CN113910729B - High-heat-seal-strength biaxially oriented polypropylene high-barrier coating film and preparation method thereof - Google Patents

High-heat-seal-strength biaxially oriented polypropylene high-barrier coating film and preparation method thereof Download PDF

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CN113910729B
CN113910729B CN202111295231.6A CN202111295231A CN113910729B CN 113910729 B CN113910729 B CN 113910729B CN 202111295231 A CN202111295231 A CN 202111295231A CN 113910729 B CN113910729 B CN 113910729B
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layer
pvdc
heat
barrier coating
coating film
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CN113910729A (en
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黎坛
王恩飞
王俊峰
黎海鸥
符旺妙
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Hainan Shiner Industrial Co Ltd
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Hainan Shiner Industrial 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
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—Films or sheets
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
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    • 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
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • 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
    • B32B2307/31—Heat sealable
    • 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
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7244—Oxygen barrier
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7246—Water vapor barrier
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/80—Medical packaging
    • 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
    • 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
    • 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
    • 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
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/14—Copolymers of propene

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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  • Laminated Bodies (AREA)

Abstract

The invention provides a high heat seal strength biaxial tension polypropylene high barrier coating film, which comprises: a substrate; the base glue layer is arranged on the surface of the base material; and the PVDC layer is arranged on the surface of the bottom rubber layer. The high-heat-seal-strength biaxially-oriented polypropylene high-barrier coating film provided by the invention is low in cost and high in heat seal strength, can be directly used for packaging food, medicines and the like without compounding CPP (chlorinated Polypropylene), CPE (chlorinated polyethylene) or PE (Poly ethylene), is more favorable for food packaging because the physical and mechanical properties of the film are unchanged or slightly improved compared with those of a traditional heat sealing film, can obviously reduce oxygen permeation and water vapor permeation, effectively protects food, medicines and the like packaged in the inner package, has stable performance of a PVDC coating on the outer surface, is not influenced by external temperature and humidity, is obviously smaller in haze than a composite film, and is transparent and clear in inner package. The invention also provides a preparation method of the biaxially oriented polypropylene high-barrier coating film with high heat-seal strength.

Description

High-heat-seal-strength biaxially oriented polypropylene high-barrier coating film and preparation method thereof
Technical Field
The invention belongs to the technical field of polymers, and particularly relates to a biaxially oriented polypropylene high-barrier coating film with high heat-seal strength and a preparation method thereof.
Background
The traditional BOPP barrier coating film is mainly used for packaging food, medicine and the like after being compounded with CPP, CPE or PE, and has a multilayer structure, and the CPP, the CPE or the PE mainly plays a role in high heat sealing strength in the product structure. The main reason that the traditional BOPP coating film cannot be directly used for packaging articles is that the heat-sealing strength of the heat-sealing type biaxial oriented polypropylene is small and is generally less than 4N/15mm, and the packaged food is easy to break during the packaging or handling process. The traditional biaxial stretching polypropylene high barrier coating film is compounded with CPP or CPE or PP film, which can increase the production cost and cause environmental protection problems.
Disclosure of Invention
The high-heat-seal-strength biaxially oriented polypropylene high-barrier coating film provided by the invention has the advantages of low cost and high heat seal strength, can be directly used for packaging food, medicines and the like without compounding CPP (chlorinated Polypropylene), CPE (chlorinated polyethylene) or PE (Poly ethylene), has unchanged or slightly improved physical and mechanical properties compared with the traditional heat-seal film, is more beneficial to food packaging, can obviously reduce oxygen permeation and water vapor permeation through a PVDC high-barrier coating, effectively protects food, medicines and the like packaged in the inner package, has stable performance of the PVDC coating on the outer surface, is not influenced by external temperature and humidity, has obviously smaller haze than a composite film, and is transparent and clear in the inner package.
The invention provides a high heat seal strength biaxial tension polypropylene high barrier coating film, which comprises:
a substrate;
the base glue layer is arranged on the surface of the base material;
the PVDC layer is arranged on the surface of the bottom rubber layer;
the substrate is a single-sided high heat seal strength biaxially oriented polypropylene film, and comprises:
an upper layer;
a middle layer;
a lower layer;
the upper strata is high heat-seal strength layer, includes: ethylene-propylene-butene terpolymers, POE modified VLDPE and silica;
the middle layer includes: homo-polypropylene;
the lower layer includes: homo polypropylene and silica;
the bottom glue layer is arranged on the surface of the lower layer.
Preferably, the thickness of the upper layer is 2 to 5 micrometers.
Preferably, the upper layer includes:
71 to 89 weight percent of ethylene-propylene-butylene terpolymer;
10 to 25wt% of POE modified VLDPE;
1-4 wt% of silica.
Preferably, the thickness of the middle layer is 33 to 42 μm.
Preferably, the thickness of the lower layer is 1 to 3 micrometers.
Preferably, the lower layer includes:
98-99 wt% of homopolymerized polypropylene;
1-2 wt% silica.
Preferably, the primer layer includes: a polyurethane.
Preferably, the PVDC layer includes: PVDC, silica and wax.
The invention provides a preparation method of a biaxially oriented polypropylene high-barrier coating film with high heat-seal strength, which comprises the following steps:
and (3) coating primer on the lower layer of the base material after corona treatment, coating PVDC emulsion after drying, rolling and curing to obtain the biaxially oriented polypropylene high-barrier coating film with high heat seal strength.
Preferably, the preparation method of the substrate comprises the following steps:
and sequentially carrying out material proportioning, extrusion, sheet casting, longitudinal stretching, transverse stretching, corona treatment and rolling to obtain the base material.
The high-heat-seal-strength biaxially oriented polypropylene high-barrier coating film provided by the invention has the advantages of low cost and high heat-seal strength, can be directly used for packaging food, medicines and the like without compounding CPP (chlorinated Polypropylene), CPE (chlorinated polyethylene) or PE (Poly ethylene), has unchanged or slightly improved physical and mechanical properties compared with the traditional heat-seal film, is more beneficial to food packaging, can obviously reduce oxygen permeation and water vapor permeation by a PVDC high-barrier coating, effectively protects inner packaged food, medicines and the like, has stable performance of the PVDC coating on the outer surface, is not influenced by external haze temperature and humidity, is obviously smaller than a composite film, and is transparent and clear in inner packaged objects.
Drawings
Fig. 1 is a schematic structural diagram of a high heat-seal strength biaxially oriented polypropylene high-barrier coating film provided by an embodiment of the invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a high heat seal strength biaxial tension polypropylene high barrier coating film, which comprises:
a substrate;
the base glue layer is arranged on the surface of the base material;
the PVDC layer is arranged on the surface of the bottom rubber layer;
the base material is a single-sided high heat seal strength biaxially oriented polypropylene film, and comprises:
an upper layer;
a middle layer;
a lower layer;
the upper layer is a high heat-seal strength layer and comprises: ethylene-propylene-butene terpolymers, POE modified VLDPE and silica;
the middle layer includes: homo-polypropylene;
the lower layer includes: homo-polypropylene and silica;
the bottom glue layer is arranged on the surface of the lower layer.
In the present invention, the thickness of the upper layer is preferably 2 to 5 micrometers, more preferably 3 to 4 micrometers, and most preferably 3.5 micrometers.
In the present invention, the upper layer preferably includes:
71 to 89 weight percent of ethylene-propylene-butylene terpolymer;
10 to 25wt% of POE modified VLDPE;
1-4 wt% of silica.
In the present invention, the ethylene-propylene-butene terpolymer is preferably contained in an amount of 75 to 85% by mass, more preferably 78 to 82% by mass, and most preferably 80% by mass.
The source of the ethylene-propylene-butene terpolymer is not particularly limited in the present invention, and an ethylene-propylene-butene terpolymer known to those skilled in the art may be used, for example, FS5612 manufactured by sumitomo chemical corporation.
In the present invention, the POE (polyolefin elastomer) -modified VLDPE (ultra low density polyethylene) content is preferably 15 to 20% by mass, more preferably 16 to 18% by mass.
In the present invention, the process for producing POE-modified VLDPE preferably comprises:
and adding POE and VLDPE into the surface layer extruder through different feeders to mix.
In the invention, the melting point of the POE is preferably 50-70 ℃, more preferably 55-65 ℃, and most preferably 60 ℃; the melt index is preferably from 4 to 10dg/min, more preferably from 5 to 8dg/min, and most preferably from 6 to 7dg/min. In the present invention, the POE may be Versify3300 product manufactured by dow chemical company.
In the present invention, the melting point of the VLDPE is preferably 110 to 120 ℃, more preferably 105 to 115 ℃, and most preferably 110 ℃; the melt index is preferably from 4 to 8dg/min, more preferably from 5 to 7dg/min, and most preferably 6dg/min. In the present invention, the VLDPE may be DFDB1088 product manufactured by Dow chemical company.
In the present invention, the mass ratio of POE to VLDPE is preferably (1 to 1.5): 2, more preferably (1.1 to 1.4): 2, and most preferably (1.2 to 1.3): 2.
In the present invention, the mass content of the silica is preferably 2.5 to 3.5%, more preferably 3%.
In the present invention, the thickness of the middle layer is preferably 33 to 42 micrometers, more preferably 35 to 40 micrometers, and most preferably 36 to 38 micrometers.
The source of the homo-polypropylene is not particularly limited in the present invention, and homo-polypropylene known to those skilled in the art can be used, and can be obtained from the market, for example, F03D product produced by Hainan chemical industry.
In the present invention, the thickness of the lower layer is preferably 1 to 3 micrometers, more preferably 1.5 to 2.5 micrometers, and most preferably 2 micrometers.
In the present invention, the lower layer preferably includes:
98-99 wt% of homopolymerized polypropylene;
1-2 wt% silica.
In the present invention, the homo-polypropylene preferably has a mass content of 98.5%.
In the present invention, the mass content of the silica is preferably 1.5%.
In the present invention, the thickness of the substrate is preferably 18 to 45 micrometers, more preferably 20 to 40 micrometers, more preferably 25 to 35 micrometers, and most preferably 30 micrometers.
According to the single-sided high-heat-seal-strength biaxially oriented polypropylene substrate provided by the invention, POE modified VLDPE is added into the upper layer, the thickness of the heat seal layer, namely the upper layer, is controlled to be 2-5 mu m, so that the single-sided heat-seal biaxially oriented polypropylene film is prepared, and the heat seal strength value of the heat seal surface is 9-15N/15 mm under the conditions that the heat seal temperature is 130 ℃ and the heat seal time is 0.3 second, so that the requirement of food packaging can be met; and simultaneously has good physical and mechanical properties.
In the present invention, the primer layer preferably includes: a polyurethane.
In the present invention, the primer layer preferably has a thickness of 0.2 to 0.6 micrometers, more preferably 0.3 to 0.5 micrometers, and most preferably 0.4 micrometers.
In the present invention, the PVDC (polyvinylidene chloride) layer preferably includes: PVDC, silica and wax.
In the present invention, the wax is preferably palm wax.
In the present invention, the mass ratio of the silica to the PVDC is preferably (0.1% to 0.4%): 1, more preferably (0.2% to 0.3%): 1, most preferably 0.25%:1; the mass ratio of the wax to the PVDC is preferably (0.5-10%): 1, more preferably (1% to 8%): 1, more preferably (2% to 6%): 1, most preferably (3% to 5%): 1.
in the present invention, the thickness of the PVDC layer is preferably 1.0 to 3.0 micrometers, more preferably 1.5 to 2.5 micrometers, and most preferably 2 micrometers.
The structure of the biaxially oriented polypropylene high-barrier coating film with high heat-seal strength provided by the embodiment of the invention is shown in fig. 1, and comprises the following components: an upper layer (BOPP high heat seal strength layer); a middle layer (middle layer, BOPP base material) disposed on the upper layer surface; a lower layer (BOPP substrate non-heat-sealing layer) arranged on the surface of the middle layer; the polyurethane primer layer is arranged on the surface of the lower layer; a PVDC layer disposed on a surface of the primer layer.
In the embodiment of the invention, the structure of the high heat-sealing strength biaxially oriented polypropylene high-barrier coating film is schematically shown in fig. 1. The invention provides a high heat-seal strength biaxially oriented polypropylene high-barrier coating film, which is prepared by coating a high-barrier material on a non-heat-seal surface of a substrate which is single-sided high heat-seal biaxially oriented polypropylene, wherein the used coating is PVDC emulsion, 10% of solid content silicon dioxide dispersion liquid and 25% of solid content wax emulsion are added into 50% of solid content PVDC emulsion, the solid ratio of silicon dioxide to PVDC is 0.1-0.4%, and the solid ratio of wax emulsion to PVDC is 0.5-10%. Wherein the single-sided high heat seal strength biaxial stretching polypropylene film structurally comprises an upper layer structure, a middle layer structure and a lower layer structure, and the total thickness is as follows: 18-45 μm; the upper layer with the thickness of 2-5 μm is a high heat-sealing strength layer and is prepared from the following raw materials in percentage by weight: 71-89% of ethylene, propylene and butylene terpolymer, 10-25% of POE modified VLDPE and 2-4% of silicon dioxide; the thickness of the middle layer is 33-42 μm,100% homopolymerized polypropylene; the thickness of the lower layer is 1-3 μm, and the lower layer is prepared from the following raw materials in percentage by weight: 98-99% of homopolymerized polypropylene and 1-2% of silicon dioxide.
The high heat-seal strength biaxially oriented polypropylene high-barrier film provided by the invention is realized by taking a single-sided heat-seal film as a base material and coating PVDC on a non-heat-seal surface of the base material.
The invention provides a preparation method of a biaxially oriented polypropylene high-barrier coating film with high heat-seal strength, which comprises the following steps:
and (3) coating primer on the lower layer of the base material after corona treatment, coating PVDC mixed solution after drying, rolling and curing to obtain the biaxially-oriented polypropylene high-barrier coating film with high heat-seal strength.
In the present invention, the method for preparing the substrate preferably includes:
the method comprises the steps of material proportioning, extrusion, sheet casting, longitudinal stretching, transverse stretching, corona treatment and winding.
In the present invention, the substrate is preferably prepared in a biaxial stretching apparatus.
In the present invention, the method of dosing preferably comprises:
and respectively feeding the upper layer raw material, the middle layer raw material and the lower layer raw material into different charging buckets, and mixing according to a preset proportion.
In the present invention, the components and the ligands of the upper layer raw material, the middle layer raw material and the lower layer raw material are consistent with the components and the proportions of the upper layer, the middle layer and the lower layer in the above technical scheme, and are not described herein again.
In the invention, the mixing method is preferably manual mixing or equipment mixing.
In the present invention, the method of extrusion preferably comprises:
and respectively enabling the upper layer raw material, the middle layer raw material and the lower layer raw material to flow into an extruder, and converging in a die head and then flowing out.
In the present invention, the extruder is preferably a twin-screw extruder or a single-screw tandem extruder.
In the invention, the middle layer raw materials are preferably mixed and then flow into a double-screw extruder or a single-screw tandem extruder; the upper layer raw material and the lower layer raw material are respectively mixed and then preferably flow into respective auxiliary extruders, and the three layers of raw materials flow out after being converged at a die head.
In the present invention, the extruder can melt, plasticize, knead, and extrude uniformly and quantitatively.
In the present invention, the extrusion temperature during the extrusion process is preferably 200 to 250 ℃, more preferably 210 to 240 ℃, more preferably 220 to 230 ℃, and most preferably 225 ℃.
In the present invention, the casting is preferably performed in a casting machine.
In the present invention, the method of casting a slab preferably includes:
the resin flowing out of the extruder die head is cooled into a sheet, so that the crystallinity, the crystal form and the crystal size of the resin reach an ideal state, thereby improving the physical property of the film and being beneficial to longitudinal and transverse stretching.
In the present invention, the cooling temperature during the slab casting is preferably 18 to 40 ℃, more preferably 20 to 35 ℃, and most preferably 25 to 30 ℃.
In the present invention, the method of longitudinal stretching preferably includes:
preheating the sheet from a sheet casting machine, and longitudinally stretching the sheet at a certain speed to longitudinally orient polymer molecules; in order to ensure the longitudinal shrinkage, the preheating temperature and the stretching temperature of longitudinal stretching are as low as possible, and the stretching ratio is as high as possible.
In the present invention, the preheating temperature during the longitudinal drawing is preferably 105 to 135 ℃, more preferably 110 to 130 ℃, more preferably 115 to 125 ℃, and most preferably 120 ℃.
In the present invention, the stretching temperature of the longitudinal stretching is preferably 90 to 115 ℃, more preferably 95 to 110 ℃, and most preferably 100 to 105 ℃.
In the present invention, the stretch ratio in the longitudinal direction is preferably 490 to 535%, more preferably 500 to 530%, more preferably 510 to 520%, and most preferably 515%.
In the present invention, the method of transverse stretching preferably includes:
transversely stretching the longitudinally stretched sheet in a stretching area with a larger expansion angle through a set chain guide rail to ensure that polymer molecules are transversely oriented; in order to ensure the transverse shrinkage rate, the preheating temperature and the stretching temperature of transverse stretching are as low as possible, but the problems of clamp release and film rupture are easy to occur when the temperature is too low.
In the present invention, the preheating temperature during the transverse drawing is preferably 160 to 180 ℃, more preferably 165 to 175 ℃, and most preferably 170 ℃.
In the present invention, the stretching temperature of the transverse stretching is preferably 145 to 160 ℃, more preferably 150 to 155 ℃, and most preferably 152 to 153 ℃.
In the present invention, the setting temperature of the transverse stretching is preferably 140 to 170 ℃, more preferably 150 to 160 ℃, and most preferably 155 ℃.
In the present invention, the stretch ratio in the transverse direction is preferably 850 to 960%, more preferably 880 to 920%, and most preferably 900%.
In the present invention, the method of corona treatment preferably comprises:
after the edge of the film which is horizontally pulled out is cut, the non-heat-sealing surface of the film is subjected to corona treatment, so that the surface tension of the film reaches over 38 dynes.
In the present invention, the surface tension is preferably 38 to 40 dynes, more preferably 39 dynes.
In the present invention, the winding is preferably performed in a winder.
In the invention, the rolling process is related to the performance of the film, and can be adjusted by setting rolling tension, attenuation rate and compression roller pressure according to the rolling condition, wherein the stretching ratio is 100 +/-2%; the winding tension is preferably 20-30N/M, more preferably 23-27N/M, and most preferably 25N/M; the attenuation ratio is preferably 19 to 22%, more preferably 20 to 21%; the pressure of the press roll is preferably 20 to 25N/M, more preferably 21 to 24N/M, and most preferably 22 to 23N/M; the stretching ratio is preferably 99 to 101%, more preferably 100%.
The preparation method of the single-sided high-heat-seal-strength biaxially oriented polypropylene substrate film provided by the invention comprises the steps of material preparation, extrusion, sheet casting, longitudinal stretching, transverse stretching, corona treatment and rolling, wherein the stretching ratio of a longitudinal stretching process is 490-535%; the stretching magnification of the transverse stretching process is 850-960%; the temperature of an extruder in the extrusion working procedure is 200-250 ℃; the cooling temperature of a sheet casting machine in the sheet casting process is 18-40 ℃; the preheating temperature in the longitudinal stretching process is 105-135 ℃, and the stretching temperature is 90-115 ℃; the preheating temperature in the transverse stretching process is 160-180 ℃, the stretching temperature is 145-160 ℃, and the setting temperature is 140-170 ℃.
In the present invention, bipolar treatment is preferably used in the corona treatment, and the discharge power is preferably 8 to 10KW, and more preferably 9KW.
In the present invention, the primer is preferably polyurethane diluted with ethyl acetate, and the mass content of the polyurethane in the primer is preferably 10 to 15%, more preferably 11 to 14%, and most preferably 12 to 13%.
In the present invention, the coating is preferably performed in a coater.
In the present invention, the primer is preferably applied to a thickness of 0.2 to 0.6. Mu.m, more preferably 0.3 to 0.5. Mu.m, and most preferably 0.4. Mu.m.
In the present invention, the drying method is preferably drying; the drying temperature is preferably 85 to 95 deg.C, more preferably 88 to 92 deg.C, and most preferably 90 deg.C.
In the present invention, the PVDC mixed solution preferably includes:
PVDC emulsions, silica dispersions and wax emulsions.
In the present invention, the PVDC emulsion preferably comprises: PVDC and water.
In the present invention, the PVDC emulsion preferably has a solid content of 40 to 60%, more preferably 45 to 55%, and most preferably 50%.
In the present invention, the silica dispersion preferably includes: silica and water.
In the present invention, the solid content of the silica is preferably 5 to 15%, more preferably 8 to 12%, most preferably 10%.
In the present invention, the wax emulsion preferably comprises: wax and water.
In the present invention, the wax emulsion preferably has a solid content of 20 to 30%, more preferably 23 to 27%, and most preferably 25%.
In the invention, the usage amount of the PVDC emulsion, the silicon dioxide dispersion liquid and the wax emulsion is consistent with the mass ratio of the PVDC, the silicon dioxide and the wax in the technical scheme.
In the present invention, the thickness of the coating PVDC mixture is preferably 1.0 to 2.5 micrometers, more preferably 1.5 to 2 micrometers, and most preferably 1.6 to 1.8 micrometers.
In the present invention, the method of drying after coating the PVDC mixture is preferably drying, and the drying temperature is preferably 110 to 120 ℃, more preferably 113 to 117 ℃, and most preferably 115 ℃.
In the invention, the winding tension in the winding process is preferably 30-80N, more preferably 40-70N, and most preferably 50-60N; the taper is preferably 30% to 70%, more preferably 40% to 60%, and most preferably 50%.
In the present invention, the curing temperature is preferably 40 to 50 ℃, more preferably 43 to 47 ℃, and most preferably 45 ℃; the curing time is preferably 45 to 50 hours, more preferably 46 to 48 hours.
In the present invention, the preparation method of the high heat seal strength biaxially oriented polypropylene high barrier coating film more preferably comprises:
and (3) unwinding the single-sided heat-sealing film on a coating machine, coating polyurethane primer diluted by ethyl acetate on the non-heat-sealing surface after corona treatment, drying by an oven, coating PVDC emulsion (PVDC mixed solution), drying again, rolling, and curing in a curing chamber to obtain the high-heat-seal-strength biaxially-oriented polypropylene high-resistance barrier coating film.
The high-heat-seal-strength biaxially oriented polypropylene high-barrier coating film provided by the invention has the advantages of low cost and high heat-seal strength, can be directly used for packaging food, medicines and the like without compounding CPP (chlorinated Polypropylene), CPE (chlorinated polyethylene) or PE (Poly ethylene), has unchanged or slightly improved physical and mechanical properties compared with the traditional heat-seal film, is more beneficial to food packaging, can obviously reduce oxygen permeation and water vapor permeation by a PVDC high-barrier coating, effectively protects inner packaged food, medicines and the like, has stable performance of the PVDC coating on the outer surface, is not influenced by external haze temperature and humidity, is obviously smaller than a composite film, and is transparent and clear in inner packaged objects.
Example 1
Production of a substrate film having a thickness of 30 μm:
preparing materials: the upper layer is 5 mu m thick, wherein the weight percentage of the ethylene-propylene-butylene terpolymer is 85 percent, the weight percentage of the POE modified VLDPE is 13 percent (the POE and the VLDPE are directly added and mixed by different feeders in a surface layer extruder according to the mass ratio of 1.5), and the weight percentage of the silicon dioxide is 2 percent; the thickness of the middle layer is 24 mu m, wherein the homo-polypropylene accounts for 100wt%; the lower layer was 1 μm thick with 98wt% homo-polypropylene and 2wt% silicon dioxide.
Film preparation: adopting a biaxial stretching coextrusion process to prepare a biaxial stretching polypropylene film substrate, and sequentially carrying out extrusion, sheet casting, longitudinal stretching, transverse stretching, corona treatment and rolling, wherein the extrusion temperature is as follows: 230 ℃; casting temperature: 25 ℃; longitudinal stretching ratio: 495%, longitudinal stretching preheating temperature: 115 ℃, longitudinal stretching temperature: 104 ℃; transverse stretching ratio: 940%, transverse stretching preheating temperature: 175 ℃, transverse drawing temperature: 159 ℃, transverse stretching and setting temperature: 160 ℃; rolling and stretching ratio: 100 percent; the lower layer was corona treated with 10KW.
Example 2
Production of a film substrate with a thickness of 35 μm:
preparing materials: upper layer thickness 4 μm, ethylene-propylene-butene terpolymer 81wt%, POE modified VLDPE (same as example 1) 15wt%, silica 4wt%; the thickness of the intermediate layer is 30 mu m, wherein the homo-polypropylene accounts for 100wt%; the lower layer is 1 μm thick and comprises 99 wt.% of homo-polypropylene and 1 wt.% of silicon dioxide.
Film preparation: adopting a biaxial stretching co-extrusion process to prepare a biaxial stretching polypropylene film substrate, and sequentially carrying out extrusion, sheet casting, longitudinal stretching, transverse stretching, corona treatment and rolling, wherein the extrusion temperature is as follows: 235 ℃; casting temperature: 21 ℃; longitudinal stretching ratio: 500%, longitudinal stretching preheating temperature: 117 ℃, longitudinal stretching temperature: 106 ℃; transverse stretching ratio: 850%, transverse stretching preheating temperature: 180 ℃, transverse stretching temperature: 155 ℃, transverse stretching and setting temperature: 160 ℃; rolling and stretching ratio: 100 percent; the lower layer was corona treated with a bipolar corona treatment of 9KW.
Example 3
Producing a film substrate with a thickness of 40 μm;
preparing materials: the upper layer was 4 μm thick, with 79wt% ethylene-propylene-butene terpolymer, 20wt% POE-modified VLDPE (same as example 1), 1wt% silica; the thickness of the intermediate layer is 34 μm, wherein the homo-polypropylene accounts for 100wt%; the lower layer is 2 μm thick, wherein 98wt% of homo-polypropylene and 2wt% of silicon dioxide are used.
Film preparation: adopting biaxial stretching coextrusion process to prepare a biaxial stretching polypropylene film, and sequentially carrying out extrusion, sheet casting, longitudinal stretching, transverse stretching, corona treatment and rolling, wherein the extrusion temperature is as follows: 240 ℃; casting temperature: 20 ℃; longitudinal stretching ratio: 510%, longitudinal stretching preheating temperature: 120 ℃, longitudinal stretching temperature: 110 ℃; transverse stretching ratio: 910%, transverse stretching preheating temperature: 180 ℃, transverse stretching temperature: 160 ℃, transverse stretching and setting temperature: 155 ℃; rolling and stretching ratio: 100 percent; the lower layer is bipolar corona treated for 8KW.
Example 4
On a coating machine, unreeling the single-sided heat-sealing film prepared in the example 1, performing corona treatment on a non-heat-sealing surface (lower layer) at 10.0kw, coating 0.4 micron polyurethane primer diluted by ethyl acetate, wherein the concentration is 12wt%, drying the polyurethane primer in a 90 ℃ oven, and then coating 50% solid content PVDC emulsion, adding 10% solid content silicon dioxide dispersion and 25% solid content wax emulsion, wherein the solid ratio of silicon dioxide to PVDC is 0.2%, the solid ratio of wax emulsion to PVDC emulsion is 0.5%, and the coating thickness is 1.0 micron; and then drying again at the temperature of 110 ℃, then rolling, and curing in a curing chamber for 48 hours at the temperature of 45 ℃ to obtain the biaxially oriented polypropylene high-resistance barrier coating film with high heat-seal strength.
Example 5
On a coating machine, the single-sided heat-sealing film prepared in example 2 is unreeled, a non-heat-sealing surface (lower layer) is subjected to corona treatment of 9.0kw, then 0.4 micron of polyurethane primer diluted by ethyl acetate is coated, the concentration is 13wt%, after drying is performed in a 95 ℃ oven, then 50% solid content PVDC emulsion is coated, silica dispersion with 10% solid content and 25% solid content wax emulsion are added, the solid ratio of silica to PVDC is 0.25%, the solid ratio of wax emulsion to PVDC emulsion is 1%, the coating thickness is 1.5 microns, then drying is performed again, the temperature is 120 ℃, then rolling is performed, and curing is performed in a curing chamber for 48 hours and 45 ℃ to obtain the high heat-sealing strength biaxially oriented polypropylene barrier coating film.
Example 6
On a coating machine, the single-sided heat-sealing film prepared in example 3 is unreeled, a non-heat-sealing surface (lower layer) is subjected to corona treatment of 9.5kw, then 0.4 micron of polyurethane primer diluted by ethyl acetate is coated, the concentration is 13wt%, after drying is performed in an oven at 85 ℃, then 50% solid content PVDC emulsion is coated, silica dispersion liquid with 10% solid content and 25% solid content wax emulsion are added, the solid ratio of silica to PVDC is 0.25%, the solid ratio of wax emulsion to PVDC emulsion is 2%, the coating thickness is 2.0 micron, then drying is performed again, the temperature is 115 ℃, then rolling is performed, and curing is performed in a curing chamber for 48 hours and 40 ℃, so that the high heat-sealing strength biaxially oriented polypropylene barrier coating film is obtained.
Performance detection
For the high heat-seal-strength biaxially oriented polypropylene high-barrier coating film prepared in the embodiments 4 to 6 of the invention and the performance detection, the detection method and the detection result are as follows:
Figure BDA0003336355010000111
Figure BDA0003336355010000121
the embodiments can know that the high heat-seal strength biaxially oriented polypropylene high barrier coating film provided by the invention has low cost and high heat-seal strength, can be directly used for packaging food, medicines and the like without compounding CPP (chlorinated Polypropylene), CPE (chlorinated polyethylene) or PE (Poly ethylene), has unchanged or slightly improved physical and mechanical properties compared with the traditional heat-seal film, is more beneficial to food packaging, can obviously reduce oxygen permeation and water vapor permeation through a PVDC high barrier coating, effectively protects food, medicines and the like packaged in an inner package, has stable performance of the PVDC coating on the outer surface, is not influenced by external temperature and humidity, has obviously smaller haze than a composite film, and is transparent and clear in an inner package.
While the invention has been described and illustrated with reference to specific embodiments thereof, such description and illustration are not intended to limit the invention. It will be clearly understood by those skilled in the art that various changes in form and details may be made therein without departing from the true spirit and scope of the invention as defined by the appended claims, to adapt a particular situation, material, composition of matter, substance, method or process to the objective, spirit and scope of this application. All such modifications are intended to be within the scope of the claims appended hereto. Although the methods disclosed herein have been described with reference to particular operations performed in a particular order, it should be understood that these operations may be combined, sub-divided, or reordered to form equivalent methods without departing from the teachings of the present disclosure. Accordingly, unless specifically indicated herein, the order and grouping of the operations is not a limitation of the present application.

Claims (3)

1. A high heat seal strength biaxially oriented polypropylene high barrier coating film comprises:
a substrate;
the primer layer is arranged on the surface of the base material and is made of polyurethane, and the thickness of the primer layer is 0.4 microns;
the PVDC layer is arranged on the surface of the primer layer and comprises: PVDC, silica and wax; the thickness of the PVDC layer is 2.0 microns;
the base material is a single-sided high heat seal strength biaxially oriented polypropylene film, and comprises:
an upper layer;
a middle layer;
a lower layer;
the upper layer is a high heat seal strength layer and specifically comprises the following components: 79% by weight of an ethylene-propylene-butene terpolymer, 20% by weight of POE modified VLDPE and 1% by weight of silica;
the middle layer is specifically as follows: 100wt% of homopolypropylene;
the lower layer is specifically as follows: 98wt% of homopolypropylene and 2wt% of silica; the thickness of the upper layer is 4 microns; the thickness of the middle layer is 34 micrometers; the thickness of the lower layer is 2 microns.
2. A method for preparing the high heat-seal strength biaxially oriented polypropylene high barrier coating film of claim 1, comprising:
and (3) coating primer on the lower layer of the base material after corona treatment, coating PVDC emulsion after drying, rolling and curing to obtain the biaxially oriented polypropylene high-barrier coating film with high heat seal strength.
3. The method of claim 2, wherein the substrate is prepared by a method comprising:
and sequentially carrying out material proportioning, extrusion, sheet casting, longitudinal stretching, transverse stretching, corona treatment and rolling to obtain the base material.
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