CN117465100B - High-barrier polypropylene recyclable packaging film and preparation method thereof - Google Patents

High-barrier polypropylene recyclable packaging film and preparation method thereof Download PDF

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Publication number
CN117465100B
CN117465100B CN202311601782.XA CN202311601782A CN117465100B CN 117465100 B CN117465100 B CN 117465100B CN 202311601782 A CN202311601782 A CN 202311601782A CN 117465100 B CN117465100 B CN 117465100B
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layer
polypropylene
film
barrier
random copolymer
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CN117465100A (en
Inventor
卓友敬
欧欣
彭森荣
林琼漫
黄竹朋
周晓笋
叶宇俊
杨浩文
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Guangdong Daoke New Material Technology Co ltd
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Guangdong Daoke New Material Technology 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
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • 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
    • 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
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/72—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the structure of the material of the parts to be joined
    • B29C66/723—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the structure of the material of the parts to be joined being multi-layered
    • 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
    • B29C69/00—Combinations of shaping techniques not provided for in a single one of main groups B29C39/00 - B29C67/00, e.g. associations of moulding and joining techniques; Apparatus therefore
    • 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
    • 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
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B9/045—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance 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
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/10—Homopolymers or copolymers of methacrylic acid esters
    • C09J133/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • 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
    • B32B2250/242—All polymers belonging to those covered by group B32B27/32
    • 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
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • 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
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/14—Gas barrier composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/80—Packaging reuse or recycling, e.g. of multilayer packaging

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Laminated Bodies (AREA)

Abstract

The application discloses a high-barrier polypropylene recyclable packaging film and a preparation method thereof, and relates to food packaging materials. The packaging film comprises a BOPP film, a first bonding layer, a high-barrier middle layer, a second bonding layer and a CPP film which are sequentially arranged from outside to inside; the BOPP film comprises an inner surface layer adjacent to the first bonding layer, wherein the inner surface layer comprises raw material random copolymer polypropylene granules A and modified polypropylene granules; the CPP film comprises a composite layer adjacent to the second bonding layer, wherein the composite layer comprises random copolymer polypropylene granules B and modified polypropylene granules; wherein the modified polypropylene granules are prepared from maleic anhydride, glycidyl methacrylate, styrene and propylene polymer and an initiator. The plastic materials adopted by the high-barrier polypropylene recyclable packaging film are polypropylene, so that the high-barrier polypropylene recyclable packaging film has the characteristic of convenient recycling, and has the advantages of good barrier durability and high-temperature steaming resistance.

Description

High-barrier polypropylene recyclable packaging film and preparation method thereof
Technical Field
The invention relates to the field of food packaging materials, in particular to a high-barrier polypropylene recyclable packaging film and a preparation method thereof.
Background
To improve the barrier properties of the packaging film, the packaging film is typically present in the form of a composite packaging film, such as PET/PVDC/CPP, BOPA/PVDC/CPP, PET/Al/BOPA/CPP, and the like. However, these composite packaging films all contain multiple plastic films, and the recycling difficulty is higher than that of films using only a single plastic material. Currently, packaging films of a single plastic material are being used in europe to improve the recyclability of the packaging films. However, packaging films of a single plastic material suffer from the disadvantage of poor barrier properties. Therefore, how to provide a packaging film which is convenient to recycle and has good barrier property has important research significance.
Among them, a polypropylene packaging film is commonly used as a packaging film made of a single plastic material. The polypropylene packaging film comprises a BOPP film, a high-barrier middle layer and a CPP film which are sequentially arranged from outside to inside. However, the BOPP film in the related art is usually prepared by adopting random copolymer polypropylene or homo-polypropylene through a melting and biaxial stretching process, and the CPP film is usually prepared by adopting random copolymer polypropylene or homo-polypropylene through a melting and tape casting process, so that the problem of poor combination stability of the BOPP film and the CPP film with the high-barrier interlayer exists, and further the poor barrier property of the polypropylene packaging film is caused.
In order to improve the bonding stability between the BOPP film and the high-barrier interlayer, and between the CPP film and the high-barrier interlayer, the BOPP film and the CPP film are usually subjected to corona treatment prior to compounding in the related art. However, the bonding fastness between the layers of the polypropylene packaging film can only be improved briefly, and the bonding fastness between the BOPP film and the high-barrier middle layer and the bonding fastness between the CPP film and the high-barrier middle layer can be gradually reduced along with the extension of time, and even layering problems occur, so that the barrier durability of the packaging film is poor. In addition, the high-temperature steaming and boiling disinfection treatment also easily causes separation between the BOPP film after corona treatment and the high-barrier middle layer, and between the CPP film after corona treatment and the high-barrier middle layer, namely the high-temperature steaming and boiling resistance of the polypropylene packaging film is poor.
Disclosure of Invention
In order to improve the barrier durability and the high-temperature steaming resistance of the polypropylene packaging film in the related art, the application provides a high-barrier polypropylene recyclable packaging film and a preparation method thereof.
The application provides a high-barrier polypropylene recyclable packaging film, which adopts the following technical scheme:
a high-barrier polypropylene recyclable packaging film comprises a BOPP film, a first bonding layer, a high-barrier middle layer, a second bonding layer and a CPP film which are sequentially arranged from outside to inside;
The BOPP film comprises an inner surface layer adjacent to a first adhesive layer, wherein the inner surface layer comprises raw material random copolymer polypropylene granules A and modified polypropylene granules, and the weight ratio of the random copolymer polypropylene granules A to the modified polypropylene granules is (85-90): (10-15); the melt index of the random copolymer polypropylene granules A is 1.8-2.5g/10min;
the CPP film comprises a composite layer adjacent to a second adhesive layer, wherein the composite layer comprises random copolymer polypropylene granules B and modified polypropylene granules, and the weight ratio of the random copolymer polypropylene granules B to the modified polypropylene granules is (80-90): (10-20); the melt index of the random copolymer polypropylene granules B is 4-8g/10min;
Wherein the modified polypropylene granules comprise raw materials of maleic anhydride, glycidyl methacrylate, styrene, propylene polymer and initiator, and the weight ratio of the maleic anhydride, the glycidyl methacrylate, the styrene, the propylene polymer and the initiator is (6.5-9.4): (8.8-12.5): (2.3-4.2): 100: (0.2-0.4).
The packaging film comprises a BOPP film, a first adhesive layer, a high-barrier middle layer, a second adhesive layer and a CPP film which are sequentially arranged from outside to inside. Firstly, the plastic materials adopted by the high-barrier polypropylene recyclable packaging film are all polypropylene materials, and the high-barrier polypropylene recyclable packaging film has the characteristic of convenient recycling.
Secondly, set up respectively between high separation intermediate level and the BOPP film, between high separation intermediate level and the CPP film and by polyurethane glue or high temperature resistant acrylic ester glue's at least one first adhesive linkage, second adhesive linkage, under the effect of adhesive linkage (i.e. first adhesive linkage and second adhesive linkage), high separation intermediate level is difficult for taking place the interlayer separation with BOPP film or CPP film, is favorable to improving packaging film's interlayer bonding fastness, can improve packaging film and take place the problem of layering easily under the circumstances of long-time storage.
In addition, the main raw materials of the inner surface layer of the BOPP film and the composite layer of the CPP film adopt random copolymer polypropylene granules with high transparency, and then modified polypropylene granules are doped for auxiliary modification. The modified polypropylene granules are modified polypropylene granules obtained by modifying maleic anhydride, glycidyl methacrylate and styrene together, the polarity of the modified polypropylene granules is improved, and the modified polypropylene granules are added into the composite layer of the inner surface layer of the BOPP film and the CPP film, so that the polarity of the composite layer of the inner surface layer of the BOPP film and the CPP film can be improved, and stable combination between the BOPP film and the first adhesive layer and stable combination between the BOPP film and the CPP film and between the BOPP film and the second adhesive layer can be realized without corona treatment of the BOPP film and the CPP film. Moreover, after the modified polypropylene granules are adopted to modify the composite layer of the inner surface layer and the CPP of the BOPP, the permeation stability and the high-temperature steaming resistance of the inner surface layer and the composite layer can be improved, and the barrier durability and the high-temperature steaming resistance of the polypropylene packaging film are effectively improved.
Optionally, the propylene polymer is a homo-polypropylene, and the melt index of the homo-polypropylene is 6-8g/10min.
In the application, the propylene polymer in the modified polypropylene granules adopts the homopolymerized polypropylene with the melt index within the range of 6-8g/10min, so that the permeation resistance, the permeation resistance and the high-temperature digestion resistance of the inner surface layer and the composite layer can be further improved, the barrier durability and the high-temperature digestion resistance of the packaging film can be further improved, and meanwhile, the dimensional stability of the packaging film can be also improved.
Preferably, the initiator comprises a photoinitiator and a peroxy initiator, wherein the weight ratio of the photoinitiator to the peroxy initiator is (1-1.5): 1.
Wherein, the photoinitiator adopts any one of diphenyl ketone and 2, 4-dihydroxydiphenyl ketone.
The peroxy initiator adopts at least one of dicumyl peroxide and dibenzoyl peroxide.
Optionally, the preparation method of the modified polypropylene granule comprises the following steps:
Uniformly mixing a propylene polymer, maleic anhydride, glycidyl methacrylate, styrene and an initiator to obtain a premix; irradiating the premix by using an ultraviolet lamp to obtain an irradiation grafting composition;
And (3) carrying out melt extrusion and crushing on the irradiation grafting composition at 180-200 ℃ to obtain modified polypropylene granules.
According to the application, the modified polypropylene granules are prepared by adopting the method, and can improve the permeation resistance stability of BOPP films and CPP films and improve the high-temperature steaming resistance of the BOPP films and the CPP films.
Optionally, the first bonding layer and the second bonding layer comprise high-temperature-resistant polyurethane glue and high-temperature-resistant acrylate glue, and the weight ratio of the high-temperature-resistant polyurethane glue to the high-temperature-resistant acrylate glue is (3-4): 1.
In the application, the first adhesive layer and the second adhesive layer are preferably prepared by adopting the glue mixed by the high-temperature-resistant polyurethane glue and the high-temperature-resistant acrylic ester glue according to the weight ratio (3-4): 1, compared with the single high-temperature-resistant polyurethane glue or the high-temperature-resistant acrylic ester glue, the preparation of the first adhesive layer and the second adhesive layer by adopting the optimized glue can ensure the stable combination between the BOPP film and the first adhesive layer and between the CPP film and the second adhesive layer, and the dimensional stability of the packaging film is good.
Optionally, the high temperature resistant acrylic ester glue comprises an acrylic ester monomer, an aromatic primary amine compound containing alkenyl, styrene, an azo initiator and a solvent, wherein the weight ratio of the acrylic ester monomer to the aromatic primary amine compound containing alkenyl to the styrene to the azo initiator to the solvent is (45-65): (12-18): (5.5-6.8): (0.4-0.8): (25-35).
In the application, the high-temperature resistant acrylic ester glue prepared from the raw materials in the proportion range is preferable, and the high-temperature resistant acrylic ester glue has high-temperature resistance, and is beneficial to further improving the combination stability between the BOPP film and the first bonding layer and between the CPP film and the second bonding layer, so that the packaging film has better barrier durability and high-temperature digestion resistance.
Preferably, ethanol is used as the solvent.
Optionally, the alkenyl-containing aromatic primary amine compound adopts at least one of p-vinylbenzylamine and (E) -4-phenyl-3-butene-1-amine.
The aromatic primary amine compound containing alkenyl and glycidyl methacrylate in the modified polypropylene can be used for further improving the combination stability between the BOPP film and the first adhesive layer and between the CPP film and the second adhesive layer, so that the packaging film has longer storage time and higher barrier stability.
Optionally, the preparation method of the high-temperature-resistant acrylic ester glue comprises the following steps:
adding an acrylic ester monomer, an aromatic primary amine compound containing alkenyl and styrene into a solvent, and uniformly stirring to obtain a mixture;
Adding azo initiator into the mixture, stirring uniformly, heating to 65-75 ℃, heating and refluxing for 3-5h, and cooling to obtain the high-temperature-resistant acrylic ester glue.
According to the application, the high-temperature-resistant acrylic ester glue is prepared by adopting the method, and the method has the advantages of simple steps and convenience in operation.
Optionally, the BOPP film further comprises an outer skin layer and a core layer, wherein the core layer is located between the outer skin layer and the inner skin layer;
wherein the outer surface layer comprises random copolymer polypropylene granules A and modified polypropylene granules, and the weight ratio of the random copolymer polypropylene granules A to the modified polypropylene granules is (83-88): (12-17);
the core layer comprises a random copolymer polypropylene granule A, a modified polypropylene granule and a polyolefin elastomer A, wherein the weight ratio of the random copolymer polypropylene granule A to the modified polypropylene granule to the polyolefin elastomer A is 100: (8-12): (15-25), and the melt index of the polyolefin elastomer A is 0.8-1.2g/10min, and the melt temperature is 95-105 ℃.
According to the application, the external surface layer of the BOPP film is doped with the modified polypropylene particles for modification, so that the polarity of the external surface layer of the BOPP film can be improved, the external surface layer of the BOPP film can be printed without corona treatment, and the printed attachment fastness is high. Meanwhile, the addition of the modified polypropylene granules can further improve the permeation resistance stability and the high-temperature steaming resistance of the outer surface layer, and can further improve the barrier durability and the high-temperature steaming resistance of the packaging film.
The core layer of the BOPP film is doped with modified polypropylene granules and polyolefin elastomer A to modify the random copolymer polypropylene granules A. The addition of the modified polypropylene particles can improve the bonding stability of each layer of the BOPP film, and has a promotion effect on further improving the barrier durability of the packaging film. However, the modified polypropylene particles are easy to cause the processing performance of the BOPP film to be reduced, so the core layer of the application is also doped with the polyolefin elastomer A, the processing performance of the BOPP film is effectively improved through the polyolefin elastomer A, the rejection rate of the BOPP film is reduced, and meanwhile, the barrier performance of the packaging film is also improved. In addition, the polyolefin elastomer A and the modified polypropylene particles are mixed together, so that the transparency of the core layer is not affected, and when the melt index of the polyolefin elastomer A is in the range of 0.8-1.2g/10min, the polyolefin elastomer A is favorably promoted to be uniformly dispersed in the core layer.
Optionally, in the BOPP film, the thickness ratio of the outer surface layer, the core layer and the inner surface layer is 1: (3-4):1.
Optionally, the CPP film further includes a heat seal layer and a support layer, the support layer being located between the composite layer and the heat seal layer;
Wherein the supporting layer comprises a random copolymer polypropylene granule B, a modified polypropylene granule and a polyolefin elastomer B, and the weight ratio of the random copolymer polypropylene granule B to the modified polypropylene granule to the polyolefin elastomer B is 100: (5-10): (10-20); the heat-seal layer comprises a random copolymer polypropylene pellet B and a polyolefin elastomer B, and the weight ratio of the random copolymer polypropylene pellet B to the polyolefin elastomer B is (88-92): (8-12); and the melt index of the polyolefin elastomer B is 2-3g/10min, and the melt temperature is 90-100 ℃.
According to the application, the modified polypropylene granules and the polyolefin elastomer B are added into the supporting layer of the CPP film to modify the random copolymer polypropylene granules B, so that the combination stability of each layer of the CPP film is improved, the barrier durability of the packaging film is further improved, the permeation resistance stability and the high-temperature steaming resistance of the outer surface layer can be further improved, and the barrier durability and the high-temperature steaming resistance of the packaging film can be further improved. However, the modified polypropylene granules are easy to be mixed to cause the reduction of the processability of the CPP film, so that the supporting layer is also mixed with the polyolefin elastomer B, the processability of the CPP film is effectively improved through the polyolefin elastomer B, the rejection rate of the CPP film is reduced, and meanwhile, the barrier property of the packaging film is also improved. In addition, the polyolefin elastomer B and the modified polypropylene particles are mixed together, so that the transparency of the supporting layer is not affected, and when the melt index of the polyolefin elastomer B is in the range of 2-3g/10min, the polyolefin elastomer B is beneficial to promoting the uniform dispersion of the polyolefin elastomer B into the supporting layer.
The heat-seal layer comprises random copolymer polypropylene pellets B and a polyolefin elastomer B, and the addition of the polyolefin elastomer B enables the polypropylene packaging film to obtain higher heat-seal strength at lower heat-seal temperature.
Optionally, in the CPP film, the thickness ratio of the composite layer, the supporting layer and the heat-sealing layer is 1: (3-4):1.
Optionally, the high-barrier intermediate layer is at least one of an alumina coating, a silica coating and a silicon nitride coating.
Optionally, the thickness of the BOPP film is 18-28 μm, the thickness of the first adhesive layer is 1-3 μm, the thickness of the high-barrier interlayer is 16-20 μm, the thickness of the second adhesive layer is 1-3 μm, and the thickness of the CPP film is 40-100 μm.
In the application, the thickness of the first adhesive layer and the second adhesive layer is controlled to be 1-3 mu m, so that the introduction of impurities can be reduced, and the convenience of recycling the packaging film can be improved.
In a second aspect, the preparation method of the high-barrier polypropylene recyclable packaging film provided by the application adopts the following technical scheme:
the preparation method of the high-barrier polypropylene recyclable packaging film comprises the following steps:
respectively mixing and melting all the raw materials of the BOPP film uniformly, extruding in a coextrusion mode, and preparing the BOPP film by a biaxial stretching process;
respectively mixing and melting all the raw materials of the CPP film uniformly, extruding in a coextrusion mode, and preparing the CPP film by adopting a tape casting process;
uniformly coating a first bonding layer on the BOPP film to obtain a first composite material;
Uniformly coating a second adhesive layer on the CPP film, and then arranging a high-barrier middle layer on one side of the second adhesive layer, which is away from the CPP film, so as to obtain a second composite material;
and compounding the high-barrier middle layer of the second composite material with the first bonding layer of the first composite material to obtain the high-barrier polypropylene recyclable packaging film.
The high-barrier polypropylene recyclable film prepared by the method has the advantage of simplicity in operation, and meanwhile, the packaging film with good barrier durability and high-temperature digestion resistance can be obtained.
In summary, the application at least comprises the following beneficial technical effects:
1. The main raw materials of the inner surface layer of the BOPP film and the composite layer of the CPP film adopt random copolymer polypropylene granules with high transparency, and then modified polypropylene granules are doped for auxiliary modification. The modified polypropylene granules are modified polypropylene granules obtained by modifying maleic anhydride, glycidyl methacrylate and styrene together, the polarity of the modified polypropylene granules is improved, and the modified polypropylene granules are added into the composite layer of the inner surface layer of the BOPP film and the CPP film, so that the polarity of the composite layer of the inner surface layer of the BOPP film and the CPP film can be improved, and stable combination between the BOPP film and the first adhesive layer and stable combination between the BOPP film and the CPP film and between the BOPP film and the second adhesive layer can be realized without corona treatment of the BOPP film and the CPP film. Moreover, after the modified polypropylene granules are adopted to modify the composite layer of the inner surface layer and the CPP of the BOPP, the permeation stability and the high-temperature steaming resistance of the inner surface layer and the composite layer can be improved, and the barrier durability and the high-temperature steaming resistance of the polypropylene packaging film are effectively improved.
2. In the application, the propylene polymer in the modified polypropylene granules adopts the homopolymerized polypropylene with the melt index within the range of 6-8g/10min, so that the permeation resistance, the permeation resistance and the high-temperature digestion resistance of the inner surface layer and the composite layer can be further improved, the barrier durability and the high-temperature digestion resistance of the packaging film can be further improved, and meanwhile, the dimensional stability of the packaging film can be also improved.
3. The first bonding layer and the second bonding layer are preferably prepared by glue mixed by the high-temperature-resistant polyurethane glue and the high-temperature-resistant acrylic ester glue according to the weight ratio (3-4): 1; the high-temperature-resistant acrylic ester glue is preferably prepared from an acrylic ester monomer, an aromatic primary amine compound containing alkenyl, styrene, an azo initiator and a solvent, has high-temperature resistance, and is favorable for further improving the combination stability between the BOPP film and the first bonding layer and between the CPP film and the second bonding layer, so that the packaging film has better barrier durability and high-temperature digestion resistance.
Drawings
FIG. 1 is a schematic structural view of the high barrier polypropylene recyclable packaging film of the present application.
Reference numerals illustrate:
1. BOPP film; 11. an outer surface layer; 12. a core layer; 13. an inner surface layer; 2. a first adhesive layer; 3. a high barrier interlayer; 4. a second adhesive layer; 5. CPP film; 51. a composite layer; 52. a support layer; 53. and (3) a heat sealing layer.
Detailed Description
The present application will be described in further detail with reference to fig. 1.
Preparation example
[ PREPARATION EXAMPLE 1]
A modified polypropylene pellet, comprising the following raw materials:
Maleic anhydride: 6.5kg;
Glycidyl methacrylate: 12.5kg;
Styrene: 2.3kg;
Propylene polymer: 100kg; in this preparation, the propylene polymer was a random polypropylene polymer, which was designated M800E and had a melt index of 8g/10min.
And (3) an initiator: 0.2kg; in the preparation example, the initiator comprises benzophenone and dicumyl peroxide, and the weight ratio of the benzophenone to the dicumyl peroxide is 1:1.
In this preparation example, the preparation method of the modified polypropylene pellet comprises the following steps:
Uniformly mixing a propylene polymer, maleic anhydride, glycidyl methacrylate, styrene and an initiator to obtain a premix; irradiating the premix for 3min by using an ultraviolet lamp with the wavelength of 250nm and the irradiation intensity of 0.5J/cm 2 to obtain an irradiation grafting composition;
and (3) carrying out melt extrusion and crushing on the irradiation grafting composition at 180 ℃ to obtain modified polypropylene granules.
[ PREPARATION EXAMPLE 2]
A modified polypropylene pellet, comprising the following raw materials:
Maleic anhydride: 9.4kg;
Glycidyl methacrylate: 8.8kg;
Styrene: 4.2kg;
Propylene polymer: 100kg; in this preparation, the propylene polymer was a random polypropylene polymer, which was designated M800E and had a melt index of 8g/10min.
And (3) an initiator: 0.4kg; in this preparation, the initiator comprises 2, 4-dihydroxybenzophenone and dibenzoyl peroxide, and the weight ratio of 2, 4-dihydroxybenzophenone to dibenzoyl peroxide is 1.5:1.
In this preparation example, the preparation method of the modified polypropylene pellet comprises the following steps:
Uniformly mixing a propylene polymer, maleic anhydride, glycidyl methacrylate, styrene and an initiator to obtain a premix; irradiating the premix for 2min by using an ultraviolet lamp with the wavelength of 300nm and the irradiation intensity of 0.3J/cm 2 to obtain an irradiation grafting composition;
and (3) carrying out melt extrusion and crushing on the irradiation grafting composition at 200 ℃ to obtain modified polypropylene granules.
[ PREPARATION EXAMPLE 3]
Modified polypropylene pellets differ from [ preparation example 1] in that: propylene polymers are different.
In this preparation, the propylene polymer was a homo-polypropylene polymer, which was designated F800E and had a melt index of 8g/10min.
[ PREPARATION EXAMPLE 4]
Modified polypropylene pellets differ from [ preparation example 1] in that: propylene polymers are different.
In this preparation, the propylene polymer was a homo-polypropylene polymer, which was identified by the trade name H4540 and had a melt index of 12g/10min.
Examples
[ Example 1]
Referring to fig. 1, the high-barrier polypropylene recyclable packaging film comprises a BOPP film 1, a first adhesive layer 2, a high-barrier middle layer 3, a second adhesive layer 4 and a CPP film 5 which are sequentially arranged from outside to inside.
In this example, the thickness of each layer in the high barrier polypropylene recyclable packaging film is as follows:
The BOPP film 1 had a thickness of 18 μm, the first adhesive layer 2 had a thickness of 1 μm, the high-barrier interlayer 3 had a thickness of 16 μm, the second adhesive layer 4 had a thickness of 1 μm, and the CPP film 5 had a thickness of 100. Mu.m.
Specifically, the BOPP film 1 includes an outer surface layer 11, a core layer 12 and an inner surface layer 13 sequentially arranged from outside to inside, wherein the thickness ratio of the outer surface layer 11, the core layer 12 to the inner surface layer 13 is 1:3:1; the CPP film 5 comprises a composite layer 51, a supporting layer 52 and a heat sealing layer 53 which are sequentially arranged from outside to inside, wherein the thickness ratio of the composite layer 51 to the supporting layer 52 to the heat sealing layer 53 is 1:4:1.
In this example, the raw materials used for each layer of BOPP film 1 are as follows:
The outer surface layer 11 adopts random copolymer polypropylene granules A;
The core layer 12 adopts random copolymer polypropylene granules A;
the inner surface layer 13 comprises a modified polypropylene pellet prepared by random copolymerization polypropylene pellet A and [ preparation example 1 ], and the weight ratio of the random copolymerization polypropylene pellet A to the modified polypropylene pellet is 85:15;
The above-mentioned random copolymer polypropylene pellet A of this example was obtained by using R520Y of Korean SK, and had a melt index of 1.8g/10min.
In the embodiment, the first adhesive layer 2 is prepared by coating and drying high-temperature-resistant polyurethane glue, wherein in the embodiment, the high-temperature-resistant polyurethane glue is purchased from nine glue dispensing industries, and the model is JD-7810;
In this embodiment, the high-barrier interlayer 3 is an alumina layer;
In this embodiment, the second adhesive layer 4 is made by coating and drying high temperature resistant polyurethane glue, wherein in this embodiment, the high temperature resistant polyurethane glue is purchased from nine glue dispensing industry, and the model is JD-7810;
in this example, the following materials were used for each layer of the CPP film 5:
the composite layer 51 comprises random copolymer polypropylene granules B and modified polypropylene granules, wherein the weight ratio of the random copolymer polypropylene granules B to the modified polypropylene granules is 90:10;
the support layer 52 is made of random copolymer polypropylene pellets B;
The heat-sealing layer 53 adopts random copolymer polypropylene granules B;
In this example, the above-mentioned random copolymer polypropylene pellet B was used as R401 in Korean hyosung , and had a melt index of 4g/10min.
In this embodiment, the preparation method of the high-barrier polypropylene recyclable packaging film includes the following steps:
Feeding all raw materials of an outer surface layer 11 of a BOPP film 1 into an extruder A1, feeding all raw materials of a core layer 12 into an extruder B1, feeding all raw materials of an inner surface layer 13 into an extruder C1, uniformly melting all the layers, co-extruding by adopting a three-way die head at the extrusion temperature of 260 ℃, casting a sheet, biaxially stretching, cooling and shaping to obtain the BOPP film 1 with the thickness of 18 mu m; wherein the longitudinal stretching temperature is 150 ℃, the stretching ratio is 4 times, the transverse stretching temperature is 180 ℃, and the stretching ratio is 4 times;
Feeding raw materials of a CPP film 5 composite layer 51 into an extruder A2, feeding raw materials of a supporting layer 52 into an extruder B2, feeding raw materials of a heat sealing layer 53 into an extruder C2, uniformly melting all the layers, co-extruding by adopting a three-way die head, wherein the extrusion temperature is 250 ℃, and then casting and cooling to form to obtain a CPP film 5 with the thickness of 100 mu m;
uniformly coating a first bonding layer 2 on the BOPP film 1, and curing to obtain a first composite material;
uniformly coating a second bonding layer 4 on the CPP film 5, and setting a high-barrier middle layer 3 on one side of the second bonding layer 4 away from the CPP film 5 after curing to obtain a second composite material;
and compounding the high-barrier middle layer 3 of the second composite material with the first bonding layer 2 of the first composite material to obtain the high-barrier polypropylene recyclable packaging film.
[ Example 2]
Referring to fig. 1, the high-barrier polypropylene recyclable packaging film comprises a BOPP film 1, a first adhesive layer 2, a high-barrier middle layer 3, a second adhesive layer 4 and a CPP film 5 which are sequentially arranged from outside to inside.
In this example, the thickness of each layer in the high barrier polypropylene recyclable packaging film is as follows:
The BOPP film 1 had a thickness of 28. Mu.m, the first adhesive layer 2 had a thickness of 3. Mu.m, the high-barrier interlayer 3 had a thickness of 20. Mu.m, the second adhesive layer 4 had a thickness of 3. Mu.m, and the CPP film 5 had a thickness of 40. Mu.m.
Specifically, the BOPP film 1 includes an outer surface layer 11, a core layer 12 and an inner surface layer 13 sequentially arranged from outside to inside, wherein the thickness ratio of the outer surface layer 11, the core layer 12 to the inner surface layer 13 is 1:4:1; the CPP film 5 comprises a composite layer 51, a supporting layer 52 and a heat sealing layer 53 which are sequentially arranged from outside to inside, wherein the thickness ratio of the composite layer 51 to the supporting layer 52 to the heat sealing layer 53 is 1:3:1.
In this example, the raw materials used for each layer of BOPP film 1 are as follows:
The outer surface layer 11 adopts random copolymer polypropylene granules A;
The core layer 12 adopts random copolymer polypropylene granules A;
the inner surface layer 13 comprises modified polypropylene granules prepared by random copolymer polypropylene granules A and [ preparation example 2 ], and the weight ratio of the random copolymer polypropylene granules A to the modified polypropylene granules is 90:10;
The random copolymer polypropylene pellets A of this example were prepared with M250E from Shanghai Jinshan and had a melt index of 2.5g/10min.
In this embodiment, the first adhesive layer 2 is made by coating and drying high temperature resistant polyurethane glue, wherein in this embodiment, the high temperature resistant polyurethane glue is purchased from the power adhesive industry, and the model is JL-6810;
In this embodiment, the high-barrier interlayer 3 is an alumina layer;
In this embodiment, the second adhesive layer 4 is made by coating and drying high temperature resistant polyurethane glue, wherein in this embodiment, the high temperature resistant polyurethane glue is purchased from the power adhesive industry, and the model is JL-6810;
in this example, the following materials were used for each layer of the CPP film 5:
the composite layer 51 comprises the modified polypropylene pellets prepared by the random copolymer polypropylene pellets B and [ preparation example 2 ], and the weight ratio of the random copolymer polypropylene pellets B to the modified polypropylene pellets is 80:20;
the support layer 52 is made of random copolymer polypropylene pellets B;
The heat-sealing layer 53 adopts random copolymer polypropylene granules B;
in this example, the above-mentioned random copolymer polypropylene pellet B was M800E from Shanghai Jinshan, and had a melt index of 8g/10min.
In this embodiment, the preparation method of the high-barrier polypropylene recyclable packaging film includes the following steps:
Feeding all raw materials of an outer surface layer 11 of a BOPP film 1 into an extruder A1, feeding all raw materials of a core layer 12 into an extruder B1, feeding all raw materials of an inner surface layer 13 into an extruder C1, uniformly melting all the layers, co-extruding by adopting a three-way die head at the extrusion temperature of 260 ℃, casting a cast sheet, and biaxially stretching to obtain the BOPP film 1 with the thickness of 28 mu m; wherein the longitudinal stretching temperature is 120 ℃, the stretching ratio is 3 times, the transverse stretching temperature is 150 ℃, and the stretching ratio is 3.5 times.
Feeding raw materials of a CPP film 5 composite layer 51 into an extruder A2, feeding raw materials of a supporting layer 52 into an extruder B2, feeding raw materials of a heat sealing layer 53 into an extruder C2, uniformly melting all the layers, co-extruding by adopting a three-way die head, wherein the extrusion temperature is 270 ℃, and then casting, cooling and shaping to obtain a CPP film 5 with the thickness of 40 mu m;
uniformly coating a first bonding layer 2 on the BOPP film 1, and curing to obtain a first composite material;
uniformly coating a second bonding layer 4 on the CPP film 5, and setting a high-barrier middle layer 3 on one side of the second bonding layer 4 away from the CPP film after curing to obtain a second composite material;
and compounding the high-barrier middle layer 3 of the second composite material with the first bonding layer 2 of the first composite material to obtain the high-barrier polypropylene recyclable packaging film.
[ Example 3]
A high barrier polypropylene recyclable packaging film, differing from [ example 1 ] in that: the modified polypropylene pellets were different.
The modified polypropylene pellets produced in [ preparation example 3] were used as modified polypropylene pellets in the inner skin layer 13 of the BOPP film 1.
The modified polypropylene pellets produced in [ preparation example 3 ] were used as modified polypropylene pellets in the CPP film 5 composite layer 51.
[ Example 4]
A high barrier polypropylene recyclable packaging film, differing from [ example 1 ] in that: the modified polypropylene pellets were different.
The modified polypropylene pellets produced in [ preparation example 4] were used as modified polypropylene pellets in the inner skin layer 13 of the BOPP film 1.
The modified polypropylene pellets produced in [ preparation example 4 ] were used as modified polypropylene pellets in the CPP film 5 composite layer 51.
[ Example 5]
A high barrier polypropylene recyclable packaging film, differing from [ example 3 ] in that: the glue used for the first adhesive layer 2 and the second adhesive layer 4 are different.
In this embodiment, the first adhesive layer 2 and the second adhesive layer 4 are both made of high temperature resistant acrylate glue.
In this embodiment, the high temperature resistant acrylate glue comprises the following raw materials:
Acrylate monomer: 45kg; in this embodiment, methyl methacrylate is specifically used as the acrylate monomer;
alkenyl-containing aromatic primary amine compound: 12kg; in the embodiment, the alkenyl-containing aromatic primary amine compound specifically adopts (E) -4-phenyl-3-butene-1-amine;
styrene: 5.5kg;
Azo initiator: 0.4kg; in the embodiment, the azo initiator specifically adopts azobisisobutyronitrile;
solvent: 25kg; in this embodiment, ethanol is specifically used as the solvent.
The preparation method of the high-temperature-resistant acrylic ester glue comprises the following steps:
adding an acrylic ester monomer, an aromatic primary amine compound containing alkenyl and styrene into a solvent, and uniformly stirring to obtain a mixture;
and adding an azo initiator into the mixture, stirring uniformly, heating to 65 ℃, carrying out heating reflux reaction for 5 hours, and cooling to obtain the high-temperature-resistant acrylic ester glue.
[ Example 6]
A high barrier polypropylene recyclable packaging film, differing from [ example 3 ] in that: the glue used for the first adhesive layer 2 and the second adhesive layer 4 are different.
In this embodiment, the first adhesive layer 2 and the second adhesive layer 4 both include high temperature resistant polyurethane glue and high temperature resistant acrylate glue, and the weight ratio of the high temperature resistant polyurethane glue to the high temperature resistant acrylate glue is 3:1.
Specifically, the high-temperature-resistant polyurethane glue is purchased from nine-point glue industry, and the model is JD-7810;
The high-temperature resistant acrylic ester glue prepared in the method [ example 5 ].
[ Example 7]
A high barrier polypropylene recyclable packaging film, differing from [ example 3 ] in that: the glue used for the first adhesive layer 2 and the second adhesive layer 4 are different.
In this embodiment, the first adhesive layer 2 and the second adhesive layer 4 both include high temperature resistant polyurethane glue and high temperature resistant acrylate glue, and the weight ratio of the high temperature resistant polyurethane glue to the high temperature resistant acrylate glue is 4:1.
Specifically, the high-temperature-resistant polyurethane glue is purchased from nine-point glue industry, and the model is JD-7810;
the high-temperature-resistant acrylic ester glue comprises the following raw materials:
acrylate monomer: 65kg; in this embodiment, the acrylic ester monomer is specifically ethyl methacrylate;
Alkenyl-containing aromatic primary amine compound: 18kg; in the embodiment, the alkenyl-containing aromatic primary amine compound specifically adopts p-vinylbenzyl amine;
styrene: 6.8kg;
Azo initiator: 0.8kg; in the embodiment, the azo initiator specifically adopts azo diisoheptonitrile;
Solvent: 35kg; in this embodiment, ethanol is specifically used as the solvent.
The preparation method of the high-temperature-resistant acrylic ester glue comprises the following steps:
adding an acrylic ester monomer, an aromatic primary amine compound containing alkenyl and styrene into a solvent, and uniformly stirring to obtain a mixture;
and adding an azo initiator into the mixture, stirring uniformly, heating to 75 ℃, carrying out heating reflux reaction for 3 hours, and cooling to obtain the high-temperature-resistant acrylic ester glue.
[ Example 8]
A high barrier polypropylene recyclable packaging film, differing from [ example 7 ] in that: the high temperature resistant acrylic ester glue is different.
In the embodiment, when the high-temperature-resistant acrylic ester glue is prepared, the alkenyl-containing aromatic primary amine compound is replaced by equal amount of styrene.
[ Example 9]
A high barrier polypropylene recyclable packaging film, differing from [ example 7 ] in that: the high temperature resistant acrylic ester glue is different.
In the embodiment, when the high-temperature-resistant acrylic ester glue is prepared, the alkenyl-containing aromatic primary amine compound is replaced by equal amount of hydroxyethyl acrylate.
[ Example 10]
A high barrier polypropylene recyclable packaging film, differing from [ example 7 ] in that: the high temperature resistant acrylic ester glue is different.
In the embodiment, when the high-temperature-resistant acrylic ester glue is prepared, the alkenyl-containing aromatic primary amine compound is replaced by the same amount of acrylamide.
[ Example 11]
A high barrier polypropylene recyclable packaging film, differing from [ example 7] in that: the exterior layer 11 of BOPP film 1 is different from the core layer 12 in terms of raw materials, and the support layer 52 and the heat seal layer 53 of the CPP film 5 are different in terms of raw materials.
In this example, the outer skin layer 11 of the BOPP film 1 comprises random copolymer polypropylene pellets a and modified polypropylene pellets; the weight ratio of the random copolymer polypropylene pellet A to the modified polypropylene pellet is 85:15;
The core layer 12 of the BOPP film 1 comprises a random copolymer polypropylene pellet a, [ preparation example 3 ] the obtained modified polypropylene pellet and polyolefin elastomer a, and the weight ratio of the random copolymer polypropylene pellet a, the modified polypropylene pellet and the polyolefin elastomer a is 100:10:20, a step of;
Wherein, the random copolymer polypropylene pellet A adopts R520Y of Korean SK, and the melt index is 1.8g/10min; polyolefin elastomer A was POE8480, dow, having a melt index of 0.9g/10min and a melt temperature of 99 ℃.
In this example, the support layer 52 of the CPP film 5 includes a random copolymer polypropylene pellet B, a modified polypropylene pellet produced [ production example 3 ], and a polyolefin elastomer B in a weight ratio of 100:7.5:15;
The heat-seal layer 53 of the CPP film 5 includes a random copolymer polypropylene pellet B and a polyolefin elastomer B in a weight ratio of 90:10;
wherein, the random copolymer polypropylene pellet B adopts R401 of Korean hyosung , and the melt index is 4g/10min; and polyolefin elastomer B is Ikesen Mobil POE5101, the melt index is 2.0g/10min, and the melt temperature is 98 ℃.
[ Example 12]
A high barrier polypropylene recyclable packaging film, differing from [ example 11 ] in that: the core layer 12 of the BOPP film 1 is made of different materials.
In this example, the core layer 12 of the BOPP film 1 comprises a random copolymer polypropylene pellet a and a polyolefin elastomer a in a weight ratio of 100:20, a step of;
The random copolymer polypropylene pellet A adopts R520Y of Korean SK, and has a melt index of 1.8g/10min; polyolefin elastomer A was POE8480, dow, having a melt index of 0.9g/10min and a melt temperature of 99 ℃.
[ Example 13]
A high barrier polypropylene recyclable packaging film, differing from [ example 11 ] in that: the core layer 12 of the BOPP film 1 is made of different materials.
In this example, the core layer 12 of the BOPP film 1 comprises a random copolymer polypropylene pellet a and a modified polypropylene pellet prepared [ preparation example 3], and the weight ratio of the random copolymer polypropylene pellet a to the modified polypropylene pellet is 100:10;
the random copolymer polypropylene pellet A used R520Y of Korean SK, had a melt index of 1.8g/10min.
[ Example 14]
A high barrier polypropylene recyclable packaging film, differing from [ example 11 ] in that: the support layer 52 of the CPP film 5 is made of different materials.
In this example, the support layer 52 of the CPP film 5 includes a random copolymer polypropylene pellet B and a polyolefin elastomer B in a weight ratio of 100:15.
Wherein, the random copolymer polypropylene pellet B adopts R401 of Korean hyosung , and the melt index is 4g/10min; and polyolefin elastomer B is Ikesen Mobil POE5101, the melt index is 2.0g/10min, and the melt temperature is 98 ℃.
[ Example 15]
A high barrier polypropylene recyclable packaging film, differing from [ example 11 ] in that: the support layer of the CPP film was different in raw materials.
In this example, the support layer 52 of the CPP film 5 includes random copolymer polypropylene pellets B and modified polypropylene pellets in a weight ratio of 100:7.5.
Among them, the random copolymer polypropylene pellet B was used as R401 in Korean hyosung , and had a melt index of 4g/10min.
Comparative example
Comparative example 1
A polypropylene recyclable packaging film, differing from [ example 1 ] in that:
The maleic anhydride in the modified polypropylene pellets was replaced with an equivalent amount of methacrylic acid.
Comparative example 2
A polypropylene recyclable packaging film, differing from [ example 1 ] in that:
The glycidyl methacrylate in the modified polypropylene pellets was replaced with an equivalent amount of methacrylic acid.
[ Comparative example 3]
A polypropylene recyclable packaging film, differing from [ example 1 ] in that:
the styrene in the modified polypropylene pellets was replaced with an equal amount of methacrylic acid.
[ Comparative example 4]
A polypropylene recyclable packaging film, differing from [ example 1 ] in that:
the raw material of the inner surface layer of the BOPP film adopts random copolymer polypropylene granules A, wherein the random copolymer polypropylene granules A adopts R520Y of Korean SK, and the melt index is 1.8g/10min;
the raw material of the composite layer of the CPP film was random copolymer polypropylene pellet B, wherein the random copolymer polypropylene pellet B was R401 of Korean hyosung , and the melt index was 4g/10min.
Performance test
1. Oxygen transmission test: the packaging films of each example and comparative example were tested for oxygen permeation after storage at normal temperature for different times and after steaming at different steaming temperatures for 30 minutes according to GB/T1038.1-2022 method for testing gas permeation of Plastic films and sheets part 1, differential pressure method, wherein a smaller oxygen permeation indicates a better oxygen barrier property. And (3) injection: no oxygen permeation test was performed after significant delamination.
2. Water vapor transmission test: the packaging films of each example and comparative example were tested according to GB/T26153-2010 method for infrared detector for determination of Water vapor Transmission of Plastic film and sheet, for different times at ambient temperature and after 30 minutes of steaming at different steaming temperatures, wherein a smaller Water vapor Transmission indicates a better Water vapor barrier property. And (3) injection: no water vapor transmission test was performed after significant delamination.
3. Dimensional stability: the high barrier polypropylene recyclable packaging films prepared in each of examples and comparative examples were treated at 120℃for 30 minutes, and the dimensional shrinkage in the longitudinal direction of the packaging films was measured.
4. Tensile strength: the tensile strength of the high barrier polypropylene recyclable packaging films produced in each of the examples and comparative examples was examined with reference to GB/T1040.3-2006 at a test speed of 50mm/min.
5. Transparency: the packaging films of each example and comparative example were subjected to light transmittance test with reference to GB/T2410 determination of light transmittance and haze of transparent plastics.
TABLE1 packaging film oxygen permeation and Water vapor permeation test data
Table 2 packaging film dimensional stability, tensile force, light transmittance test data
Sample preparation Dimensional shrinkage/% Breaking force (N/15 mm) Transmittance/%
Example 1 1.12 65.4 89.8
Example 2 1.26 64.8 89.3
Example 3 0.34 62.4 89.5
Example 4 0.38 62.2 89.8
Example 5 0.29 62.6 89.4
Example 6 0.24 62.9 89.7
Example 7 0.26 62.1 89.4
Example 8 0.31 62.7 89.3
Example 9 0.39 62.9 89.6
Example 10 0.41 62.4 89.7
Example 11 0.11 65.8 89.5
Example 12 0.25 70.9 86.4
Example 13 0.07 62.8 89.9
Example 14 0.32 71.2 85.5
Example 15 0.05 62.6 89.8
Comparative example 1 1.15 65.1 89.7
Comparative example 2 1.18 65.4 89.5
Comparative example 3 1.28 65.2 89.8
Comparative example 4 1.99 65.7 90.7
Combining example 1 with comparative examples 1-3 and combining the data in tables 1-2, it can be seen that: the maleic anhydride, the glycidyl methacrylate and the styrene can improve the barrier durability and the high-temperature digestion resistance of the packaging film in a synergistic way.
Combining example 1 with examples 3-4 and combining the data in tables 1-2, it can be seen that: the propylene polymer in the modified polypropylene granules adopts homopolymerized polypropylene with the melt index within the range of 6-8g/10min, so that the permeation resistance, the permeation resistance and the high-temperature digestion resistance of the inner surface layer and the composite layer can be further improved, the barrier durability and the high-temperature digestion resistance of the packaging film can be further improved, and meanwhile, the dimensional stability of the packaging film can be also improved.
Combining example 7 with example 10 and combining the data in table 1, it can be seen that: in the high temperature resistant acrylic ester glue, when the aromatic primary amine compound containing alkenyl is replaced by any one of styrene, hydroxyethyl acrylate or acrylamide, the barrier durability and the high temperature resistant steaming performance of the packaging film are difficult to be further and effectively improved.
It can be seen in connection with examples 11-15 and in connection with the data in tables 1-2 that: when the BOPP film or the CPP film is prepared, the incorporation of the modified polypropylene particles can improve the barrier durability and the high-temperature steaming resistance of the packaging film, but the breaking force is easy to be reduced. The addition of the polyolefin elastomer can improve the breaking force of the packaging film, but can easily reduce the light transmittance of the packaging film. According to the application, the core layer of the BOPP film and the supporting layer of the CPP film are simultaneously doped with the modified polypropylene granules and the polyolefin elastomer for modification, so that the barrier durability and the high-temperature steaming resistance of the packaging film can be further improved, and the packaging film with better breaking force and higher transparency can be obtained.
The present embodiment is merely illustrative of the present application and not limiting, and one skilled in the art, after having read the present specification, may make modifications to the embodiment without creative contribution as required, but is protected by patent law within the scope of the claims of the present application.

Claims (8)

1. A high barrier polypropylene recyclable packaging film, characterized in that: comprises a BOPP film (1), a first bonding layer (2), a high-barrier middle layer (3), a second bonding layer (4) and a CPP film (5) which are sequentially arranged from outside to inside;
The BOPP film (1) comprises an inner surface layer (13) adjacent to a first bonding layer (2), wherein the inner surface layer (13) comprises raw material random copolymer polypropylene granules A and modified polypropylene granules, and the weight ratio of the random copolymer polypropylene granules A to the modified polypropylene granules is (85-90): (10-15); the melt index of the random copolymer polypropylene granules A is 1.8-2.5g/10min;
The CPP film (5) comprises a composite layer (51) adjacent to the second adhesive layer (4), wherein the composite layer (51) comprises a random copolymer polypropylene granule B and a modified polypropylene granule, and the weight ratio of the random copolymer polypropylene granule B to the modified polypropylene granule is (80-90): (10-20); the melt index of the random copolymer polypropylene granules B is 4-8g/10min;
Wherein the modified polypropylene granules comprise raw materials of maleic anhydride, glycidyl methacrylate, styrene, propylene polymer and initiator, and the weight ratio of the maleic anhydride, the glycidyl methacrylate, the styrene, the propylene polymer and the initiator is (6.5-9.4): (8.8-12.5): (2.3-4.2): 100: (0.2-0.4);
The first bonding layer (2) and the second bonding layer (4) comprise high-temperature-resistant polyurethane glue and high-temperature-resistant acrylic ester glue, and the weight ratio of the high-temperature-resistant polyurethane glue to the high-temperature-resistant acrylic ester glue is (3-4): 1;
The high-temperature-resistant acrylic ester glue comprises an acrylic ester monomer, an alkenyl-containing aromatic primary amine compound, styrene, an azo initiator and a solvent, wherein the weight ratio of the acrylic ester monomer to the alkenyl-containing aromatic primary amine compound to the styrene to the azo initiator to the solvent is (45-65): (12-18): (5.5-6.8): (0.4-0.8): (25-35);
the high-barrier interlayer (3) is at least one of an alumina coating, a silica coating and a silicon nitride coating.
2. The high barrier polypropylene recyclable packaging film as defined in claim 1, wherein: the propylene polymer adopts homopolymerized polypropylene, and the melt index of the homopolymerized polypropylene is 6-8g/10min.
3. The high barrier polypropylene recyclable packaging film as claimed in claim 1, wherein the preparation method of the modified polypropylene pellet comprises the following steps:
uniformly mixing a propylene polymer, maleic anhydride, glycidyl methacrylate, styrene and an initiator to obtain a premix;
Irradiating the premix by using an ultraviolet lamp to obtain an irradiation grafting composition;
And (3) carrying out melt extrusion and crushing on the irradiation grafting composition at 180-200 ℃ to obtain modified polypropylene granules.
4. The high barrier polypropylene recyclable packaging film as defined in claim 1, wherein: the aromatic primary amine compound containing alkenyl adopts at least one of p-vinylbenzylamine and (E) -4-phenyl-3-butene-1-amine.
5. The high barrier polypropylene recyclable packaging film as defined in claim 1, wherein: the preparation method of the high-temperature-resistant acrylic ester glue comprises the following steps:
adding an acrylic ester monomer, an aromatic primary amine compound containing alkenyl and styrene into a solvent, and uniformly stirring to obtain a mixture;
Adding azo initiator into the mixture, stirring uniformly, heating to 65-75 ℃, heating and refluxing for 3-5h, and cooling to obtain the high-temperature-resistant acrylic ester glue.
6. The high barrier polypropylene recyclable packaging film as defined in claim 1, wherein: the BOPP film (1) further comprises an outer surface layer (11) and a core layer (12), wherein the core layer (12) is positioned between the outer surface layer (11) and the inner surface layer (13);
wherein the outer surface layer (11) comprises random copolymer polypropylene granules A and modified polypropylene granules, and the weight ratio of the random copolymer polypropylene granules A to the modified polypropylene granules is (83-88): (12-17);
the core layer (12) comprises a random copolymer polypropylene pellet A, a modified polypropylene pellet and a polyolefin elastomer A, wherein the weight ratio of the random copolymer polypropylene pellet A to the modified polypropylene pellet to the polyolefin elastomer A is 100: (8-12): (15-25), and the melt index of the polyolefin elastomer A is 0.8-1.2g/10min, and the melt temperature is 95-105 ℃.
7. The high barrier polypropylene recyclable packaging film as defined in claim 1, wherein: the CPP film (5) further comprises a heat sealing layer (53) and a supporting layer (52), wherein the supporting layer (52) is positioned between the composite layer (51) and the heat sealing layer (53);
wherein the support layer (52) comprises a random copolymer polypropylene pellet B, a modified polypropylene pellet and a polyolefin elastomer B, and the weight ratio of the random copolymer polypropylene pellet B, the modified polypropylene pellet and the polyolefin elastomer B is 100: (5-10): (10-20);
The heat-seal layer (53) comprises a random copolymer polypropylene pellet B and a polyolefin elastomer B, and the weight ratio of the random copolymer polypropylene pellet B to the polyolefin elastomer B is (88-92): (8-12);
The melt index of the polyolefin elastomer B is 2-3g/10min, and the melt temperature is 90-100 ℃.
8. A method for producing a high barrier polypropylene recyclable packaging film as defined in any one of claims 1 to 7, characterized in that: the method comprises the following steps:
After the raw materials of all layers of the BOPP film (1) are respectively mixed and melted uniformly, extruding in a coextrusion mode, and then preparing the BOPP film (1) by a biaxial stretching process;
After the raw materials of all layers of the CPP film (5) are respectively mixed and melted uniformly, extruding in a coextrusion mode, and then preparing the CPP film (5) by adopting a tape casting process;
uniformly coating the first bonding layer (2) on the BOPP film (1) to obtain a first composite material;
Uniformly coating the second bonding layer (4) on the CPP film (5), and then arranging the high-barrier middle layer (3) on one side of the second bonding layer (4) away from the CPP film (5) to obtain a second composite material;
and compounding the high-barrier middle layer (3) of the second composite material with the first bonding layer (2) of the first composite material to obtain the high-barrier polypropylene recyclable packaging film.
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Publication number Priority date Publication date Assignee Title
JPH0848873A (en) * 1994-08-05 1996-02-20 Dainippon Ink & Chem Inc Thermoplastic resin composition, molding material, molding and production of thermoplastic molding material
KR20130000288A (en) * 2011-06-22 2013-01-02 엘지디스플레이 주식회사 Adhesive, manufacturing method of display device using the same
CN114379182A (en) * 2021-11-26 2022-04-22 江阴市申美包装材料有限公司 Biscuit packaging film and preparation method thereof
WO2022184599A1 (en) * 2021-03-01 2022-09-09 Borealis Ag High-barrier blown film polyolefin solutions for barrier coating
CN219467214U (en) * 2022-09-29 2023-08-04 杭州金杭包装印业有限公司 Single-material high-barrier transparent composite film and bag

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EP3957475A1 (en) * 2020-08-21 2022-02-23 Constantia Tobepal S.L.U. Recyclable multilayer packaging material

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0848873A (en) * 1994-08-05 1996-02-20 Dainippon Ink & Chem Inc Thermoplastic resin composition, molding material, molding and production of thermoplastic molding material
KR20130000288A (en) * 2011-06-22 2013-01-02 엘지디스플레이 주식회사 Adhesive, manufacturing method of display device using the same
WO2022184599A1 (en) * 2021-03-01 2022-09-09 Borealis Ag High-barrier blown film polyolefin solutions for barrier coating
CN114379182A (en) * 2021-11-26 2022-04-22 江阴市申美包装材料有限公司 Biscuit packaging film and preparation method thereof
CN219467214U (en) * 2022-09-29 2023-08-04 杭州金杭包装印业有限公司 Single-material high-barrier transparent composite film and bag

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