CN115625955A - Multilayer environment-friendly heat-resistant and heat-insulating shrinkable film and preparation method thereof - Google Patents
Multilayer environment-friendly heat-resistant and heat-insulating shrinkable film and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000010410 layer Substances 0.000 claims abstract description 141
- 230000004888 barrier function Effects 0.000 claims abstract description 68
- 229920006257 Heat-shrinkable film Polymers 0.000 claims abstract description 51
- 239000002344 surface layer Substances 0.000 claims abstract description 44
- 239000012793 heat-sealing layer Substances 0.000 claims abstract description 42
- 239000012790 adhesive layer Substances 0.000 claims description 23
- 238000001125 extrusion Methods 0.000 claims description 23
- 239000004952 Polyamide Substances 0.000 claims description 18
- 239000004698 Polyethylene Substances 0.000 claims description 18
- 238000003851 corona treatment Methods 0.000 claims description 18
- 229920002647 polyamide Polymers 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 18
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims description 14
- 239000000498 cooling water Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000012528 membrane Substances 0.000 claims description 10
- -1 polyethylene Polymers 0.000 claims description 10
- 229920001526 metallocene linear low density polyethylene Polymers 0.000 claims description 9
- 229920000573 polyethylene Polymers 0.000 claims description 9
- 238000007664 blowing Methods 0.000 claims description 6
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 5
- 238000009998 heat setting Methods 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- 230000007613 environmental effect Effects 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 5
- 238000011084 recovery Methods 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000003475 lamination Methods 0.000 abstract description 3
- 239000003607 modifier Substances 0.000 abstract description 3
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- 239000004033 plastic Substances 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 3
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 8
- 238000004064 recycling Methods 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- TYAHIHMYMVZOEC-UHFFFAOYSA-N 2-[2-(2-hydroxyphenyl)ethyl]phenol Chemical compound OC1=CC=CC=C1CCC1=CC=CC=C1O TYAHIHMYMVZOEC-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000005003 food packaging material Substances 0.000 description 1
- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical compound OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920006112 polar polymer Polymers 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
- B32B37/1284—Application of adhesive
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/0008—Electrical discharge treatment, e.g. corona, plasma treatment; wave energy or particle radiation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/0012—Mechanical treatment, e.g. roughening, deforming, stretching
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
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- B32B2307/70—Other properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
The invention relates to the technical field of preparation of heat shrinkable film materials, in particular to a multilayer environment-friendly barrier heat shrinkable film and a preparation method thereof, wherein the multilayer environment-friendly barrier heat shrinkable film comprises seven layers of heat shrinkable films or nine layers of heat shrinkable films; the nine layers of heat shrinkable films sequentially comprise a first surface layer, a first structural layer, a first barrier layer, a second structural layer and a first heat sealing layer from top to bottom, wherein first bonding layers are arranged among the first surface layer, the first structural layer, the first barrier layer, the second structural layer and the first heat sealing layer; the seven layers of heat-shrinkable films sequentially comprise a second surface layer, a second barrier layer, a third structural layer and a second heat-sealing layer from top to bottom; and second bonding layers are arranged among the second surface layer, the second barrier layer, the third structural layer and the second heat sealing layer. The invention adopts polymer modifier for compatibilization and ultrathin lamination, so that the prepared heat shrinkable film has good coating and dispersing effects of polar components, can be incorporated into a PE recovery system, and is used for manufacturing new film materials or plastic products.
Description
Technical Field
The invention relates to the technical field of preparation of heat shrinkable film materials, in particular to a multilayer environment-friendly barrier heat shrinkable film and a preparation method thereof.
Background
Heretofore, film scraps containing polar polymers such as EVOH, nylon and the like have been difficult to recycle, and they have not been dispersed in a polyolefin matrix for recycling and reuse. Previous recycling attempts have found that the processability of the material can be reduced and the optical properties can be affected. For many brand owners and manufacturers, processability and optical properties are two key performance requirements. Millions of kilograms of barrier films end up being landfilled, both as a waste and as a pollution to the environment, so there is an urgent need to develop a multilayer barrier film that can be effectively recycled to incorporate a PE recycling system without affecting the quality of the recycled product.
Disclosure of Invention
The invention aims to solve the defects in the prior art, and provides a multilayer environment-friendly heat-resistant and heat-insulating shrinkable film and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a multilayer environment-friendly heat-resistant and heat-insulating shrinkable film comprises seven layers of heat-shrinkable films or nine layers of heat-shrinkable films;
the nine layers of heat shrinkable films sequentially comprise a first surface layer, a first structural layer, a first barrier layer, a second structural layer and a first heat sealing layer from top to bottom, wherein first bonding layers are arranged among the first surface layer, the first structural layer, the first barrier layer, the second structural layer and the first heat sealing layer;
the seven layers of heat-shrinkable films sequentially comprise a second surface layer, a second barrier layer, a third structural layer and a second heat-sealing layer from top to bottom; second adhesive layers are arranged among the second surface layer, the second barrier layer, the third structural layer and the second heat sealing layer;
the first surface layer and the second surface layer are both Metallocene Linear Low Density Polyethylene (MLLDPE) or Polyamide (PA), and 0.02-0.5% of erucamide is added into the first surface layer and the second surface layer, so that the first surface layer and the second surface layer can bear the high temperature of more than 70 ℃, and the transparency degree and the opening effect are ensured; the total proportion of the first surface layer or the second surface layer is 5-15%;
the first barrier layer and the second barrier layer are both ethylene-vinyl alcohol copolymer (EVOH) and provide gas barrier capacity, and the total proportion of the first barrier layer or the second barrier layer is 5-15%;
the first structural layer, the second structural layer and the third structural layer are all Polyamide (PA) and provide certain mechanical strength, and the total proportion of the first structural layer, the second structural layer or the third structural layer is 10-30%;
the first heat-sealing layer and the second heat-sealing layer are both polyethylene (m-PE) added with ethylene acrylic acid copolymer (EBA), and have certain heat shrinkage, the total proportion of the first heat-sealing layer or the second heat-sealing layer is 20-40%, and the ethylene acrylic acid copolymer (EBA) accounts for 10-80% of the first heat-sealing layer or the second heat-sealing layer;
the first adhesive layer (TIE) and the second adhesive layer (TIE) are both maleic anhydride grafted linear polyethylene (PE-G-MAH), have adhesive effect, can compatibilize EVOH and PA and enhance the dispersibility in a polyolefin matrix, and the proportion of the first adhesive layer or the second adhesive layer is 5-15%.
Preferably, the total thickness of the heat-shrinkable film is 80 μm or less, and the thickness of each monolayer material is controlled to improve the covering property of the polar component during the recycling process.
The invention also provides a preparation method of the multilayer environment-friendly barrier heat shrinkable film, which comprises the following steps:
step 1), preparing a first tube membrane: melting raw materials of each layer by a screw rod, feeding the raw materials into a seven-layer or nine-layer circular extruder for extrusion, superposing the raw materials to form a film blank, carrying out first inflation stretching, and immediately carrying out rapid cooling molding by using cooling water to form a first tubular film;
step 2), preparing a second tube membrane: the first tube film enters a heating system, and compressed air is filled into the tube film for secondary blowing to obtain a second tube film;
step 3), corona treatment: and performing heat setting and corona treatment on the second tube film to obtain the multilayer environment-friendly barrier heat shrinkable film.
Preferably, in step 1), the circular extruder inlet is an hourglass-shaped inlet.
Preferably, in step 1), the polyamide of the raw material used has an extrusion temperature of 210 to 250 ℃; the extrusion temperature of the ethylene-vinyl alcohol copolymer is 170-225 ℃; the extrusion temperature of the metallocene linear low density polyethylene and the polyethylene is 160-220 ℃; the extrusion temperature of the first adhesive layer or the second adhesive layer is 150-210 ℃.
Preferably, in step 1), the first inflation stretching forms 1-2 times of longitudinal stretching and 1-1.5 times of transverse stretching; the cooling water temperature is 5-20 ℃.
Preferably, in step 2), the heating system temperature is 60-90 ℃.
Preferably, in step 2), the second blow forms 3 to 6 times the transverse stretch and 2 to 4 times the longitudinal stretch.
Wherein, in the step 3), the corona treatment is only carried out on the surface of the heat-sealing layer with the corona treatment of not less than 35 dynes, so that the adhesion is improved.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention adopts polymer modifier for compatibilization and ultrathin lamination, so that the prepared heat shrinkable film has good coating and dispersing effects of polar components, can be incorporated into a PE recovery system, and is used for manufacturing new film materials or plastic products.
2. The multilayer environment-friendly barrier heat shrinkable film prepared by the invention contains more than 7 layers of film materials, the tensile strength of the film materials is more than 80MPa, and the oxygen transmission capacity is less than 20cm 3 /(m 2 24h 0.1 MPa) water vapor transmission rate of less than 15 g/(m) 2 24 h), penetrationThe lightness is more than 85 percent, can be used as a high-performance environment-friendly food packaging material, and has larger market application potential.
Drawings
FIG. 1 is a flow chart of the production process of the present invention;
FIG. 2 is a schematic structural view of a 9-layer environmental-friendly heat-shrinkable barrier film according to the present invention;
FIG. 3 is a schematic view of a 7-layer environmentally friendly barrier heat shrinkable film of the present invention;
fig. 4 is a schematic cross-sectional view of an hourglass-shaped inlet according to the present invention.
In the figure: 1 a first surface layer, 2 a first structural layer, 3 a first barrier layer, 4 a second structural layer, 5 a first heat sealing layer, 6 a first adhesive layer, 7 a second surface layer, 8 a second barrier layer, 9 a third structural layer, 10 a second heat sealing layer and 11 a second adhesive layer.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings, so that those skilled in the art can better understand the advantages and features of the present invention, and thus the scope of the present invention is more clearly defined. The embodiments described herein are only a few embodiments of the present invention, rather than all embodiments, and all other embodiments that can be derived by one of ordinary skill in the art based on the embodiments described herein are intended to be within the scope of the present invention.
A multilayer environment-friendly heat-resistant heat-insulating shrinkable film comprises seven layers of heat-shrinkable films or nine layers of heat-shrinkable films;
the nine layers of heat shrinkable films sequentially comprise a first surface layer 1, a first structural layer 2, a first barrier layer 3, a second structural layer 4 and a first heat sealing layer 5 from top to bottom, and first bonding layers 6 are arranged among the first surface layer 1, the first structural layer 2, the first barrier layer 3, the second structural layer 4 and the first heat sealing layer 5;
the seven layers of heat-shrinkable films sequentially comprise a second surface layer 7, a second barrier layer 8, a third structural layer 9 and a second heat-sealing layer 10 from top to bottom; second bonding layers 11 are arranged among the second surface layer 7, the second barrier layer 8, the third structural layer 9 and the second heat sealing layer 10;
the first surface layer 1 and the second surface layer 7 are both Metallocene Linear Low Density Polyethylene (MLLDPE) or Polyamide (PA), and 0.02-0.5% of erucamide is added to the first surface layer 1 and the second surface layer 7, so that the paint can bear the high temperature of more than 70 ℃, and the transparency and the opening effect are ensured; the total proportion of the first surface layer 1 or the second surface layer 7 is 5-15%;
the first barrier layer 3 and the second barrier layer 8 are both ethylene-vinyl alcohol copolymer (EVOH) and provide gas barrier capacity, and the total proportion of the first barrier layer 3 or the second barrier layer 8 is 5-15%;
the first structural layer 2, the second structural layer 4 and the third structural layer 9 are all Polyamide (PA) and provide certain mechanical strength, and the total proportion of the first structural layer 2, the second structural layer 4 or the third structural layer 9 is 10-30%;
the first heat-sealing layer 5 and the second heat-sealing layer 10 are both polyethylene (m-PE) added with ethylene acrylic acid copolymer (EBA), and have certain heat shrinkage, the total proportion of the first heat-sealing layer 5 or the second heat-sealing layer 10 is 20-40%, and the ethylene acrylic acid copolymer (EBA) accounts for 10-80% of the first heat-sealing layer 5 or the second heat-sealing layer 10;
the first adhesive layer 6 (TIE) and the second adhesive layer 11 (TIE) are both maleic anhydride grafted linear polyethylene (PE-G-MAH), have an adhesive effect, can compatibilize EVOH and PA and enhance the dispersibility in a polyolefin matrix, and the proportion of the first adhesive layer 6 or the second adhesive layer 11 is 5-15%.
Wherein the first surface layer 1 or the second surface layer 7 as a whole accounts for 5-15%, such as 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, etc.
The total proportion of the first barrier layer 3 or the second barrier layer 8 is 5 to 15%, for example, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, etc.
The first structural layer 2, second structural layer 4 or third structural layer 9 may be present in an overall proportion of 10-30%, such as 10%, 12%, 14%, 16%, 18%, 20%, 22%, 24%, 26%, 28%, 30% etc.
The first heat-seal layer 5 or the second heat-seal layer 10 may be present in an overall proportion of 20-40%, for example 20%, 22%, 24%, 26%, 28%, 30%, 32%, 34%, 36%, 38%, 40%, etc.
The proportion of the first adhesive layer 6 or the second adhesive layer 11 is 5 to 15%, for example, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, etc.
Specifically, the total thickness of the heat-shrinkable film is less than or equal to 80 μm, the thickness of each single-layer material is controlled, and the coating property of the polar components in the recycling process is improved.
A preparation method of a multilayer environment-friendly barrier heat-shrinkable film comprises the following steps:
step 1), preparing a first tube membrane: melting raw materials of each layer by a screw rod, extruding the raw materials in a seven-layer or nine-layer circular extruder, superposing the raw materials to form a film blank, carrying out primary inflation stretching, and immediately carrying out rapid cooling molding by cooling water to form a first tubular film;
step 2), preparing a second tube membrane: the first tube film enters a heating system, and compressed air is filled into the tube film for secondary blowing to obtain a second tube film;
step 3), corona treatment: and performing heat setting and corona treatment on the second tube film to obtain the multilayer environment-friendly barrier heat shrinkable film.
Wherein in the step 1), the inlet of the circular extruder is an hourglass-shaped inlet; the extrusion temperature of polyamide of the raw materials is 210-250 ℃; the extrusion temperature of the ethylene-vinyl alcohol copolymer is 170-225 ℃; the extrusion temperature of the metallocene linear low-density polyethylene and the polyethylene is 160-220 ℃; the extrusion temperature of the first adhesive layer or the second adhesive layer is 150-210 ℃; the first blowing and stretching forms 1-2 times of longitudinal stretching and 1-1.5 times of transverse stretching; the cooling water temperature is 5-20 ℃.
Wherein, in the step 2), the temperature of the heating system is 60-90 ℃; the second blow-up results in 3-6 times transverse stretch and 2-4 times longitudinal stretch.
Wherein, in the step 3), the corona treatment is only carried out on the surface of the heat-sealing layer with the corona treatment of not less than 35 dynes, so that the adhesion is improved.
Example 1
The preparation method of the 7-layer environment-friendly barrier heat shrinkable film comprises the following steps:
step 1), preparing a first tube membrane: melting raw materials of each layer by a screw, feeding the raw materials into a 7-layer circular extruder through a hourglass-shaped inlet of each layer, extruding, stacking the raw materials to form a film blank, performing first inflation stretching, and immediately performing rapid cooling molding by using cooling water to form a first tubular film;
wherein the function of the 7 layers is positioned as second surface layer/second TIE/second barrier layer/second TIE/third structural layer/second TIE/second heat seal layer; the second surface layer adopts PA, contains 0.02 percent of erucamide, accounts for 10 percent, and the extrusion temperature is 230 ℃; the second barrier layer is made of EVOH with the proportion of 10%, and the extrusion temperature is 220 ℃; the third structural layer adopts PA, the proportion is 20%, and the extrusion temperature is 230 ℃; the second heat sealing layer is made of m-PE, contains 60% of EBA (ethylene-bis-phenol) in a proportion of 30%, and has an extrusion temperature of 210 ℃; the second TIE adopts PE-G-MAH, each layer accounts for 10%, and the extrusion temperature is 200 ℃;
wherein the first blow-stretch forms 1.5 times of longitudinal stretch and 1.2 times of transverse stretch;
wherein the cooling water temperature is 10 ℃.
Step 2), preparing a second tube membrane: the first tube film enters a heating system, and compressed air is filled into the tube film for secondary blowing to obtain a second tube film;
wherein the temperature of the heating system is 70 ℃;
wherein the second blow forms 3.5 times the transverse stretch and 2.5 times the longitudinal stretch.
Step 3), corona treatment: the second tube film is subjected to heat setting and corona treatment to prepare a multilayer environment-friendly barrier heat shrinkable film;
wherein, the corona treatment is only to carry out 35 dyne corona treatment on the surface of the heat-sealing layer;
wherein the thickness of the multilayer environment-friendly barrier heat shrinkable film is less than 70 mu m.
The multilayer environment-friendly barrier heat shrinkable film can be brought into a PE recovery system for recycling, the tensile strength of the multilayer environment-friendly barrier heat shrinkable film can reach 70MPa, and the oxygen transmission capacity is less than 20cm 3 /(m 2 24 h.0.1 MPa), water vapor transmission rate of less than 15 g/(m) 2 24 h) transparency greater than 85%.
Example 2
The preparation method of the 9-layer environment-friendly barrier heat shrinkable film comprises the following steps:
step 1), preparing a first tube membrane: melting raw materials of each layer by a screw, feeding the raw materials into a 9-layer circular extruder through a hourglass-shaped inlet of each layer, extruding, stacking the raw materials to form a film blank, performing first inflation stretching, and immediately performing rapid cooling molding by using cooling water to form a first tubular film;
wherein the 9 layers are functionally oriented as first surface layer/first TIE/first structural layer/first TIE/first barrier layer/first TIE/second structural layer/first TIE/first heat seal layer; the first surface layer adopts MLLDPE, contains 0.08 percent of erucamide, accounts for 15 percent, and has the extrusion temperature of 205 ℃; the first barrier layer is made of EVOH (ethylene vinyl alcohol), the proportion is 15%, and the extrusion temperature is 210 ℃; the first structural layer or the second structural layer adopts PA, the total proportion is 30%, and the extrusion temperature is 220 ℃; the first heat sealing layer is made of m-PE and contains 40% of EBA (ethylene-butylene-styrene) accounting for 20%, and the extrusion temperature is 210 ℃; the first TIE adopts PE-G-MAH, each layer accounts for 5%, and the extrusion temperature is 180 ℃;
wherein the first blow-stretch forms 2 times of longitudinal stretch and 1.5 times of transverse stretch;
wherein the cooling water temperature is 5 ℃.
Step 2), preparing a second tube membrane: the first tube film enters a heating system, and compressed air is filled into the tube film for secondary blowing to obtain a second tube film;
wherein the temperature of the heating system is 80 ℃;
wherein the second blow forms 5 times the transverse stretch and 3 times the longitudinal stretch.
Step 3), corona treatment: the second tube film is subjected to heat setting and corona treatment to prepare a multilayer environment-friendly barrier heat shrinkable film;
wherein, the corona treatment only carries out 36 dyne corona treatment on the surface of the heat-sealing layer;
wherein the thickness of the multilayer environment-friendly barrier heat shrinkable film is less than 50 μm.
The above multilayer ringThe barrier heat shrinkable film can be brought into a PE recovery system for recycling, the tensile strength of the barrier heat shrinkable film can reach 75MPa, and the oxygen transmission capacity is less than 20cm 3 /(m 2 24 h.0.1 MPa), water vapor transmission rate of less than 15 g/(m) 2 24 h) transparency greater than 85%.
In conclusion, the invention adopts the polymer modifier for compatibilization and ultrathin lamination, so that the prepared heat shrinkable film has good coating and dispersing effects of polar components, can be incorporated into a PE recovery system, and can be used for manufacturing new film materials or plastic products.
The description and practice of the disclosure herein will be readily apparent to those skilled in the art from consideration of the specification and understanding, and may be modified and modified without departing from the principles of the disclosure. Therefore, modifications or improvements made without departing from the spirit of the invention should also be considered as the protection scope of the invention.
Claims (8)
1. A multilayer environment-friendly heat-resistant heat-insulating shrinkable film is characterized by comprising seven layers of heat-shrinkable films or nine layers of heat-shrinkable films;
the nine layers of heat shrinkable films sequentially comprise a first surface layer, a first structural layer, a first barrier layer, a second structural layer and a first heat sealing layer from top to bottom, wherein first bonding layers are arranged among the first surface layer, the first structural layer, the first barrier layer, the second structural layer and the first heat sealing layer;
the seven layers of heat-shrinkable films sequentially comprise a second surface layer, a second barrier layer, a third structural layer and a second heat-sealing layer from top to bottom; second bonding layers are arranged among the second surface layer, the second barrier layer, the third structural layer and the second heat sealing layer;
the first surface layer and the second surface layer are both metallocene linear low-density polyethylene or polyamide, the total proportion of the first surface layer or the second surface layer is 5-15%, and 0.02-0.5% of erucamide is added into the first surface layer and the second surface layer;
the first barrier layer and the second barrier layer are both ethylene-vinyl alcohol copolymer, and the total proportion of the first barrier layer or the second barrier layer is 5-15%;
the first structural layer, the second structural layer and the third structural layer are all made of polyamide, and the total proportion of the first structural layer, the second structural layer or the third structural layer is 10-30%;
the first heat-sealing layer and the second heat-sealing layer are both polyethylene added with ethylene acrylic acid copolymer, the total proportion of the first heat-sealing layer or the second heat-sealing layer is 20-40%, and the ethylene acrylic acid copolymer accounts for 10-80% of the first heat-sealing layer or the second heat-sealing layer;
the first adhesive layer and the second adhesive layer are both maleic anhydride grafted linear polyethylene, and the proportion of the first adhesive layer or the second adhesive layer is 5-15%.
2. The multilayer environmental protection heat barrier heat shrinkable film of claim 1 wherein the total thickness of the heat shrinkable film is less than or equal to 80 μm.
3. The preparation method of the multilayer environment-friendly barrier heat-shrinkable film according to claim 1, comprising the steps of:
step 1), preparing a first tube membrane: melting raw materials of each layer by a screw rod, extruding the raw materials in a seven-layer or nine-layer circular extruder, superposing the raw materials to form a film blank, carrying out primary inflation stretching, and immediately carrying out rapid cooling molding by cooling water to form a first tubular film;
step 2), preparing a second tube membrane: the first tube film enters a heating system, and compressed air is filled into the tube film for secondary blowing to obtain a second tube film;
step 3), corona treatment: and the second tube film is subjected to heat setting and corona treatment to obtain the multilayer environment-friendly barrier heat shrinkable film.
4. The method for preparing the multilayer environmental-friendly barrier heat-shrinkable film according to claim 3, wherein in the step 1), the inlet of the circular extruder is an hourglass-shaped inlet.
5. The preparation method of the multilayer environment-friendly barrier heat-shrinkable film as claimed in claim 3, wherein in the step 1), the extrusion temperature of polyamide as the raw material is 210-250 ℃; the extrusion temperature of the ethylene-vinyl alcohol copolymer is 170-225 ℃; the extrusion temperature of the metallocene linear low-density polyethylene and the polyethylene is 160-220 ℃; the extrusion temperature of the first adhesive layer or the second adhesive layer is 150-210 ℃.
6. The method for preparing the multilayer environmental-friendly barrier heat shrinkable film according to claim 3, wherein in the step 1), the first inflation stretching forms 1-2 times of longitudinal stretching and 1-1.5 times of transverse stretching; the cooling water temperature is 5-20 ℃.
7. The method for preparing the multilayer environmental-friendly barrier heat-shrinkable film according to claim 3, wherein in the step 2), the temperature of the heating system is 60-90 ℃.
8. The method for preparing the multilayer environmental-friendly barrier heat shrinkable film according to claim 3, wherein in the step 2), the second blow-up is performed by 3-6 times of transverse stretching and 2-4 times of longitudinal stretching.
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| WO2018088152A1 (en) * | 2016-11-09 | 2018-05-17 | 株式会社クレハ | Heat shrinkable multilayer film |
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| CN102555379A (en) * | 2011-12-16 | 2012-07-11 | 江阴升辉包装材料有限公司 | Highly obstructed multilayer coextrusion thermal shrink film |
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| WO2018088152A1 (en) * | 2016-11-09 | 2018-05-17 | 株式会社クレハ | Heat shrinkable multilayer film |
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