CN110920185A - High-barrier puncture-resistant irradiation-resistant crosslinked multilayer heat shrinkable film and preparation method thereof - Google Patents

High-barrier puncture-resistant irradiation-resistant crosslinked multilayer heat shrinkable film and preparation method thereof Download PDF

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CN110920185A
CN110920185A CN201910967792.2A CN201910967792A CN110920185A CN 110920185 A CN110920185 A CN 110920185A CN 201910967792 A CN201910967792 A CN 201910967792A CN 110920185 A CN110920185 A CN 110920185A
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film layer
film
thickness
heat shrinkable
multilayer
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翟庆盼
陈波
王清
齐家鹏
余文健
董亮亮
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JIANGYIN BAOBO PACKING CO Ltd
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JIANGYIN BAOBO PACKING CO Ltd
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/0866—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using particle radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/10—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation for articles of indefinite length
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/28—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of blown tubular films, e.g. by inflation
    • 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
    • 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
    • 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
    • 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
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/0866—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using particle radiation
    • B29C2035/0877—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using particle radiation using electron radiation, e.g. beta-rays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2007/00—Flat articles, e.g. films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2009/00—Layered products
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/54—Yield strength; Tensile strength
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7244—Oxygen barrier
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/734—Dimensional stability
    • B32B2307/736—Shrinkable
    • 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
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging

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  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Physics & Mathematics (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Thermal Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention discloses a high-barrier puncture-resistant irradiation-crosslinked multilayer heat shrinkable film, which comprises a first PE film layer, a first adhesive film layer, a first PA film layer, an intermediate EVOH film layer, a second PA film layer, a second adhesive film layer and a second PE film layer which are formed by co-extrusion; the total thickness of the multilayer heat shrinkable film is 30-200 mu m, wherein the thicknesses of the first PE film layer and the second PE film layer are both 5-40% of the total thickness; the thickness of the first bonding film layer and the second bonding film layer is 2-10% of the total thickness, the thickness of the first PA film layer and the thickness of the second PA film layer are 2-15% of the total thickness, and the thickness of the EVOH film layer is 2-10% of the total thickness. The invention provides a multilayer heat shrinkable film with high barrier performance and excellent puncture resistance.

Description

High-barrier puncture-resistant irradiation-resistant crosslinked multilayer heat shrinkable film and preparation method thereof
Technical Field
The invention relates to the technical field of packaging, in particular to a high-barrier puncture-resistant irradiation-resistant crosslinked multilayer heat shrinkable film and a preparation method thereof.
Background
The existing high-barrier puncture-resistant heat shrinkable film is PE/PE/PE, PP/PE/PP or PE/PVDC/PE, PE/EVOH/PE, the barrier property and the puncture resistance of the former two films are poor, the puncture resistance of the latter two films is poor, and the existing high-barrier puncture-resistant heat shrinkable film is difficult to package foods with acute angles, such as meat, fish, nuts and the like with bones.
The multilayer co-extrusion film is produced by adopting a multilayer co-extrusion process, has excellent barrier property, mechanical property, forming property and heat sealing property, does not need to carry out an additional composite process in the processing process, does not relate to the problem of residual solvents such as printing ink, adhesive, auxiliary agent and the like, and is widely applied to the fields of food packaging, electronic packaging, medical packaging and the like.
Patent CN102700210A discloses a seven-layer co-extrusion transparent high-barrier film and a preparation method thereof, and although the preparation method is environment-friendly, the obtained transparent high-barrier film has good transparency and barrier property, but the puncture resistance effect cannot meet the requirement of packaging of food with an acute angle. Therefore, a thermal shrinkage film with high barrier and good puncture resistance for packaging acute-angled foods is urgently needed in the field of food packaging.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a multilayer heat shrinkable film with high barrier property and excellent puncture resistance.
The invention also aims to provide a preparation method of the high-barrier puncture-resistant multilayer heat shrinkable film.
In order to achieve the purpose, the technical scheme of the invention is to design a high-barrier puncture-irradiation-resistant cross-linked multilayer heat shrinkable film, which comprises a first PE film layer, a first adhesive film layer, a first PA film layer, a middle EVOH film layer, a second PA film layer, a second adhesive film layer and a second PE film layer which are formed by co-extrusion;
the total thickness of the multilayer heat shrinkable film is 30-200 mu m, wherein the thicknesses of the first PE film layer and the second PE film layer are both 5-40% of the total thickness; the thickness of the first bonding film layer and the second bonding film layer is 2-10% of the total thickness, the thickness of the first PA film layer and the thickness of the second PA film layer are 2-15% of the total thickness, and the thickness of the EVOH film layer is 2-10% of the total thickness.
The polyethylene has good moisture resistance, and can prevent water vapor and the like from permeating; the polyethylene has good low-temperature heat sealing performance; the melting point of the polyethylene is 100-130 ℃, the low-temperature resistance of the polyethylene is excellent, the good mechanical property can be still maintained at-60 ℃, and the chemical stability of the polyethylene is good.
The invention changes the polyethylene with linear molecular structure into three-dimensional network structure after radiation cross-linking by the radiation cross-linking treatment of the prior polyethylene, so that the polyethylene has strong anti-deformation capability under high temperature condition.
The polyamide has higher mechanical strength and good compatibility with the ethylene-vinyl alcohol copolymer, and can be used as a supporting protective layer of the ethylene-vinyl alcohol copolymer layer; the polyamide has good wear resistance.
As a preferable technical scheme, the invention is formed by mixing one or more of PA6, PA66 or PA 610. PA66 has good mechanical strength and stiffness; PA6 has a lower melting point than PA66, a wide process temperature range, easy processing, good toughness, but poor dimensional stability. The first PA film layerThe density of the polyamide in the second PA film layer is 1.15g/cm3The temperature range of use is wide, and the temperature can be tolerated from minus 60 ℃ to 200 ℃. The polyamide has better tensile strength, puncture resistance and oxygen resistance, and the application of the two PA film layers ensures that the nylon EVOH high-barrier film has better oxygen barrier property.
According to a preferable technical scheme, the first adhesive film layer and the second adhesive film layer are both PE-g-MAH layers with grafting rate of 0.1-1.5%. The binding resin is not particularly limited in the present invention, and includes, but is not limited to, maleic anhydride graft-modified polymers, acrylic acid graft-modified polymers, and acrylate graft-modified polymers.
Ethylene vinyl alcohol copolymers have been the most used high barrier material. The material has the obvious characteristics of excellent barrier property to gas and excellent processability. However, the ethylene-vinyl alcohol copolymer resin has poor adhesion to most polymers, and a special adhesive resin is required, but the ethylene-vinyl alcohol copolymer film can adhere well to a nylon film, i.e., the ethylene-vinyl alcohol copolymer has a relatively good affinity with polyamide. The ethylene-vinyl alcohol copolymer has high glass transition temperature, can adapt to molding processing, and can change the defect that a PA film layer is easy to deform when being heated, so that the EVOH film layer is arranged between two PA film layers in the invention.
The thickness of the ethylene-vinyl alcohol copolymer layer has great influence on the performance of the obtained transparent high-barrier film, and when the thickness is too thin, the oxygen resistance of the transparent high-barrier film is not ideal; if the thickness is too large, the amount of resin used is increased although the oxygen barrier property is good, and the cost is high.
Preferably, the intermediate EVOH film layer is composed of an ethylene-vinyl alcohol copolymer, and the specific gravity of the intermediate EVOH film layer is 1.14-1.19 g/cm3And the ethylene content in the EVOH film layer is 30-40%. EVOH is added into the heat shrinkable film, so that the barrier property to various odors is greatly improved, and the taste of the contents is prevented from being influenced by external odors.
Preferably, the total thickness of the multilayer heat shrinkable film is 80-120 mu m.
A preparation method of a high-barrier puncture-resistant irradiation cross-linked multilayer heat shrinkable film comprises the following steps:
(1) multilayer coextrusion film blowing: mixing polyethylene raw materials, adding the mixture into a hopper of an extruder, melting the mixture at the temperature of 200-220 ℃, and feeding the mixture into a neck mold; adding maleic anhydride modified polyethylene into a hopper of an extruder, melting at 235-250 ℃, and feeding into a neck mold; mixing polyamide raw materials, adding the mixture into a hopper of an extruder, melting the mixture at 220-230 ℃, and feeding the mixture into a neck mold; adding an ethylene-vinyl alcohol copolymer into a hopper of an extruder, melting at 210-230 ℃, and feeding into a neck mold; each extruder respectively heats, melts and plasticizes the raw material particles in the charging hopper, and extrudes the raw material particles through a die head; extruding and fusing multiple layers of molten raw materials at an extrusion opening of the die head, and simultaneously blowing up the film;
(2) electron beam irradiation crosslinking: the multilayer co-extruded film is tiled, an electron beam is used as an irradiation source to perform irradiation crosslinking treatment on the multilayer co-extruded film, the energy of the electron beam is 0.15-2 MeV, the absorbed dose is 90-200 kGy, and the irradiation speed is 10-300 m/min under the air atmosphere and the environment with the temperature of 25 ℃;
(3) and carrying out secondary blowing on the irradiated and crosslinked multilayer co-extruded film, and carrying out trimming and rolling to obtain the multilayer heat shrinkable film.
The polyethylene mainly undergoes radiation crosslinking within a certain absorption dose range, and radiation degradation is gradually dominant as the absorption dose is further increased. Under the irradiation of electron beams, the crystallization process of polyethylene is inhibited along with the increase of absorbed dose, because the occurrence of irradiation crosslinking reaction leads to the formation of a three-dimensional network structure among molecular chains, thereby hindering the movement of the molecular chains. When the absorbed dose is lower, the physical property change is smaller, and when the absorbed dose is higher, the mechanical property, the thermal stability and the rheological property of the sample are reduced, which is caused by the cracking of molecular chains due to the radiation crosslinking reaction under high dose. Polyethylene irradiation crosslinking is studied more in the current research, but the irradiation crosslinking is carried out after the polyethylene, the polyamide and the ethylene-vinyl alcohol copolymer are co-extruded into a film, and the method is rarely reported.
The invention has the advantages and beneficial effects that:
(1) the PE film layer after irradiation crosslinking treatment has good longitudinal and transverse tensile strength, and the puncture resistance strength is also obviously improved.
(2) The polyethylene and the polyamide are co-extruded to form the film, the polyamide has better tensile strength, puncture resistance and oxygen resistance, and the application of the two PA film layers ensures that the heat shrinkable film has better oxygen barrier property.
(3) The middle EVOH film layer is composed of ethylene-vinyl alcohol copolymer, and the ethylene-vinyl alcohol copolymer has quite good affinity with polyamide. The ethylene-vinyl alcohol copolymer has high glass transition temperature, can adapt to molding processing, and can change the defect that a PA film layer is easy to deform when being heated.
(4) Compared with the heat shrinkable film which is not subjected to irradiation crosslinking treatment, the co-extruded heat shrinkable film is subjected to irradiation crosslinking treatment, so that the puncture resistance is increased by 90%, the elongation at break is reduced by 50%, the heat shrinkage rate is doubled, the barrier property is improved by 60%, and the heat sealing temperature is improved to 150-250 ℃.
Drawings
FIG. 1 is a schematic view of the construction of a multilayer heat shrinkable film of the present invention;
in the figure: 1. a first PE film layer; 2. a first adhesive film layer; 3. a first PA film layer; 4. an intermediate EVOH film layer; 5. a second PA film layer; 6. a second adhesive film layer; 7. a second PE film layer.
Detailed Description
The following description of the embodiments of the present invention will be made with reference to the accompanying drawings. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
Example 1
A high-barrier puncture-resistant irradiation cross-linked multilayer heat shrinkable film comprises a first PE film layer 1, a first adhesive film layer 2, a first PA film layer 3, an intermediate EVOH film layer 4, a second PA film layer 5, a second adhesive film layer 6 and a second PE film layer 7 which are formed by co-extrusion;
the total thickness of the heat shrinkable film is 200 mu m, wherein the thickness of the first PE film layer is 80 mu m, the thickness of the first adhesive film layer is 4 mu m, the thickness of the first PA film layer is 10 mu m, the thickness of the EVOH film layer is 12 mu m, the thickness of the second PA film layer is 10 mu m, the thickness of the second adhesive film layer is 4 mu m, and the thickness of the second PE film layer is 80 mu m.
(1) Multilayer coextrusion film blowing: mixing polyethylene raw materials, adding the mixture into a hopper of an extruder, melting the mixture at the temperature of 200-220 ℃, and feeding the mixture into a neck mold; adding maleic anhydride modified polyethylene into a hopper of an extruder, melting at 235-250 ℃, and feeding into a neck mold; mixing polyamide raw materials, adding the mixture into a hopper of an extruder, melting the mixture at 220-230 ℃, and feeding the mixture into a neck mold; adding an ethylene-vinyl alcohol copolymer into a hopper of an extruder, melting at 210-230 ℃, and feeding into a neck mold; each extruder respectively heats, melts and plasticizes the raw material particles in the charging hopper, and extrudes the raw material particles through a die head; extruding and fusing multiple layers of molten raw materials at an extrusion opening of the die head, and simultaneously blowing up the film;
(2) electron beam irradiation crosslinking: the multilayer co-extruded film is tiled, an electron beam is used as an irradiation source to carry out irradiation crosslinking treatment on the multilayer co-extruded film, the energy of the electron beam is 2MeV, the absorbed dose is 200kGy, and the irradiation speed is 150m/min under the air atmosphere and the environment with the temperature of 25 ℃;
(3) and carrying out secondary blowing on the irradiated and crosslinked multilayer co-extruded film, and carrying out trimming and rolling to obtain the multilayer heat shrinkable film.
The first adhesive film layer and the second adhesive film layer are both PE-g-MAH layers with the grafting rate of 0.1%.
The middle EVOH film layer consists of ethylene-vinyl alcohol copolymer, and the specific gravity of the middle EVOH film layer is 1.14-1.15 g/cm3The ethylene content in the EVOH film layer was 30%.
The first PA film layer and the second PA film layer are PA 6.
Example 2
Example 2 differs from example 1 in that:
the total thickness of the heat shrinkable film is 200 mu m, wherein the thickness of a first PE film layer is 40 mu m, the thickness of a first adhesive film layer is 20 mu m, the thickness of a first PA film layer is 30 mu m, the thickness of an EVOH film layer is 20 mu m, the thickness of a second PA film layer is 30 mu m, the thickness of a second adhesive film layer is 20 mu m, and the thickness of a second PE film layer is 40 mu m.
(1) Multilayer coextrusion film blowing: mixing polyethylene raw materials, adding the mixture into a hopper of an extruder, melting the mixture at the temperature of 200-220 ℃, and feeding the mixture into a neck mold; adding maleic anhydride modified polyethylene into a hopper of an extruder, melting at 235-250 ℃, and feeding into a neck mold; mixing polyamide raw materials, adding the mixture into a hopper of an extruder, melting the mixture at 220-230 ℃, and feeding the mixture into a neck mold; adding an ethylene-vinyl alcohol copolymer into a hopper of an extruder, melting at 210-230 ℃, and feeding into a neck mold; each extruder respectively heats, melts and plasticizes the raw material particles in the charging hopper, and extrudes the raw material particles through a die head; extruding and fusing multiple layers of molten raw materials at an extrusion opening of the die head, and simultaneously blowing up the film;
(2) electron beam irradiation crosslinking: the multilayer co-extruded film is tiled, an electron beam is used as an irradiation source to carry out irradiation crosslinking treatment on the multilayer co-extruded film, the energy of the electron beam is 1.5MeV, the absorbed dose is 100kGy and the irradiation speed is 180m/min under the air atmosphere and the environment with the temperature of 25 ℃;
(3) and carrying out secondary blowing on the irradiated and crosslinked multilayer co-extruded film, and carrying out trimming and rolling to obtain the multilayer heat shrinkable film.
The first adhesive film layer and the second adhesive film layer are both PE-g-MAH layers with the grafting rate of 0.5%.
The middle EVOH film layer consists of ethylene-vinyl alcohol copolymer, and the specific gravity of the middle EVOH film layer is 1.15-1.18 g/cm3The ethylene content in the EVOH film layer was 30%.
The first PA film layer and the second PA film layer are PA6 and PA66 mixed at a 1:1 ratio.
Example 3
Example 3 differs from example 1 in that:
the total thickness of the heat shrinkable film is 100 microns, wherein the thickness of a first PE film layer is 30 microns, the thickness of a first adhesive film layer is 5 microns, the thickness of a first PA film layer is 10 microns, the thickness of an EVOH film layer is 10 microns, the thickness of a second PA film layer is 10 microns, the thickness of a second adhesive film layer is 5 microns, and the thickness of a second PE film layer is 30 microns.
(1) Multilayer coextrusion film blowing: mixing polyethylene raw materials, adding the mixture into a hopper of an extruder, melting the mixture at the temperature of 200-220 ℃, and feeding the mixture into a neck mold; adding maleic anhydride modified polyethylene into a hopper of an extruder, melting at 235-250 ℃, and feeding into a neck mold; mixing polyamide raw materials, adding the mixture into a hopper of an extruder, melting the mixture at 220-230 ℃, and feeding the mixture into a neck mold; adding an ethylene-vinyl alcohol copolymer into a hopper of an extruder, melting at 210-230 ℃, and feeding into a neck mold; each extruder respectively heats, melts and plasticizes the raw material particles in the charging hopper, and extrudes the raw material particles through a die head; extruding and fusing multiple layers of molten raw materials at an extrusion opening of the die head, and simultaneously blowing up the film;
(2) electron beam irradiation crosslinking: the multilayer co-extruded film is tiled, an electron beam is used as an irradiation source to carry out irradiation crosslinking treatment on the multilayer co-extruded film, the energy of the electron beam is 1.8MeV, the absorbed dose is 100kGy and the irradiation speed is 150m/min under the air atmosphere and the environment with the temperature of 25 ℃;
(3) and carrying out secondary blowing on the irradiated and crosslinked multilayer co-extruded film, and carrying out trimming and rolling to obtain the multilayer heat shrinkable film.
The first adhesive film layer and the second adhesive film layer are both PE-g-MAH layers with the grafting rate of 0.8%.
The middle EVOH film layer consists of ethylene-vinyl alcohol copolymer, and the specific gravity of the middle EVOH film layer is 1.15-1.18 g/cm3The ethylene content in the EVOH film layer was 35%.
The first PE film layer and the second PE film layer are made of low-density polyethylene.
The first PA film layer and the second PA film layer are both PA 66.
Example 4
Example 4 differs from example 1 in that:
the total thickness of the heat shrinkable film is 100 microns, wherein the thickness of a first PE film layer is 30 microns, the thickness of a first adhesive film layer is 10 microns, the thickness of a first PA film layer is 15 microns, the thickness of an EVOH film layer is 5 microns, the thickness of a second PA film layer is 10 microns, the thickness of a second adhesive film layer is 10 microns, and the thickness of a second PE film layer is 20 microns.
(1) Multilayer coextrusion film blowing: mixing polyethylene raw materials, adding the mixture into a hopper of an extruder, melting the mixture at the temperature of 200-220 ℃, and feeding the mixture into a neck mold; adding maleic anhydride modified polyethylene into a hopper of an extruder, melting at 235-250 ℃, and feeding into a neck mold; mixing polyamide raw materials, adding the mixture into a hopper of an extruder, melting the mixture at 220-230 ℃, and feeding the mixture into a neck mold; adding an ethylene-vinyl alcohol copolymer into a hopper of an extruder, melting at 210-230 ℃, and feeding into a neck mold; each extruder respectively heats, melts and plasticizes the raw material particles in the charging hopper, and extrudes the raw material particles through a die head; extruding and fusing multiple layers of molten raw materials at an extrusion opening of the die head, and simultaneously blowing up the film;
(2) electron beam irradiation crosslinking: the multilayer co-extruded film is tiled, an electron beam is used as an irradiation source to carry out irradiation crosslinking treatment on the multilayer co-extruded film, the energy of the electron beam is 1MeV, the absorbed dose is 80kGy, and the irradiation speed is 120m/min under the air atmosphere and the environment with the temperature of 25 ℃;
(3) and carrying out secondary blowing on the irradiated and crosslinked multilayer co-extruded film, and carrying out trimming and rolling to obtain the multilayer heat shrinkable film.
The first adhesive film layer and the second adhesive film layer are both PE-g-MAH layers with the grafting rate of 0.8%.
The intermediate EVOH film layer is composed of ethylene-vinyl alcohol copolymer, and the intermediate EVOH film layer is composed of ethylene-vinyl alcohol copolymerThe specific gravity of the EVOH film layer is 1.15-1.18 g/cm3The ethylene content in the EVOH film layer was 35%.
Example 5
Example 5 differs from example 1 in that:
the total thickness of the heat shrinkable film is 40 mu m, wherein the thickness of a first PE film layer is 12.4 mu m, the thickness of a first adhesive film layer is 5 mu m, the thickness of a first PA film layer is 10 mu m, the thickness of an EVOH film layer is 10 mu m, the thickness of a second PA film layer is 10 mu m, the thickness of a second adhesive film layer is 5 mu m, and the thickness of a second PE film layer is 30 mu m.
(1) Multilayer coextrusion film blowing: mixing polyethylene raw materials, adding the mixture into a hopper of an extruder, melting the mixture at the temperature of 200-220 ℃, and feeding the mixture into a neck mold; adding maleic anhydride modified polyethylene into a hopper of an extruder, melting at 235-250 ℃, and feeding into a neck mold; mixing polyamide raw materials, adding the mixture into a hopper of an extruder, melting the mixture at 220-230 ℃, and feeding the mixture into a neck mold; adding an ethylene-vinyl alcohol copolymer into a hopper of an extruder, melting at 210-230 ℃, and feeding into a neck mold; each extruder respectively heats, melts and plasticizes the raw material particles in the charging hopper, and extrudes the raw material particles through a die head; extruding and fusing multiple layers of molten raw materials at an extrusion opening of the die head, and simultaneously blowing up the film;
(2) electron beam irradiation crosslinking: the multilayer co-extruded film is tiled, an electron beam is used as an irradiation source to carry out irradiation crosslinking treatment on the multilayer co-extruded film, the energy of the electron beam is 0.8MeV, the absorbed dose is 90kGy and the irradiation speed is 150m/min under the air atmosphere and the environment with the temperature of 25 ℃;
(3) and carrying out secondary blowing on the irradiated and crosslinked multilayer co-extruded film, and carrying out trimming and rolling to obtain the multilayer heat shrinkable film.
The first adhesive film layer and the second adhesive film layer are both PE-g-MAH layers with the grafting rate of 0.8%.
The intermediate EVOH film layer is composed of ethylene-vinyl alcohol copolymer, and the specific gravity of the intermediate EVOH film layer is 1.15～1.18g/cm3The ethylene content in the EVOH film layer was 35%.
The first PA film layer and the second PA film layer are both PA 66.
Example 6
Example 6 differs from example 1 in that:
the total thickness of the heat shrinkable film is 40 mu m, wherein the thickness of a first PE film layer is 10 mu m, the thickness of a first adhesive film layer is 4 mu m, the thickness of a first PA film layer is 4 mu m, the thickness of an EVOH film layer is 4 mu m, the thickness of a second PA film layer is 4 mu m, the thickness of a second adhesive film layer is 4 mu m, and the thickness of a second PE film layer is 10 mu m.
(1) Multilayer coextrusion film blowing: mixing polyethylene raw materials, adding the mixture into a hopper of an extruder, melting the mixture at the temperature of 200-220 ℃, and feeding the mixture into a neck mold; adding maleic anhydride modified polyethylene into a hopper of an extruder, melting at 235-250 ℃, and feeding into a neck mold; mixing polyamide raw materials, adding the mixture into a hopper of an extruder, melting the mixture at 220-230 ℃, and feeding the mixture into a neck mold; adding an ethylene-vinyl alcohol copolymer into a hopper of an extruder, melting at 210-230 ℃, and feeding into a neck mold; each extruder respectively heats, melts and plasticizes the raw material particles in the charging hopper, and extrudes the raw material particles through a die head; extruding and fusing multiple layers of molten raw materials at an extrusion opening of the die head, and simultaneously blowing up the film;
(2) electron beam irradiation crosslinking: the multilayer co-extruded film is tiled, an electron beam is used as an irradiation source to carry out irradiation crosslinking treatment on the multilayer co-extruded film, the energy of the electron beam is 0.5MeV, the absorbed dose is 60kGy, and the irradiation speed is 150m/min under the air atmosphere and the environment with the temperature of 25 ℃;
(3) and carrying out secondary blowing on the irradiated and crosslinked multilayer co-extruded film, and carrying out trimming and rolling to obtain the multilayer heat shrinkable film.
The first adhesive film layer and the second adhesive film layer are both PE-g-MAH layers with the grafting rate of 0.8%.
The intermediate EVOH film layer is made of ethylene-vinyl alcoholThe specific gravity of the middle EVOH film layer is 1.15-1.18 g/cm3The ethylene content in the EVOH film layer was 35%.
The first PA film layer and the second PA film layer are both PA 66.
Comparative example
The comparative example differs from example 1 in that:
the total thickness of the heat shrinkable film is 100 mu m, wherein the thickness of the first PE film layer is 30 mu m, the thickness of the first adhesive film layer is 5 mu m, the thickness of the first PA film layer is 10 mu m, the thickness of the EVOH film layer is 10 mu m, the thickness of the second PA film layer is 10 mu m, the thickness of the second adhesive film layer is 5 mu m, and the thickness of the second PE film layer is 30 mu m.
Multilayer coextrusion film blowing: mixing polyethylene raw materials, adding the mixture into a hopper of an extruder, melting the mixture at the temperature of 200-220 ℃, and feeding the mixture into a neck mold; adding maleic anhydride modified polyethylene into a hopper of an extruder, melting at 235-250 ℃, and feeding into a neck mold; mixing polyamide raw materials, adding the mixture into a hopper of an extruder, melting the mixture at 220-230 ℃, and feeding the mixture into a neck mold; adding an ethylene-vinyl alcohol copolymer into a hopper of an extruder, melting at 210-230 ℃, and feeding into a neck mold; each extruder respectively heats, melts and plasticizes the raw material particles in the charging hopper, and extrudes the raw material particles through a die head; extruding and fusing multiple layers of molten raw materials at an extrusion opening of the die head, and simultaneously blowing up the film;
the first adhesive film layer and the second adhesive film layer are both PE-g-MAH layers with the grafting rate of 0.8%.
The middle EVOH film layer consists of ethylene-vinyl alcohol copolymer, and the specific gravity of the middle EVOH film layer is 1.15-1.18 g/cm3The ethylene content in the EVOH film layer was 35%.
The first PA film layer and the second PA film layer are both PA 66.
Test results of mechanical properties and barrier properties of the examples and the comparative examples of the invention
Figure BDA0002231074700000121
Tests show that the barrier property and the puncture resistance of the multilayer heat shrinkable film are related to the thicknesses of the PE film layer, the PA film layer and the EVOH film layer and related to the absorbed dose, and the tensile strength, the elongation at break, the puncture resistance, the heat shrinkage and other properties of the multilayer heat shrinkable film are obviously improved after irradiation treatment.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the technical principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (6)

1. A high-barrier puncture-resistant irradiation cross-linked multilayer heat shrinkable film is characterized by comprising a first PE film layer, a first adhesive film layer, a first PA film layer, an intermediate EVOH film layer, a second PA film layer, a second adhesive film layer and a second PE film layer which are formed by co-extrusion;
the total thickness of the multilayer heat shrinkable film is 30-200 mu m, wherein the thicknesses of the first PE film layer and the second PE film layer are both 5-40% of the total thickness; the thickness of the first bonding film layer and the second bonding film layer is 2-10% of the total thickness, the thickness of the first PA film layer and the thickness of the second PA film layer are 2-15% of the total thickness, and the thickness of the EVOH film layer is 2-10% of the total thickness.
2. The high-barrier puncture-radiation-resistant crosslinked multilayer heat shrinkable film according to claim 1, wherein the first adhesive film layer and the second adhesive film layer are both PE-g-MAH layers with a grafting ratio of 0.1-1.5%.
3. The high-barrier puncture-radiation-resistant crosslinked multilayer heat shrinkable film according to claim 2, wherein the middle EVOH film layer is composed of ethylene-vinyl alcohol copolymer, and the specific gravity of the middle EVOH film layer is 1.14-1.19 g/cm3And the ethylene content in the EVOH film layer is 30-40%.
4. The high-barrier puncture-radiation-resistant crosslinked multilayer heat shrinkable film according to claim 3, wherein the total thickness of the multilayer heat shrinkable film is 80-120 μm.
5. The heat shrinkable multilayer film of claim 4, wherein the first PA film layer and/or the second PA film layer is one or a mixture of PA6, PA66 and PA 610.
6. The preparation method of the high-barrier puncture-resistant irradiation crosslinked multilayer heat shrinkable film according to any one of claims 1 to 5, characterized by comprising the following steps:
(1) multilayer coextrusion film blowing: mixing polyethylene raw materials, adding the mixture into a hopper of an extruder, melting the mixture at the temperature of 200-220 ℃, and feeding the mixture into a neck mold; adding maleic anhydride modified polyethylene into a hopper of an extruder, melting at 235-250 ℃, and feeding into a neck mold; mixing polyamide raw materials, adding the mixture into a hopper of an extruder, melting the mixture at 220-230 ℃, and feeding the mixture into a neck mold; adding an ethylene-vinyl alcohol copolymer into a hopper of an extruder, melting at 210-230 ℃, and feeding into a neck mold; each extruder respectively heats, melts and plasticizes the raw material particles in the charging hopper, and extrudes the raw material particles through a die head; extruding and fusing multiple layers of molten raw materials at an extrusion opening of the die head, and simultaneously blowing up the film;
(2) electron beam irradiation crosslinking: the multilayer co-extruded film is tiled, an electron beam is used as an irradiation source to perform irradiation crosslinking treatment on the multilayer co-extruded film, the energy of the electron beam is 0.15-2 MeV, the absorbed dose is 90-200 kGy, and the irradiation speed is 10-300 m/min under the air atmosphere and the environment with the temperature of 25 ℃;
(3) and carrying out secondary blowing on the irradiated and crosslinked multilayer co-extruded film, and carrying out trimming and rolling to obtain the multilayer heat shrinkable film.
CN201910967792.2A 2019-10-12 2019-10-12 High-barrier puncture-resistant irradiation-resistant crosslinked multilayer heat shrinkable film and preparation method thereof Pending CN110920185A (en)

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CN115179628A (en) * 2022-05-31 2022-10-14 江阴宝柏新型包装材料有限公司 High-strength corrosion-resistant aluminum-plastic sheet and preparation method thereof
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CN113755090A (en) * 2021-08-11 2021-12-07 东南大学 Preparation method of plastic packaging film
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