/Tie/PO from top to bottom.
Embodiment preferred also has in the present invention, in said hot sealing layer, extexine and barrier layer, is added with at least a in slipping agent, antitack agent, antistatic additive and the color masterbatch.
Embodiment 1
Structure is the five-layer co-squeezing heat-shrinkable film shown in accompanying drawing 1, and this multi-layer co-extruded shrinkable film is by two-layer vistanex (A and E), and one deck ethylene-vinyl alcohol copolymer barrier layer (C) constitutes with two-layer binding material (B and D).The thickness proportion of each layer is A: B: C: D: E=30%: 15%: 10%: 15%: 30%, and the heat sealability of this structural membrane is good, has to hinder oxygen and the wet ability of resistance preferably.
Ground floor A is by the mixture (weight content scope be 0%～60%) of an extruder with primary raw material resin ethylene-alpha-olefin copolymer or multiple ethylene-alpha-olefin copolymer, and wherein the alhpa olefin weight content is 1%～20%; The copolymer of ethene and EMAA [being ethene-(methyl) acrylic acid zinc salt, sodium salt, lithium salts plasma key condensate], EVA (ethene and acetate copolymer), EBA (butyl acrylate and ethylene copolymer); Wherein carboxylic acid monomer's weight content is 5%～25%; After in extruder front end mixed-hopper, evenly stirring; Under 160～280 ℃,, clamp-on in the runner of ground floor A of mould resin plasticizing;
Second layer B by an extruder, under 160～280 ℃, with jointing material resin plasticizing, clamp-ons in the runner of second layer B of mould;
The 3rd layer of C respectively by an extruder, under 160～280 ℃, with EVOH resin plasticizing, clamp-ons in the runner of the 3rd layer of C of mould;
The 4th layer of D by an extruder, under 160～280 ℃, with jointing material resin plasticizing, clamp-ons in the runner of the 4th layer of D of mould;
Layer 5 E,, under 160～280 ℃, with the resin plasticizing, is clamp-oned in the runner of five layers of E of mould after in extruder front end mixed-hopper, evenly stirring primary raw material resin PO and additive by an extruder.
Embodiment 2
Structure is the five-layer co-squeezing heat-shrinkable film shown in accompanying drawing 2, and this multi-layer co-extruded shrinkable film is by two-layer vistanex (A and G), and two-layer PA barrier layer (C and E), one deck ethylene-vinyl alcohol copolymer barrier layer (D) constitute with two-layer binding material (B and F).The thickness proportion of each layer is A: B: C: D: E: F: G=27%: 15%: 8%: 8%: 8%: 15%: 17%.Have good oxygen and steam barrier, high shrinkage factor can be used for the fresh-keeping shrink wrapping of cold fresh meat and cheese.
The A of the superiors is by the mixture (weight content scope be 0%～60%) of an extruder with primary raw material resin ethylene-alpha-olefin copolymer or multiple ethylene-alpha-olefin copolymer, and wherein the alhpa olefin weight content is 1%～20%; The copolymer of ethene and EMAA, EVA, EBA, wherein carboxylic acid monomer's weight content is 5%～25%, after in extruder front end mixed-hopper, evenly stirring, under 160～280 ℃, with the resin plasticizing, clamp-ons in the runner of the A of the superiors of mould;
Second layer B by an extruder, under 160～280 ℃, with jointing material resin plasticizing, clamp-ons in the runner of second layer B of mould;
The 3rd layer of C and layer 5 E respectively by an extruder, after primary raw material resin PA and additive evenly stirred in extruder front end mixed-hopper, under 220～280 ℃, with the resin plasticizing, clamp-on in the runner of the 3rd layer of C and layer 5 E of mould;
The 4th layer of D respectively by an extruder, under 160～280 ℃, with EVOH resin plasticizing, clamp-ons in the runner of the 4th layer of D of mould;
Layer 6 F by an extruder, under 160～280 ℃, with jointing material resin plasticizing, clamp-ons in the runner of layer 6 F of mould;
Layer 7 G,, under 160～280 ℃, with the resin plasticizing, is clamp-oned in the runner of seven layers of G of mould after in extruder front end mixed-hopper, evenly stirring main vistanex PO and additive by an extruder.
Embodiment 3
Structure is the five-layer co-squeezing heat-shrinkable film shown in accompanying drawing 3; This multi-layer co-extruded shrink film is by outer ethylene diester (PET (A)) two-layer vistanex (C and I), and two-layer PA barrier layer (E and G), one deck ethylene-vinyl alcohol copolymer barrier layer (F) constitute with three layers of binding material (B, D and H).Have good oxygen and steam barrier, high shrinkage factor, the surface is undertaken the printing of effective, can be used for the fresh-keeping shrink wrapping of cold fresh meat and cheese.
The A of the superiors,, under 160～280 ℃, with the resin plasticizing, is clamp-oned in the runner of the A of the superiors of mould after in extruder front end mixed-hopper, evenly stirring primary raw material resin PET and additive by an extruder;
Second layer B by an extruder, under 160～280 ℃, with jointing material resin plasticizing, clamp-ons in the runner of second layer B of mould;
The 3rd layer of C is by the mixture (weight content scope be 0%～60%) of an extruder with primary raw material resin ethylene-alpha-olefin copolymer or multiple ethylene-alpha-olefin copolymer, and wherein the alhpa olefin weight content is 1%～20%; The copolymer of ethene and EMAA, EVA, EBA, wherein carboxylic acid monomer's weight content is 5%～25%, after in extruder front end mixed-hopper, evenly stirring, under 160～280 ℃, with the resin plasticizing, clamp-ons in the runner of three layers of C of mould;
The 4th layer of D by an extruder, under 160～280 ℃, with jointing material resin plasticizing, clamp-ons in the runner of the 4th layer of D of mould;
Layer 5 E and layer 7 G respectively by an extruder, after primary raw material resin PA and additive evenly stirred in extruder front end mixed-hopper, under 220～280 ℃, with the resin plasticizing, clamp-on in the runner of layer 5 E and layer 7 G of mould;
Layer 6 F respectively by an extruder, under 160～280 ℃, with EVOH resin plasticizing, clamp-ons in the runner of layer 6 F of mould;
The 8th layer of H by an extruder, under 160～280 ℃, with jointing material resin plasticizing, clamp-ons in the runner of the 8th layer of H of mould;
The 9th layer of I,, under 160～280 ℃, with the resin plasticizing, clamp-oned in the runner of nine layers of I of mould after in extruder front end mixed-hopper, evenly stirring primary raw material resin PO and additive by an extruder.
According to the demands of different of product, can carry out corona treatment with suitable power with film through corona treatment plant, make film reach suitable moistened surface tension force.
The hot water shrinkage of the multi-layer co-extruded heat-shrinkable film of the above high-barrier, vertical in 80 ℃ of water/horizontal＞20～50%, its hot strength>=28pa, elongation at break>=500, light transmittance＞88, OTR oxygen transmission rate≤20cm
3/ m
224H0.1mpa, rate of perviousness≤4g/m
224H.
The above only is a preferred implementation of the present invention; Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from know-why of the present invention; Can also make some improvement and retouching, these improvement and retouching also should be regarded as protection scope of the present invention.
Claims (10)
1. the multi-layer co-extruded heat-shrinkable film of a high-barrier is characterized in that, said film comprises hot sealing layer, extexine, barrier layer and is connected the tack coat of said extexine, hot sealing layer and barrier layer.
2. the multi-layer co-extruded heat-shrinkable film of high-barrier as claimed in claim 1 is characterized in that, said hot sealing layer comprises vistanex, its molecular weight 50,000～200,000, melt index 0.3～10g/10min.
3. the multi-layer co-extruded heat-shrinkable film of high-barrier as claimed in claim 2; It is characterized in that; Said hot sealing layer comprises low density polyethylene (LDPE), medium density polyethylene; Any one or its any mixture in the Ionomer of high density polyethylene (HDPE), LLDPE, metallocene PE, polypropylene, vinylacetate-ethylene copolymer, methacrylic acid-ethylene copolymer, ethylene-butyl acrylate copolymer, acid modification, said polyolefinic fusing point is 85～96 ℃.
4. the multi-layer co-extruded heat-shrinkable film of high-barrier as claimed in claim 3 is characterized in that, the shared weight percent content of medium density polyethylene is 5wt%～35wt% in said hot sealing layer.
5. the multi-layer co-extruded heat-shrinkable film of high-barrier as claimed in claim 1 is characterized in that, said barrier layer comprises a kind of by in ethylene-vinyl alcohol copolymer or the polyamide of one deck at least, or its mixture.
6. the multi-layer co-extruded heat-shrinkable film of high-barrier as claimed in claim 5 is characterized in that, the weight percent content of ethene is 20%～38% in said barrier layer.
7. the multi-layer co-extruded heat-shrinkable film of high-barrier as claimed in claim 1; It is characterized in that; Said extexine comprises medium density polyethylene; Any one or its any mixture in the Ionomer of high density polyethylene (HDPE), LLDPE, metallocene PE, polypropylene, vinylacetate-ethylene copolymer, methacrylic acid-ethylene copolymer, acid modification, the fusing point of said extexine is 85 ℃～125 ℃.
8. the multi-layer co-extruded heat-shrinkable film of high-barrier as claimed in claim 1; It is characterized in that; Said tack coat comprises vinylacetate-ethylene copolymer or maleic anhydride modified ethene polymers, and the density of said vinylacetate-ethylene copolymer is 0.93～0.94g/cm
3, the shared weight percentage of vinylacetate-ethylene copolymer is 5%～25% in said multi-layer co-extruded heat-shrinkable film.
9. the multi-layer co-extruded heat-shrinkable film of high-barrier as claimed in claim 1 is characterized in that, the structure of said multilayer coextruding pyrocondensation film is the 5-9 layer.
10. the multi-layer co-extruded heat-shrinkable film of high-barrier as claimed in claim 1 is characterized in that, in said hot sealing layer, extexine and barrier layer, is added with at least a in slipping agent, antitack agent, antistatic additive and the color masterbatch.
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Application publication date: 20120711 |