CN114889278A - Polyethylene type recyclable packaging material and preparation method thereof - Google Patents

Polyethylene type recyclable packaging material and preparation method thereof Download PDF

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Publication number
CN114889278A
CN114889278A CN202210626765.0A CN202210626765A CN114889278A CN 114889278 A CN114889278 A CN 114889278A CN 202210626765 A CN202210626765 A CN 202210626765A CN 114889278 A CN114889278 A CN 114889278A
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China
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surface layer
polyethylene
packaging material
inner layer
density polyethylene
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Granted
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CN202210626765.0A
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CN114889278B (en
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卓友敬
杨浩文
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Huizhou Logos Packaging Material Co ltd
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Huizhou Logos Packaging Material 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
    • B32B27/32—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
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • 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
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • 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
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/48—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
    • 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
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/40—General aspects of joining substantially flat articles, e.g. plates, sheets or web-like materials; Making flat seams in tubular or hollow articles; Joining single elements to substantially flat surfaces
    • B29C66/41—Joining substantially flat articles ; Making flat seams in tubular or hollow articles
    • B29C66/45—Joining of substantially the whole surface of the articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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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    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
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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
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    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
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    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B32B2250/242—All polymers belonging to those covered by group B32B27/32
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    • 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
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
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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
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    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/51—Elastic
    • 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
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    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
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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
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    • B32B2307/00—Properties of the layers or laminate
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    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
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    • B32B2439/70—Food packaging
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/08—Copolymers of ethene
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    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
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    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
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    • C08J2423/08—Copolymers of ethene
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract

The application relates to the field of packaging, in particular to a polyethylene type recyclable packaging material and a preparation method thereof. The surface layer and the inner layer of the packaging material are both polyethylene components and are polyethylene packaging layers, the prepared packaging material is easy to recycle by adopting series of high polymers of the same kind, the prepared packaging material has excellent performances such as impact strength, tensile strength and toughness, the interlayer combination is stable, the coating effect on articles is good, the articles are not easy to be damaged by piercing, abrasion and the like, and the protective performance is good.

Description

Polyethylene type recyclable packaging material and preparation method thereof
Technical Field
The application relates to the field of packaging, in particular to a polyethylene type recyclable packaging material and a preparation method thereof.
Background
With the rapid development of society, the variety of manufactured products in various manufacturing industries on the market is increased day by day, and the purchased logistics transportation is also developed rapidly, so that various packaging materials are used in the manufacturing industries and the logistics transportation industries to package and protect the products, and the transportation is convenient.
The polyethylene film has good toughness, moisture resistance and heat sealing performance, is convenient to process and form, is low in price, is a plastic packaging film with large use amount in the market at present, is widely applied as a polyethylene skin packaging film and a circuit board vacuum packaging film, and is used for packaging articles such as hardware products, printed circuit boards, food, magnetic cores and the like.
When the polyethylene film is used as a paste film, the polyethylene film is commonly used in food packaging, if people often make a large amount of food at one time, the food is packaged by adopting the packaging film, the food is tightly wrapped by the packaging film in a vacuumizing mode, on one hand, a protective appearance can be formed around the food, the surface protection of the food is improved, and the purposes of dust prevention, oil prevention, moisture prevention, water prevention and scattering prevention are achieved, and the paste packaging is mainly utilized to ensure that the stress in the food packaging process is uniform, so that the damage to the food caused by uneven stress is reduced; on the other hand, the food is attached and packaged by the aid of the retraction force of the stretched packaging film to form a compact unit whole without occupying space, so that mutual dislocation and movement of the food in the transportation process can be effectively prevented; on the other hand, the vacuum packaging is performed to realize the skin packaging, so that the contact between air and food can be reduced, the weathering or deterioration of the food can be reduced, the good protection packaging of the food can be realized, the storage time of the packaged food can be prolonged, and the food can be conveniently sold through logistics transportation.
However, in the current polyethylene film, the packaging film shrinks toward the food during the vacuum-pumping process, the packaging film deforms during the shrinking process, and the wrinkle position of the packaging film generated by the deformation is easily worn and broken by the external pressure, so that the packaging protection performance is reduced, and the packaging protection performance of the food is affected.
Disclosure of Invention
In order to solve the problem that the wrapping fold position of the current polyethylene adhesive film is easy to wear and break, the application provides a polyethylene type recyclable packaging material and a preparation method thereof.
In a first aspect, the present application provides a polyethylene type recyclable packaging material, which adopts the following technical scheme:
a polyethylene type recyclable packaging material comprises a surface layer and an inner layer which are attached to each other, wherein the surface layer comprises linear low-density polyethylene, medium-density polyethylene and metallocene linear low-density polyethylene, and the mixing weight ratio of the linear low-density polyethylene to the medium-density polyethylene to the metallocene linear low-density polyethylene is 1: 4-6: 0.3-0.8;
the inner layer comprises low-density polyethylene and linear low-density polyethylene, and the mixing weight ratio of the low-density polyethylene to the linear low-density polyethylene is 1: 2-4.
The surface layer and the inner layer of the packaging material are both made of polyethylene components, so that the prepared packaging material is easy to recycle, wherein Linear Low Density Polyethylene (LLDPE) + Medium Density Polyethylene (MDPE) + Metallocene Linear Low Density Polyethylene (MLLDPE) is adopted as the surface layer, the LLDPE and the MDPE are matched for use to enable the surface layer of the packaging material to have excellent tensile strength, tear strength, heat resistance and puncture resistance, the strength of the surface layer is enhanced, the packaging material is used as a body attaching film, and after vacuum pumping treatment, the surface layer is not easy to wear due to the fact that wrinkles are generated by vacuum pumping deformation.
The branched chains of the Metallocene Linear Low Density Polyethylene (MLLDPE) on the surface layer are longer and are distributed uniformly, the mechanical property is good, the heat sealing capability is good, the heat adhesiveness and the low-temperature heat sealability of the Low Density Polyethylene (LDPE) on the inner layer are combined, so that the surface layer and the inner layer are combined stably, the prepared packaging material has good heat sealing property after being coated with food, the coating protection effect is good, and the packaging material can be used as a sticker film.
The inner layer also adopts Linear Low Density Polyethylene (LLDPE), on one hand, the LLDPE on the surface layer is compatible and combined with the LLDPE on the inner layer, so that the interlayer combination of the prepared packaging material is stable, and the stability of the whole product is high; on the other hand, the Linear Low Density Polyethylene (LLDPE) has excellent strength, good wear resistance and good barrier property, and can improve the strength, wear resistance and barrier property of the inner layer, so that when the packaging material is used for packaging food, the food is not easy to be affected with moisture by oxygen, is not easy to mutually permeate with external water and oil, is not easy to generate the phenomenon of tainting odor, and has good packaging protection performance.
Preferably, in the skin layer, the linear low density polyethylene has a melt index of 0.8 to 1.0g/10min and a density of 0.915 to 0.928g/cm 3 ；
The medium density polyethylene has a melt index of 0.8-1.0g/10min and a density of 0.928-0.935g/cm 3 ；
The metallocene linear low density polyethylene has a melt index of 1.8-2.0g/10min and a density of 0.923-0.928g/cm 3 。
By adopting the polyethylene component with the melt index and the density range, the prepared surface layer has higher impact strength, so that the surface layer of the packaging material is not easy to be abraded or pierced by external friction and collision, the coating protection performance is good, the surface layer is easy to combine with an inner layer stably, the interlayer separation is not easy to occur, and the whole coating protection effect is good.
Preferably, in the inner layer, the low density polyethylene has a melt index of 0.9-1.1g/10min and a density of 0.915-0.925g/cm 3 ；
The linear low density polyethylene has a melt index of 0.8-1.0g/10min and a density of 0.922-0.928g/cm 3 。
By adopting the polyethylene with the melting index and the density range, the prepared inner layer material is soft, can be tightly attached to a packaged object in a vacuum-pumping process when used as an adhesive film, has good formability, and plays a role in stably protecting the packaged object.
Preferably, the inner layer further comprises an ethylene/vinyl alcohol copolymer, and the mixing weight ratio of the low density polyethylene, the linear low density polyethylene and the ethylene/vinyl alcohol copolymer is 1: 2-4: 0.3-0.5, and the ethylene content of the ethylene/vinyl alcohol copolymer is 12-20%.
By adding ethylene/vinyl alcohol copolymer with specific ethylene content into the inner layer, the barrier property of the inner layer can be improved, and oxygen and CO can be effectively prevented 2 And the inner layer has good protection effect on food, so that sauce, moisture and oil in the food are not easy to permeate into the packaging material when the packaging material is used for packaging the food, and the protection performance is good.
Preferably, modified shell powder is added into the surface layer, and the addition amount of the modified shell powder is 0.5-3% of the weight of the surface layer; the modified shell powder is prepared by the following steps:
step S1: cleaning and drying shell raw materials, pulverizing, and sieving with 20-50 mesh sieve to obtain shell micropowder;
step S2: calcining the shell micro powder prepared in the step S1, cooling to room temperature, and performing nano crushing treatment to obtain nano shell powder;
step S3: and (4) soaking the nano shell powder prepared in the step (S2) into a modifier, preserving heat for 1-2h at the temperature of 70-85 ℃, filtering and drying to obtain the modified shell powder.
Through adding modified shell powder in the top layer, can improve the high temperature resistance on top layer, antifriction performance, and can adsorb external peculiar smell and have antibiotic antibacterial property, and this application packaging material has the barrier action, and the article of inlayer cladding protection is difficult for permeating to adsorbed peculiar smell, when being used for cladding food with packaging material, also is difficult for producing the tainting of smell phenomenon, and the packaging material who makes is behind the evacuation packing, and the fold position that forms is difficult for receiving external friction and wearing and tearing, and cladding protection performance is good.
And the antistatic property of the surface layer can be improved by the porous structure of the multi-fine structure of the shell powder, so that when the packaging material prepared by co-extrusion film forming is rolled, the surface layer is in contact with the inner layer, static electricity is not easy to generate, and the packaging material coiled material is easy to process.
The step S1 is to crush the shell material into shell micro powder with a specific particle size range, so that the calcination treatment in the step S2 can be conveniently carried out to fully calcine the shell micro powder, a micropore structure is formed in the shell micro powder, and the shell micro powder is further crushed into a nano particle size by combining a nano treatment means, so that the dispersion uniformity of the shell powder in a surface layer is improved; and step S3 is combined to carry out infiltration modification treatment on the nano shell powder so as to further improve the compatibility of the shell powder in the surface layer material and improve the wear resistance, the barrier property and the antibacterial and bacteriostatic properties of the surface layer, so that when the prepared packaging material is used as a skin film, the wrinkle positions formed after vacuumizing are not easy to wear and damage the packaging protection effect on articles.
Preferably, in the step S2, the calcination treatment is specifically to calcine at 450 ℃ for 15-20min, then raise the temperature to 820 ℃ at a temperature-raising speed of 5-10 ℃/min, and continue the calcination for 25-30 min.
By adopting a sectional calcination mode for the shell micro powder and controlling the temperature and time of each section of calcination treatment, the shell micro powder can be gradually calcined from the outer side to the inner side to form a microporous structure, so that the shell micro powder can be conveniently pulverized into the nano shell powder with uniform particle size by the subsequent nano pulverization treatment.
Preferably, in the step S3, the infiltration weight ratio of the nano shell powder to the modifier is 1:2.5-3, and the modifier is prepared from isopropyl tris (dioctyl pyrophosphato acyloxy) titanate, stearic acid and polysiloxane in a weight ratio of 1-1.5: 1: 2-3, mixing.
By adopting the modifier to carry out heat preservation, infiltration and modification treatment on the nano shell powder, the nano shell powder has excellent self-lubricating property, wear resistance and high polymer compatibility, the binding property of the shell powder and a polyethylene system in a surface layer is improved, and the modified shell powder is uniformly dispersed in the surface layer so as to improve the wear resistance of the surface layer.
Preferably, the surface layer is also added with a compatibilization resin, and the addition amount of the compatibilization resin is 0.3-1.5% of the weight of the surface layer; the compatibilization resin is PE-g-MAH and/or PE-g-MAA.
In the conventional packaging material, when the packaging material is opened to take out a packaged article, the surface layer is opened and the inner layer is still covered, that is, the inner layer and the surface layer of the packaging material are separated, so that the use feeling is low.
By adding the compatible resin with the above dosage and types into the surface layer, on one hand, the maleic anhydride group can react with the polyethylene matrix in the surface layer, and the compatibility of the powder component and the polyethylene matrix component in the surface layer material can be improved; on the other hand, the maleic anhydride group reacts with the polyvinyl phase of the inner layer in the hot-pressing laminating forming process of the surface layer and the inner layer, so that the compatibility and combination stability of the surface layer and the inner layer can be further improved, the packaging material is not easy to generate interlayer separation, the protection effect is good, and the use feeling is good.
Preferably, modified silica is added into the inner layer, and the addition amount of the modified silica is 1.2-2.0% of the weight of the inner layer; the modified silicon dioxide is prepared by the following steps:
adding 1-3 parts by weight of coupling agent into 30-35 parts by weight of mixed solvent, uniformly dispersing, adding 12-15 parts by weight of nano silicon dioxide, stirring at 55-68 ℃ for 30-40min, filtering, and drying to obtain pretreated silicon dioxide;
dispersing 5-10 parts by weight of methyl methacrylate in 25-30 parts by weight of acetone, then adding 3-8 parts by weight of thionyl chloride, and uniformly dispersing to obtain a modified material;
adding the pretreated silicon dioxide into the modified material, carrying out reflux reaction at 75-85 ℃ for 90-150min, filtering, washing with ethanol for 2-3 times, and drying to obtain the modified silicon dioxide.
Through adding modified silicon dioxide in the inlayer, can improve the toughness and the compactedness of inlayer, when packaging material carries out the cladding protection as the laminating membrane to food, the inlayer can closely laminate in the food surface during evacuation processing to isolated food contacts with external water oxygen, prolongs the food retention period, and during the sauce of food was difficult for permeating to packaging material, reduces the tainting of smell phenomenon of packing food, and the cladding protection performance is good.
The silica is easy to agglomerate due to a large number of active hydroxyl groups on the surface of the silica, and is not easy to disperse in the inner layer material, so that part of the silica is possibly suspended on the surface of the inner layer, and the inner layer and the surface layer are unstable to combine, or the surface of the inner layer is possibly migrated and suspended with silica powder, and the silica powder suspended on the surface of the inner layer is easy to contact with food, so that the quality of the food is influenced.
Therefore, the mixed solvent containing the coupling agent component is adopted to soak the silicon dioxide, the hydroxyl content on the surface of the silicon dioxide is reduced, the agglomeration phenomenon of the silicon dioxide can be reduced, the pretreated silicon dioxide is treated by the modifying material, the methyl methacrylate can be grafted on the surface of the silicon dioxide, the compatibility of the silicon dioxide in a high polymer of an inner layer material is improved, the compatibility and the dispersibility of the silicon dioxide in the inner layer material are realized, and the condition that silicon dioxide powder migrates and suspends on the surface of the inner layer material due to the uneven compatibility and the dispersion of the silicon dioxide is reduced.
Preferably, the coupling agent is prepared by mixing isopropyl triisostearate, isopropyl tri (dioctyl pyrophosphato acyloxy) titanate and hexamethyldisiloxane in a weight ratio of 2-3:1.5-1.8: 1; the mixed solvent is formed by mixing ethanol and water according to the weight ratio of 2-3:1.
By adopting the coupling agent and the mixed solvent to perform infiltration modification on the silicon dioxide, the silicon dioxide acts with hydroxyl on the surface of the silicon dioxide, the hydroxyl amount on the surface of the silicon dioxide is reduced, the agglomeration phenomenon of the silicon dioxide is improved, and the dispersibility of the silicon dioxide in an inner layer material is improved.
In addition, the shell powder component is contained in the surface layer and the silica component is contained in the inner layer, and the compatibilization resin is adopted in the surface layer, so that the combination stability of the shell powder-containing surface layer and the silica-containing inner layer can be improved.
Preferably, the inner layer is also added with an opening agent, and the using amount of the opening agent is 2-3% of the weight of the inner layer; the opening agent is silicon dioxide, oleamide or erucamide.
The packaging film has a large number of exposed molecular chains on the surface after being formed, and macromolecular chains are intertwined after the two films are closed, so that the packaging film is difficult to open, or the packaging film is difficult to separate because the films form a vacuum sealing state after the films are closed. Therefore, by adding the opening agent of the above kind to the inner layer, blocking of the packaging film can be prevented, the problem of blocking of the plastic packaging film can be solved, and the packaging film can be easily unfolded and packaged.
Preferably, the surface layer and the inner layer respectively comprise PPA fluoropolymer processing aid master batches, and the addition amount is 0.3-0.5%.
And 0.3-0.5% of PPA is added to the outer layer and the inner layer, so that a lubricating layer is formed between the inner wall of a cylinder of the extrusion equipment and the polymer melt by each layer of raw materials, in the continuous extrusion film-forming process, the lubricating layer is in dynamic balance, after the dynamic balance is stable, the extrusion process and the product quality reach a stable state, and after the PPA is added, the processability of the polymer can be improved, the melt plasticity is better, the melt fracture phenomenon is eliminated, and the mechanical property of the product is favorably improved.
In a second aspect, the present application provides a method for preparing a polyethylene type recyclable packaging material, which adopts the following technical scheme:
a preparation method of polyethylene type recyclable packaging material comprises the following steps:
mixing the surface layer raw materials, melting and extruding the mixture into sheets, then carrying out longitudinal stretching treatment and transverse stretching treatment, carrying out heat preservation and shaping at the temperature of 110-130 ℃, and finally cooling and drawing to obtain the surface layer;
mixing the raw materials of the inner layer, melting and extruding the raw materials into sheets, then carrying out longitudinal stretching treatment and transverse stretching treatment, carrying out heat preservation and shaping at the temperature of 120-140 ℃, and finally cooling and drawing to obtain the inner layer;
and coating glue on one surface of the surface layer, then attaching the surface coated with the glue on the surface layer to the inner layer, and then thermally pressing the surface layer and the inner layer to obtain the polyethylene type recyclable packaging material.
At present, in the process of preparing film packaging materials such as high density polyethylene, low density polyethylene, linear low density polyethylene, plastic composite films and the like, a multilayer coextrusion film blowing mode is usually adopted for preparation, so that the prepared film material has excellent barrier properties such as moisture resistance, frost resistance, water resistance and the like, but the inventor finds that each film layer of the film packaging material prepared by the coextrusion film blowing mode has low strength and is easy to deform and damage under pressure or easily separate from each other, so that when the packaging material is opened for use, the phenomenon of interlayer separation that the surface layer can be opened but the inner layer cannot be opened or the inner layer is opened but the surface layer cannot be opened easily occurs, and the interlayer binding property of the packaging material is influenced.
In contrast, according to the method, the surface layer material and the inner layer material are subjected to stretching treatment after being melted and extruded into sheets, so that molecular chains of the surface layer and the inner layer are orderly arranged in an orientation mode on a plane parallel to a film, then heat preservation and heat setting are carried out in a tensioning state, the oriented macromolecular structures are fixed, and finally, the impact strength, the tensile strength and the bending strength of the prepared surface layer and the inner layer are increased through cooling and film forming; and the two are thermally bonded by adopting a dry-type composite process to prepare the formed recyclable packaging material, so that the recyclable packaging material has good strength and toughness, can be tightly bonded on the surface of an article under the action of vacuum pumping when used as a bonded film, has good wrapping protection effect on the article, is not easy to be damaged by puncture, abrasion and the like, is not easy to generate interlayer separation when the packaging material is opened, is difficult to completely open, and has good use feeling.
Preferably, in the preparation of the surface layer, the temperature of longitudinal stretching treatment is 130-150 ℃, the stretching ratio of the longitudinal stretching treatment is 6-8 times, the temperature of transverse stretching treatment is 120-150 ℃, and the stretching ratio of the longitudinal stretching treatment is 6-8 times;
in the preparation of the inner layer, the temperature of longitudinal stretching treatment is 160-180 ℃, the stretching ratio of longitudinal stretching treatment is 4-6 times, the temperature of transverse stretching treatment is 150-170 ℃, and the stretching ratio of longitudinal stretching treatment is 4-6.
By controlling the longitudinal stretching temperature and stretching multiple, and the transverse stretching temperature and stretching multiple of the surface layer material and the inner layer material after the surface layer material and the inner layer material are melted and extruded into sheets, molecular chains of the surface layer and the inner layer can be orderly arranged in the stretching orientation, and the strength performances of the surface layer and the inner layer, such as the stretching strength, the impact strength, the bending strength and the like, are improved, so that the prepared packaging material has high strength and good toughness, has good coating protection effect on an article, and can be tightly attached to the surface of the article when being used as an adhesive film.
Preferably, the glue coated on the surface layer is polyurethane glue, and the hot-pressing temperature of the surface layer and the inner layer is 120-160 ℃.
The surface layer and the inner layer can be stably bonded by polyurethane glue and the hot-pressing temperature is controlled, so that the interlayer bonding property of the packaging material is improved.
In summary, the current polyethylene skin packaging film generally adopts a three-layer structure to achieve higher strength so as to realize excellent protection effect, but the three-layer structure is easy to cause unstable interlayer bonding, so that the packaging film has interlayer separation. The application adopts a two-layer structure of the surface layer and the inner layer, so that the problem of unstable combination between the multi-layer structures is solved, Linear Low Density Polyethylene (LLDPE), Medium Density Polyethylene (MDPE) and Metallocene Linear Low Density Polyethylene (MLLDPE) are adopted in the surface layer, and Low Density Polyethylene (LDPE) and Linear Low Density Polyethylene (LLDPE) are adopted in the inner layer, wherein the LLDPE of the surface layer and the LLDPE of the inner layer are compatible and combined similarly, so that the combination property of the surface layer and the inner layer is improved; meanwhile, the surface layer is preferably added with the compatibilization resin, so that the compatibility of materials in the surface layer is improved, the polyethylene component of the surface layer is similarly compatible and combined with the polyethylene component of the inner layer, and the interlayer bonding property of the surface layer and the inner layer is further improved. In addition, when the modified shell powder is added into the surface layer and the modified silica is added into the inner layer, the packaging material is easy to have unstable combination and interlayer separation because inorganic components are added into the surface layer and the inner layer, so that the compatibilization resin added into the surface layer can improve the interlayer combination between the surface layer added with the modified shell powder and the inner layer added with the modified silica and reduce the interlayer separation. And finally, in the preparation process of the packaging material, a dry-type composite process is adopted, the surface layer and the inner layer are combined through glue, and the surface layer added with the modified shell powder and the inner layer added with the modified silicon dioxide are bonded stably.
Therefore, the application has the following beneficial effects:
1. the surface layer and the inner layer of the polyethylene packaging material are both polyethylene components and are polyethylene packaging layers, and the prepared packaging material is easy to recycle by adopting similar series of high polymers.
2. The surface layer of the application adopts LLDPE, MDPE and MLLDPE to match, so that the surface layer of the packaging material has excellent tensile strength, tear strength, heat resistance and puncture resistance, and when the packaging material is used as a skin film, the surface layer is not easy to wear due to the wrinkles generated by vacuum-pumping deformation.
3. The utility model provides an inner layer adopts intensity fine, the wearability is good, the Linear Low Density Polyethylene (LLDPE) that the barrier property is good, can make the inner layer play good guard action to food, during sauce, moisture, the oil content among the food is difficult for permeating to packaging material, reduce food taint of flavor phenomenon, the cladding protective properties is good, and can combine together with the Linear Low Density Polyethylene (LLDPE) on top layer, improve the associativity on top layer and inner layer, the combination is stable between the layer, whole product stability is high.
4. The surface layer of the food packaging material is added with the compatibilization resin, so that the binding property of the surface layer and the inner layer can be improved, the heat sealing performance of the prepared packaging material after coating food is good, and the coating protection effect is good.
5. According to the preparation method of the packaging material, the surface layer and the inner layer are prepared by adopting the post-stretching treatment of melt extrusion sheets, so that molecular chains of the surface layer and the inner layer are orderly arranged in an orientation manner on a plane parallel to a film, and the impact strength, the tensile strength and the bending strength of the surface layer and the inner layer are improved; and then a dry-type composite process is adopted, the surface layer and the inner layer are combined stably through glue and hot-pressing treatment, so that the prepared packaging material has better strength and toughness, can be tightly attached to the surface of an article under the vacuum-pumping action when being used as a film-attached body, has good wrapping protection effect on the article, is not easy to be damaged by piercing, abrasion and the like, and is not easy to generate the conditions of interlayer separation and difficult complete opening when being opened in the process of using the packaging material.
Detailed Description
The present application is described in further detail below with reference to preparation examples and examples.
Preparation example of modified Shell powder
Preparation example 1
The modified shell powder is prepared by the following steps:
step S1: cleaning and drying shell raw materials, crushing, and sieving with a 50-mesh sieve to obtain shell micro powder;
step S2: calcining the shell micro powder prepared in the step S1 at 420 ℃ for 20min, heating to 800 ℃ at the heating rate of 5 ℃/min, continuing calcining for 30min, cooling to room temperature, and performing nano crushing treatment to obtain nano shell powder;
step S3: soaking 5kg of the nano shell powder prepared in the step S2 into 12.5kg of a modifier, wherein the modifier is prepared by mixing 4.16kg of isopropyl tri (dioctyl pyrophosphato acyloxy) titanate, 2.78kg of stearic acid and 5.56kg of polydimethylsiloxane, then preserving heat for 2h at the temperature of 70 ℃, filtering and drying to prepare the modified shell powder.
The polydimethylsiloxane in this example was selected from creosote-chemical viscosity 50cs polydimethylsiloxane.
Preparation examples 2 to 3
Preparation examples 2 to 3 differed from preparation example 1 in that: the process condition parameters and the raw material composition are specifically shown in the following table 1.
TABLE 1 comparison of Process Condition parameters and raw Material compositions of preparation examples 1-3
Figure BDA0003676345020000081
Figure BDA0003676345020000091
Preparation example 4
This preparation differs from the above preparation 2 in that: calcining and nano-crushing the shell micro powder to prepare the modified shell powder, which comprises the following steps:
step S1: cleaning and drying shell raw materials, crushing, and sieving with a 40-mesh sieve to obtain shell micro powder;
step S2: calcining the shell micro powder prepared in the step S1 at 450 ℃ for 18min, heating to 810 ℃ at the heating rate of 8 ℃/min, continuing calcining for 28min, cooling to room temperature, and performing nano-crushing treatment to obtain the modified shell powder.
Preparation example of modified silica
Preparation example 5
The modified silicon dioxide is prepared by the following steps:
uniformly mixing 0.42kg of isopropyl triisostearate, 0.37kg of isopropyl tri (dioctyl pyrophosphato acyloxy) titanate and 0.21kg of hexamethyldisiloxane to prepare a coupling agent;
uniformly mixing 20kg of ethanol and 10kg of water to prepare a mixed solvent;
adding the coupling agent into the mixed solvent, uniformly dispersing, adding 12kg of nano silicon dioxide, stirring at the temperature of 55 ℃ for 40min, filtering, and drying to obtain pretreated silicon dioxide;
dispersing 5kg of methyl methacrylate in 25kg of acetone, then adding 3kg of thionyl chloride, and uniformly dispersing to obtain a modified material;
adding the pretreated silicon dioxide into the modified material, carrying out reflux reaction at 75 ℃ for 150min, filtering, washing with ethanol for 2 times, and drying to obtain the modified silicon dioxide.
Preparation examples 6 to 7
Preparation examples 6 to 7 differed from preparation example 5 in that: the process condition parameters and the raw material composition are specifically shown in the following table 2.
TABLE 2 comparison of Process Condition parameters and raw Material compositions of preparation examples 5-7
Figure BDA0003676345020000092
Figure BDA0003676345020000101
Preparation example 8
This preparation differs from the above preparation 6 in that: the modified silicon dioxide is prepared after the silicon dioxide is modified by a coupling agent, and the specific steps are as follows:
uniformly mixing 0.98kg of isopropyl triisostearate, 0.63kg of isopropyl tri (dioctyl pyrophosphato acyloxy) titanate and 0.39kg of hexamethyldisiloxane to prepare a coupling agent;
uniformly mixing 22.86kg of ethanol and 9.14kg of water to prepare a mixed solvent;
adding the coupling agent into the mixed solvent, uniformly dispersing, adding 15kg of nano silicon dioxide, stirring at the temperature of 60 ℃ for 35min, filtering and drying to obtain the modified silicon dioxide.
Examples
Example 1
A polyethylene type recyclable packaging material comprises a surface layer and an inner layer which are attached, wherein the surface layer comprises 5kg of linear low density polyethylene, 20kg of medium density polyethylene and 1.5kg of metallocene linear low density polyethylene;
wherein, in the surface layer, the linear low density polyethylene has a melt index of 0.8-1.0g/10min and a density of 0.915-0.928g/cm 3 (ii) a The medium density polyethylene has a melt index of 0.8-1.0g/10min and a density of 0.928-0.935g/cm 3 ；
Melt fingers for metallocene linear low density polyethyleneThe number is 1.8-2.0g/10min, and the density is 0.923-0.928g/cm 3 。
The inner layer comprised 5kg of low density polyethylene and 10kg of linear low density polyethylene;
wherein, in the inner layer, the low density polyethylene has a melt index of 0.9-1.1g/10min and a density of 0.915-0.925g/cm 3 ；
The linear low density polyethylene has a melt index of 0.8-1.0g/10min and a density of 0.922-0.928g/cm 3 。
The preparation method of the polyethylene type recyclable packaging material comprises the following steps:
mixing the surface layer raw materials, melting and extruding the mixture into sheets, then carrying out longitudinal stretching treatment under the conditions that the temperature is 130 ℃ and the stretching ratio is 6 times, carrying out transverse stretching treatment under the conditions that the temperature is 120 ℃ and the stretching ratio is 6 times, carrying out heat preservation and shaping at the temperature of 110 ℃, and finally cooling and drawing to obtain the surface layer;
mixing the raw materials of the inner layer, performing melt extrusion to obtain a sheet, performing longitudinal stretching treatment at the temperature of 160 ℃ and the stretching ratio of 4 times, performing transverse stretching treatment at the temperature of 150 ℃ and the stretching ratio of 4 times, performing heat preservation and shaping at the temperature of 120 ℃, and finally cooling and drawing to obtain the inner layer;
coating polyurethane glue on one surface of the surface layer, then adhering the surface layer coated with the glue to the surface layer, and then thermally pressing the surface layer and the inner layer at the temperature of 120 ℃ to obtain the polyethylene type recyclable packaging material.
Wherein the polyurethane glue is selected from 7550 transparent polyurethane glue from Lord corporation.
Examples 2 to 3
Examples 2-3 differ from example 1 above in that: the process conditions and raw material parameters are as shown in table 3 below.
Example 4
Example 4 differs from the above example 2 in that: the inner layer also comprises 1.5kg of ethylene/vinyl alcohol copolymer, and the ethylene content of the ethylene/vinyl alcohol copolymer is 12-20%.
Example 5
Example 5 differs from the above example 2 in that: the inner layer also comprises 2.5kg of ethylene/vinyl alcohol copolymer, and the ethylene content of the ethylene/vinyl alcohol copolymer is 12-20%.
TABLE 3 comparison of Process parameters and feed conditions for examples 1-5
Figure BDA0003676345020000111
Figure BDA0003676345020000121
Example 6
The present embodiment 6 differs from the above embodiment 4 in that: 0.16kg of the modified shell powder obtained in preparation example 1 was added to the surface layer.
Example 7
The present embodiment 7 differs from the above embodiment 4 in that: 0.16kg of the modified shell powder prepared in preparation example 1 and 0.08kg of PE-g-MAH selected from 1052H type PE-g-MAH of plastic and plastics raw material Co., Ltd, Dongguan were added to the surface layer.
Example 8
The present embodiment 8 differs from the above embodiment 4 in that: 0.16kg of modified shell powder prepared in preparation example 1 and 0.08kg of PE-g-MAH are added into the surface layer, wherein the PE-g-MAH is selected from 1052H type PE-g-MAH of plastic and plastic raw material Co.Ltd of Dongguan city; 0.24kg of the modified silica prepared in production example 5 was added to the inner layer.
Example 9
The present embodiment 9 differs from the above embodiment 4 in that: the surface layer is added with 0.08kg of PE-g-MAH, and the PE-g-MAH is selected from 1052H type PE-g-MAH of plastic and plastic raw material Co.Ltd of Dongguan city.
Example 10
The present embodiment 10 differs from the above embodiment 4 in that: the surface layer is added with 0.08kg of PE-g-MAH, and the PE-g-MAH is selected from 1052H type PE-g-MAH of plastic and plastic raw material Co.Ltd of Dongguan city; 0.24kg of the modified silica prepared in production example 5 was added to the inner layer.
Example 11
This embodiment 11 differs from the above embodiment 4 in that: to the inner layer were added 0.16kg of the modified shell powder obtained in production example 1 and 0.24kg of the modified silica obtained in production example 5.
Example 12
The present embodiment 12 differs from the above embodiment 4 in that: 0.24kg of the modified silica prepared in production example 5 was added to the inner layer.
Example 13
This embodiment 13 differs from the above embodiment 8 in that: the modified shell powder in the surface layer was 0.65kg of the modified shell powder of preparation example 2 and 0.27kg of PE-g-MAH, and the modified silica in the inner layer was 0.32kg of the modified silica obtained in preparation example 6; wherein the PE-g-MAH is selected from 1052H type PE-g-MAH of plastic and large plastic raw material Co.
Example 14
Example 14 differs from the above example 8 in that: the modified shell powder in the surface layer was 0.98kg of the modified shell powder obtained in preparation example 3 and 0.40kg of PE-g-MAA, and the modified silica in the inner layer was 0.40kg of the modified silica obtained in preparation example 7.
Example 15
This embodiment 15 differs from the above embodiment 13 in that: the modified shell powder in the surface layer was 0.65kg of the modified shell powder of production example 4.
Example 16
This embodiment 16 differs from the above embodiment 13 in that: the modified silica in the inner layer was 0.32kg of the modified silica obtained in production example 8.
The above packaging material raw material parameters of examples 6 to 16 are specifically referred to in table 4 below.
TABLE 4 comparison of Process parameters and feed conditions for examples 6-16
Figure BDA0003676345020000131
Figure BDA0003676345020000141
Comparative example
Comparative example 1
Comparative example 1 differs from example 13 above in that: in the preparation step of the packaging material, a double-layer blown film co-extrusion process is adopted to co-extrude and blow the surface layer and the inner layer, and then hot pressing is carried out at the temperature of 140 ℃ to prepare the polyethylene type recyclable packaging material.
Comparative example 2
Comparative example 2 differs from example 13 above in that: 0.65kg of titanium dioxide and.27 kg of PE-g-MAH were added to the surface layer, and 0.32kg of the modified silica obtained in production example 6 was added to the inner layer.
Comparative example 3
This comparative example 3 differs from the above example 13 in that: 0.65kg of montmorillonite and 0.27kg of PE-g-MAH were added to the surface layer, and 0.32kg of modified silica prepared in preparation example 6 was added to the inner layer.
Comparative example 4
A polyethylene film comprises a surface layer, a middle layer and an inner layer which are arranged in sequence, wherein the surface layer comprises 1.5kg of low-density polyethylene, 0.5kg of metallocene polyethylene and 8.0kg of linear polyethylene;
the middle layer comprised 0.5kg of low density polyethylene and 9.5kg of linear polyethylene;
the inner layer comprised 2.0kg of low density polyethylene, 6.0kg of linear polyethylene and 0.5kg of metallocene polyethylene;
the linear polyethylene in the surface layer, the middle layer and the inner layer is ultrahigh molecular weight polyethylene with molecular weight of 10-18 ten thousand and density of 0.927-0.929g/cm 3 (ii) a The metallocene polyethylene has a density of 0.920-0.923g/cm 3 The melt index is 1.0-1.2g/10 min; the low density polyethylene has a density of 0.916-0.918g/cm 3 The melt index is 0.8-0.9g/10 min.
The preparation of the polyethylene film comprises the following steps:
step 1: mixing the raw materials according to respective formulas of the surface layer, the core layer and the inner layer to respectively obtain a surface layer mixed material, a core layer mixed material and an inner layer mixed material;
step 2: respectively adding the surface layer mixed material, the core layer mixed material and the inner layer mixed material into three hoppers of an extruder, and performing blow molding according to a conventional three-layer co-extrusion process after the temperature of the extruder is 150 ℃ to obtain a film, wherein the thicknesses of the surface layer, the core layer and the inner layer are respectively 0.01mm, 0.02mm and 0.01 mm;
and step 3: and cooling and rolling the film to obtain the polyethylene film.
Performance test the packaging materials prepared in examples 1 to 16 and comparative examples 1 to 4 were subjected to transparency, tensile properties, abrasion resistance, and interlayer bonding property tests, and the test results are shown in Table 5.
(1) The transparency is measured by adopting an SDR850 high-precision light transmittance tester to carry out visible light transmittance test at the visible light wavelength of 550 nm;
(2) the tensile property is tested according to the test method of GB/T1040.3-2006 film tensile property, the width of a film sample is 10mm, the length of the film sample is 180mm, the memorability test of an XLM (PC) intelligent electronic tensile tester is adopted, the initial distance between clamps is 100mm, the tensile speed is 5mm/min, each sample is respectively tested five times in the Transverse Direction (TD) and the longitudinal direction (MD), and the average value of the tensile strength in the two directions is respectively obtained;
(3) the abrasion resistance test is to clamp a film sample (with the width of 10mm and the length of 180mm) onto a rotary table platform by adopting a Taber 1700 single-rotary-table type abrasion machine, wherein the surface layer of the film sample faces upwards, the inner layer of the film sample faces downwards, namely the surface layer is abutted against an abrasive wheel; installing a 500 g weight as abrasion test pressure, installing S-42 type abrasive paper on the abrasive wheel, and controlling the rotating speed of a turntable platform clamping the film sample to be 72 rpm; original gram weight m of film before abrasion test 0 And grammage m of the film after abrasion test 1 The abrasion loss Δ m is m 0 -m 1 。
(4) The interlayer bonding performance was measured by a BLD-200H electron peel tester according to the method A of GB/T8808-1988 Soft composite Plastic peeling test methods, for peel strength between the surface layer and the inner layer of each sample.
TABLE 5 tables of Property data of the packaging materials obtained in examples 1 to 16 and comparative examples 1 to 4
Figure BDA0003676345020000161
As can be seen from the above examples 1 to 16 in combination with table 5, the packaging material prepared by the present invention has excellent light transmittance, waterproof insulation property, tensile strength, surface abrasion resistance and interlayer stability, has good coating protection effect on articles, is not easily damaged by piercing, abrasion and the like, can reduce the phenomenon of tainting of food and the like when used for coating and protecting food, and can be completely opened as a whole when used, and has good use feeling.
Among them, as is clear from examples 2, 4 and 5, the addition of ethylene/vinyl alcohol copolymer (EVOH) having a specific ethylene content to the inner layer improves the tensile strength properties of the packaging material, and the resulting packaging material has good protective properties, and when the packaging material is used for vacuum skin-packaging of foods, the packaging material is less likely to be pierced or abraded by the outside world, and has good protective properties.
On the other hand, it is known from examples 4, 6, 7, 8, 11, 12, 13, 14, 15, and 16 that the addition of the modified shell powder to the surface layer can effectively improve the waterproof property, tensile strength, and wear resistance of the packaging material, and when the packaging material is used as a skin film, the packaging material is less likely to be worn due to wrinkles caused by deformation due to vacuuming, so that the protective effect on a coated article is improved, and the use effect is good.
In contrast, in comparative example 2, titanium dioxide is added to the surface layer, and in comparative example 3, montmorillonite is added to the surface layer, and compared with example 13, the performance of the prepared packaging material is reduced in tensile strength and increased in abrasion loss, which shows that the tensile strength and the surface abrasion resistance of the packaging material can be effectively improved by adding the modified shell powder to the surface layer.
As is clear from examples 4, 6, 7, 8, 9 and 10, the addition of the compatibilizer resin to the inner layer improves the interlayer adhesiveness between the surface layer and the inner layer, and thus the packaging material is less likely to suffer from interlayer separation, and when the packaging material is opened, the packaging material is less likely to suffer from interlayer separation in which some layers are opened and some layers are not opened.
In example 12, even though the modified silica was added to the inner layer, the tensile strength and other properties of the packaging material were excellent, but the interlayer peel strength between the surface layer and the inner layer was lower than those of example 10, and the interlayer adhesiveness was lower than that of example 10; in the same way, compared with the example 6 and the example 7, the modified shell powder is added to the surface layer, so that the tensile strength and other properties of the packaging material are excellent, and the compatibilization resin is also added to the surface layer of the example 7, so that the interlayer peeling strength of the surface layer and the inner layer of the packaging material prepared in the example 7 is improved compared with the example 6, and the interlayer bonding property is better than that of the example 6; in the same manner as in examples 10 and 13, the interlayer peel strength between the surface layer and the inner layer of the packaging material obtained in example 13 was higher than that of example 11 by adding a compatibilizing resin to the surface layer. The above results show that the addition of the compatibilizer resin to the surface layer can improve the interlayer bonding between the surface layer and the inner layer, so that the packaging material is not easy to have interlayer separation and the interlayer bonding is stable.
Compared with the comparative example 1 adopting three-layer co-extrusion blow molding to form the film, the embodiment 13 shows that the packaging material is prepared by adopting the dry-type composite process of melting and extruding the surface layer material and the inner layer material to form the sheet, then stretching and hot-pressing and laminating the sheet, the prepared packaging material has excellent tensile strength and interlayer bonding property, can be tightly attached to the surface of an article under the vacuum pumping action when being used as an adhesive film, has good coating protection effect on the article, is not easy to be damaged by puncture, abrasion and the like, is not easy to generate interlayer separation when being opened for use, and has good use feeling.
Compared with the examples 2 and 4, the application shows that the surface layer is prepared by adopting the linear low-density polyethylene, the medium-density polyethylene and the metallocene linear low-density polyethylene with specific melt indexes and density ranges, the inner layer is prepared by adopting the low-density polyethylene and the linear low-density polyethylene with specific melt indexes and density ranges and combining the ethylene/vinyl alcohol copolymer with specific ethylene content, the prepared packaging material has excellent performances such as impact strength, tensile strength and toughness, the interlayer combination is stable, the coating protection effect on an article is good, the article is not easy to be damaged by puncture, abrasion and the like, the whole body can be completely opened during use, and the use feeling is good; and the surface layer and the inner layer both adopt polyethylene components, so that the prepared packaging material is easy to recycle and is green and environment-friendly.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.

Claims (10)

1. A polyethylene-based recyclable packaging material, characterized in that: the surface layer comprises linear low-density polyethylene, medium-density polyethylene and metallocene linear low-density polyethylene, and the mixing weight ratio of the linear low-density polyethylene to the medium-density polyethylene to the metallocene linear low-density polyethylene is 1: 4-6: 0.3-0.8;
the inner layer comprises low-density polyethylene and linear low-density polyethylene, and the mixing weight ratio of the low-density polyethylene to the linear low-density polyethylene is 1: 2-4.
2. The polyethylene-based recyclable packaging material of claim 1, wherein: in the surface layer, the linear low density polyethylene has a melt index of 0.8-1.0g/10min and a density of 0.915-0.928g/cm 3 ；
The medium density polyethylene has a melt index of 0.8-1.0g/10min and a density of 0.928-0.935g/cm 3 ；
The metallocene linear low density polyethylene has a melt index of 1.8-2.0g/10min and a density of 0.923-0.928g/cm 3 ；
In the inner layer, the low density polyethylene has a melt index of 0.9-1.1g/10min and a density of 0.915-0.925g/cm 3 ；
The linear low density polyethylene has a melt index of 0.8-1.0g/10min and a density of 0.922-0.928g/cm 3 。
3. The polyethylene-based recyclable packaging material of claim 1 or 2, wherein: the inner layer also comprises ethylene/vinyl alcohol copolymer, and the mixing weight ratio of the low-density polyethylene, the linear low-density polyethylene and the ethylene/vinyl alcohol copolymer is 1: 2-4: 0.3 to 0.5, and the ethylene content in the ethylene/vinyl alcohol copolymer is 12 to 20%.
4. The polyethylene-based recyclable packaging material of claim 3, wherein: modified shell powder is added into the surface layer, and the addition amount of the modified shell powder is 0.5-3% of the weight of the surface layer; the modified shell powder is prepared by the following steps:
step S1: cleaning and drying shell raw materials, pulverizing, and sieving with 20-50 mesh sieve to obtain shell micropowder;
step S2: calcining the shell micro powder prepared in the step S1, cooling to room temperature, and performing nano crushing treatment to obtain nano shell powder;
step S3: and (4) soaking the nano shell powder prepared in the step (S2) into a modifier, preserving heat for 1-2h at the temperature of 70-85 ℃, filtering and drying to obtain the modified shell powder.
5. The polyethylene-based recyclable packaging material of claim 4, wherein: in the step S2, the calcination treatment is specifically to calcine at 450 ℃ for 15-20min, then raise the temperature to 820 ℃ at a temperature rise rate of 5-10 ℃/min, and continue to calcine for 25-30 min; in the step S3, the infiltration weight ratio of the nano shell powder to the modifier is 1:2.5-3, and the modifier is prepared by mixing isopropyl tri (dioctyl pyrophosphato acyloxy) titanate, stearic acid and polysiloxane in a weight ratio of 1-1.5: 1: 2-3, mixing.
6. The polyethylene-based recyclable packaging material of claim 4, wherein: the surface layer is also added with a compatibilization resin, and the addition amount of the compatibilization resin is 0.3-1.5% of the weight of the surface layer; the compatibilization resin is PE-g-MAH and/or PE-g-MAA.
7. The polyethylene-based recyclable packaging material of claim 6, wherein: modified silicon dioxide is added into the inner layer, and the addition amount of the modified silicon dioxide is 1.2-2.0% of the weight of the inner layer; the modified silicon dioxide is prepared by the following steps:
adding 1-3 parts by weight of coupling agent into 30-35 parts by weight of mixed solvent, uniformly dispersing, adding 12-15 parts by weight of nano silicon dioxide, stirring at 55-68 ℃ for 30-40min, filtering, and drying to obtain pretreated silicon dioxide;
dispersing 5-10 parts by weight of methyl methacrylate in 25-30 parts by weight of acetone, then adding 3-8 parts by weight of thionyl chloride, and uniformly dispersing to obtain a modified material;
adding the pretreated silicon dioxide into the modified material, carrying out reflux reaction at 75-85 ℃ for 90-150min, filtering, washing with ethanol for 2-3 times, and drying to obtain the modified silicon dioxide.
8. The polyethylene-based recyclable packaging material of claim 7, wherein: the coupling agent is prepared by mixing isopropyl triisostearate, isopropyl tri (dioctyl pyrophosphoryl oxy) titanate and hexamethyldisiloxane in a weight ratio of 2-3:1.5-1.8: 1; the mixed solvent is formed by mixing ethanol and water according to the weight ratio of 2-3:1.
9. A process for the preparation of a recyclable packaging material of the polyethylene type according to any of claims 1 to 8, characterized in that: the method comprises the following steps:
mixing the surface layer raw materials, melting and extruding the mixture into sheets, then carrying out longitudinal stretching treatment and transverse stretching treatment, carrying out heat preservation and shaping at the temperature of 110-130 ℃, and finally cooling and drawing to obtain the surface layer;
mixing the raw materials of the inner layer, melting and extruding the raw materials into sheets, then carrying out longitudinal stretching treatment and transverse stretching treatment, carrying out heat preservation and shaping at the temperature of 120-140 ℃, and finally cooling and drawing to obtain the inner layer;
and coating glue on one surface of the surface layer, then attaching the surface coated with the glue on the surface layer to the inner layer, and then thermally pressing the surface layer and the inner layer to obtain the polyethylene type recyclable packaging material.
10. The method of making a polyethylene-based recyclable packaging material as defined in claim 9, wherein: in the preparation of the surface layer, the temperature of longitudinal stretching treatment is 130-150 ℃, the stretching ratio of the longitudinal stretching treatment is 6-8 times, the temperature of transverse stretching treatment is 120-150 ℃, and the stretching ratio of the longitudinal stretching treatment is 6-8 times;
in the preparation of the inner layer, the temperature of longitudinal stretching treatment is 160-180 ℃, the stretching ratio of longitudinal stretching treatment is 4-6 times, the temperature of transverse stretching treatment is 150-170 ℃, and the stretching ratio of longitudinal stretching treatment is 4-6 times.
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