CN116423945A - Low-cost multilayer composite fluororesin film and preparation method thereof - Google Patents

Low-cost multilayer composite fluororesin film and preparation method thereof Download PDF

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Publication number
CN116423945A
CN116423945A CN202310199107.2A CN202310199107A CN116423945A CN 116423945 A CN116423945 A CN 116423945A CN 202310199107 A CN202310199107 A CN 202310199107A CN 116423945 A CN116423945 A CN 116423945A
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film
composite
fluororesin
layer
multilayer
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郭金强
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Beijing Heguang Fangda Technology Co ltd
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Beijing Heguang Fangda 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
    • 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
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/30—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core
    • B29C70/34—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core and shaping or impregnating by compression, i.e. combined with compressing after the lay-up operation
    • 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
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/05—5 or more layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/712—Weather resistant
    • 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
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Composite Materials (AREA)
  • Mechanical Engineering (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention provides a low-cost multilayer composite fluororesin film and a preparation method thereof, and relates to the technical field of resin film preparation. The low-cost multilayer composite fluorine resin film comprises an extrusion composite fluorine film, a multilayer composite fluorine film/laminated composite fluorine film and a multilayer coextrusion composite fluorine film, wherein the extrusion resin is a single layer or a plurality of layers of fluorine resin (modified or unmodified), molten flaky fluorine resin melt is uniformly and flatly coated on a substrate film, or conversely, resin melt of the extrusion resin (PE, PP, nylon, EVA, EVOH and the like) is uniformly and flatly coated on the fluorine resin substrate film to form the composite fluorine film, or the multilayer coextrusion composite fluorine film is prepared by directly coextruding the fluorine resin and other resins by adopting a multilayer coextrusion machine. According to the invention, the cost of the fluororesin is effectively reduced, the mechanical strength is greatly improved, the barrier performance of the multilayer composite fluororesin is obviously improved, and the ultraviolet resistance of the single-layer fluororesin is improved.

Description

Low-cost multilayer composite fluororesin film and preparation method thereof
Technical Field
The invention relates to the technical field of resin film preparation, in particular to a low-cost multilayer composite fluororesin film and a preparation method thereof.
Background
The fluororesin has the characteristics of low surface tension self-cleaning property, high toughness, high ductility, impact resistance, excellent heat resistance, weather resistance, light transmittance, non-stick property, insulativity, barrier property, chemical resistance, incombustibility and the like, and is widely applied to the fields of semiconductor packaging release, LDE packaging release, solar light Fu Zheng backboard, medical treatment, building and the like.
The existing fluororesin film preparation technology mainly takes a single-layer casting film as a main material, and takes a single-sided/double-sided mirror surface or frosted surface or a biaxially oriented casting film as an auxiliary material, for example: ETFE, FEP, PVDF, PVF, PCTFE, ECTFE, PFA, and the like, can be used as a release film, a protective film for a solar cell after surface treatment, a protective layer for an aerostat, and the like.
The film prepared by the prior art has the advantages of single structure, higher cost, poorer mechanical property of materials, low tensile strength, poor environmental resistance, and reduced or invalid mechanical property, heat sealing property and gas barrier property of the materials after ultraviolet and high and low temperature.
Accordingly, a low-cost multi-layer composite fluororesin film and a method for manufacturing the same are provided by those skilled in the art to solve the problems set forth in the background art.
Disclosure of Invention
(one) solving the technical problems
Aiming at the defects of the prior art, the invention provides a low-cost multilayer composite fluororesin film and a preparation method thereof, which solve the problems that the film prepared by the prior art is single in structure, high in cost, poor in mechanical property of materials, low in tensile strength, poor in environmental resistance, and reduced in mechanical property of materials, heat sealing and gas barrier property or failed after being subjected to ultraviolet rays and high and low temperatures.
(II) technical scheme
In order to achieve the above purpose, the invention is realized by the following technical scheme:
a low-cost multilayer composite fluororesin film comprises an extrusion composite fluororesin film and a multilayer composite fluororesin film
Laminating a composite fluorine film and a multilayer coextrusion composite fluorine film, wherein the extrusion composite fluorine film adopts an extrusion compounding machine to prepare a multilayer composite fluorine film, extrusion resin is a single layer or a plurality of layers of fluorine resin (modified or unmodified), molten flaky fluorine resin melt is uniformly and flatly coated on a substrate film, or conversely, resin melt of extrusion resin (PE, PP, nylon, EVA, EVOH and the like) is uniformly and flatly coated on the fluorine resin substrate film to form the composite fluorine film;
the material structure types of the extruded composite fluorine film are as follows:
single-sided one-shot extrusion composite, comprising extrusion of fluororesin/base film, extrusion of resin/fluororesin-based film;
single-sided multiple extrusion composite, including extrusion of fluororesin/base film, extrusion of resin/fluororesin-based film;
sandwich composite comprising extruded fluororesin/base film/extruded fluororesin;
multilayer extrusion composite comprising extruded fluororesin/base film and extruded resin
Fluorine resin-based film/extrusion resin/fluorine resin-based film;
the above extruded resin or extruded fluororesin may be a single-layer or multi-layer coextrusion, the base film may be a single-layer or multi-layer film, paper, extruded resin, metal thin, or the like, and the fluororesin is a modified or unmodified resin.
The multilayer composite fluorine film/laminated composite fluorine film is formed of two or more layers so that the composite film is not separable as one film. The single-layer or multi-layer unmodified fluororesin film is compounded with a base film through an adhesive (the adhesive can be Polyurethane (PU) or UV light curing), the adhesive is cured through chemical reaction in the adhesive bonding process, the adhesive on the surface of the base material is mainly a physical process, only a small part of the adhesive is a chemical process, at the moment, the components of the adhesive and the components in the plastic film are drilled together and are further cured, and the fluororesin (unmodified or modified) film and the base film are subjected to multi-layer compounding through a multi-layer compounding machine or a lamination compounding machine to prepare a multi-layer composite fluororesin film or a laminated composite fluororesin film structure of the fluororesin;
the material structure types of the multilayer composite fluorine film/laminated composite fluorine film are as follows:
bilayer composites, including fluororesin film/base film;
three layers of composite including a fluororesin film/a base film/a fluororesin film;
a multilayer composite comprising a fluororesin film/base film, a fluororesin film/base film/fluororesin film;
the above extruded resin or extruded fluororesin may be a single-layer or multi-layer coextrusion, the base film may be a single-layer or multi-layer film, paper, extruded resin, metal thin, or the like, and the fluororesin is a modified or unmodified resin.
The multilayer coextrusion composite fluorine film adopts multilayer coextrusion casting/blow molding equipment to prepare the high-performance multilayer coextrusion casting/blow molding composite fluorine film, and the multilayer composite fluorine film utilizes the advantages of a multilayer structure, so that the cost is effectively reduced, the comprehensive performance is improved, and the multilayer coextrusion casting/blow molding composite fluorine film can be applied to separation films, isolation films, release films, barrier films, building films, agricultural films, rubber plug medical anti-corrosion films, solar panel positive backboard protective films, adjacent space aerostats, high-altitude balloons, medium-low-altitude balloons and the like.
Preferably, the preparation method of the extrusion composite fluorine film comprises the following steps:
s1, using 1 or more extruders and a T-shaped die head, extruding one or more thermoplastic resins into a flat die after melting in the extruder.
S2, casting and coating the film on the surface of another substrate through a T-type die, and pressing the composite film in a hot-sticking state.
S3, single-sided one-time coating composite type, which is a basic constitution device of an extrusion compounding machine, is most used in the field of flexible packaging, and mainly consists of two parts in production:
(1) the melt-casting film-making device of the resin comprises an extruder, a connector, a lower die head, an extruder moving device, an extruder accessory device, a heating and temperature control device and the like;
(2) the coating compounding device comprises an unreeling device, a base coating drying device, a preheating or corona treatment device, a coating compounding device, a powder spraying device, a reeling device and the like, and can realize three-layer interlayer compounding by configuring a second base material unreeling device.
S4, single-sided twice coating composite type, in production, the composite type film consists of two coating composite devices and two extruders, wherein the two continuous coating can be carried out on the same side of a base material, and the base material is compounded by high-temperature molten resin of a first extruder and then is compounded by a second extruder, so that a three-layer, four-layer or five-layer composite film can be produced at one time.
Preferably, the single-sided two-coating composite extrusion compounding machine has the following advantages:
A. in the same process, two resins may be applied;
B. the temperature of the same or different resins can be changed;
C. the coating thickness of the same kind or different kinds of resin can be freely combined, and the upper layer and the lower layer of different colors can be realized by adding the coloring master batch;
D. the processing speed and the extrusion coating thickness can be effectively considered;
E. by arranging the second base material and the third base material to unwind, multi-layer compounding can be realized.
Preferably, the preparation method of the multilayer composite fluorine film/laminated composite fluorine film comprises the following steps:
s1, coating an adhesive on the surface of a substrate by a compounding machine by adopting a dry compounding method, and laminating the adhesive on other films by a heating roller to form the adhesive;
s2, adopting wet compounding, coating a water-soluble adhesive, a water-dispersible adhesive and the like on the surface of the substrate, compounding with other materials in a wet state, and then using a press roller to press and dry.
Preferably, the adhesive is an environment-friendly adhesive, for example, polyurethane or hot melt adhesives, the base material is a low-cost material such as PE, PP, PET, the temperature of the heating roller is 25-280 ℃, the aqueous adhesive is gelatin, starch and the like, the water-dispersible adhesive is vinyl acetate emulsion and the like, and the drying temperature is 25-280 ℃.
Preferably, the preparation method of the multilayer coextrusion casting composite fluorine film comprises the following steps:
s1, respectively feeding the raw materials into hoppers of a multilayer co-extrusion extruder according to a certain proportion, wherein the extruder is provided with a plurality of extruder screws, and a heating device is started to preheat a die and the extruder by 30-60 min;
s2, after the process temperature is reached, co-casting and extruding the melt obtained by different raw materials under the action of pressure through a die orifice of an extruder, draining the melt onto a cooling roller through a traction roller, rapidly quenching, and simultaneously performing auxiliary cooling and compaction through an air knife to form a film with a flat surface;
s3, monitoring the thickness of the film in real time through an infrared film thickness gauge, performing high-voltage electric shock treatment on the surface layer through a corona device to form a corona layer, and forming a coiled material through the traction action of a winding roller after cutting corners and trimming to obtain the multilayer co-extrusion casting composite fluorine film.
Preferably, the preheating temperature is 150-350 ℃, the process temperature is 150-350 ℃, the method further comprises the step of printing or compounding operation on the surface of the formed corona layer, the flatness error of the flat film is not more than +/-3%, and the traction force of the winding roller is 20N/m 2 ～40N/m 2 The thickness of the multilayer coextrusion casting film is as follows: the multi-layer co-extrusion casting film reduces the cost of the pure single-layer fluororesin and increases the mechanical strength of the single-layer fluororesin.
Preferably, the preparation method of the multilayer coextrusion blow molding composite fluorine film comprises the following steps:
s1, introducing raw materials into a screw extruder through an existing device, then enabling the temperature to reach 150-350 ℃, heating to enable the materials to be in a molten state, introducing required materials into the screw extruder through a multilayer co-extrusion process of special equipment and special raw materials, and carrying out screw melting plasticization;
s2, starting a screw extruder, enabling the screw extruder to work, and then extruding a polymer material;
s3, longitudinally stretching the melted resin under the action of mechanical force of extrusion blow molding in an extruder, transversely stretching the resin simultaneously or later by blowing with compressed air to enable the multilayer composite film to be blown into a film, co-extruding the film by a plurality of extruders of the multilayer film extruder, extruding the film on a machine head, cooling the multilayer film in a cooling line by a fan of the extruder, and finally obtaining a rectangular fluororesin film;
s4, after the shaping is carried out by a multi-roll shaft pair of the multi-layer film extruder, carrying out high-voltage electric shock treatment on the surface layer by a corona device, rolling the film forming the corona layer, cutting edges of the shaped film by a multi-layer film extruder self-carrying trimming device, or carrying out unilateral slitting, and carrying out flattening rolling on the cut edges by a flattening machine;
s5, cutting samples with the length of about 5m respectively before and after the multi-layer composite film is rolled, checking, taking a film on the samples to test the surface energy, mechanical strength, high and low temperature shrinkage, ultraviolet resistance and the like of the film, judging whether the production of the fluororesin film meets the standard or not, and then reprocessing the fluororesin film which does not meet the standard;
s6, finally, the multilayer composite film which meets the related requirements after inspection and the multilayer composite film which does not meet the related requirements are pasted with a sample, and the film which meets the related requirements is packaged and enters a finished product raw material area.
Preferably, the preheating temperature is 150-350 ℃, the process temperature is 150-350 ℃, the air ring adopts an inner air ring, an outer air ring or a double air ring, and the printing or compound operation is carried out on the surface of the formed corona layer, the flatness error of the flat film is not more than +/-5%, and the traction force of the winding roller is 20N/m 2 ～40N/m 2 The thickness of the multilayer coextrusion casting film is as follows: 5-300 mu m, the multi-layer co-extrusion blow molding film reduces the cost of pure single-layer fluororesin and the like.
(III) beneficial effects
The invention provides a low-cost multilayer composite fluororesin film and a preparation method thereof. The device comprises the following
The beneficial effects are that:
1. according to the low-cost multilayer composite fluororesin film and the preparation method thereof, the comprehensive characteristics of the film are improved through the composite technology, the multilayer composite film can effectively reduce the high cost of pure fluororesin, the transverse and longitudinal mechanical properties of the composite film, such as tensile strength, tensile modulus, breaking strength, breaking elongation and the like, are effectively improved, the gas barrier property of the composite film is effectively improved, and the environmental resistance, chemical stability and the like are effectively improved.
2. According to the low-cost multilayer composite fluororesin film and the preparation method thereof, the fluororesin multilayer coextrusion technology is adopted to prepare the fluororesin symmetrical multilayer or asymmetrical multilayer composite film, the cost is reduced, the environmental resistance is improved, the ultraviolet ageing resistance and the like are improved, and the small molecular gases such as helium or hydrogen are blocked highly, so that the heat sealing performance is good; the heat sealing strength is high; the interlayer adhesion effect is good.
3. According to the low-cost multilayer composite fluorine resin film and the preparation method thereof, the mechanical strength of the multilayer composite fluorine film is greatly improved, the barrier property of the multilayer composite fluorine film is obviously improved, and the ultraviolet resistance of the single-layer fluorine resin is improved, so that the comprehensive performance of the single-layer fluorine resin film is further improved.
Drawings
FIG. 1 is a schematic illustration of a symmetrical double-sided multilayer coextruded composite fluorine film of the invention;
FIG. 2 is a schematic illustration of an asymmetric single-sided multilayer coextruded composite fluorine film of the invention;
FIG. 3 is a schematic view of a multilayer composite fluorine film of the invention.
Detailed Description
The following will clearly and completely describe the technical solutions in the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1:
the embodiment of the invention provides an extrusion composite fluorine film, which adopts an extrusion composite machine to prepare a multilayer composite fluorine film, wherein extrusion resin is a single layer or multiple layers of fluorine resin (modified or unmodified), molten flaky fluorine resin melt is uniformly and smoothly coated on a substrate film, or conversely, resin melt of extrusion resin (PE, PP, nylon, EVA, EVOH and the like) is uniformly and smoothly coated on the fluorine resin substrate film to form the composite fluorine film;
the material structure types of the extruded composite fluorine film are as follows:
single-sided one-shot extrusion composite, comprising extrusion of fluororesin/base film, extrusion of resin/fluororesin-based film;
single-sided multiple extrusion composite, including extrusion of fluororesin/base film, extrusion of resin/fluororesin-based film;
sandwich composite comprising extruded fluororesin/base film/extruded fluororesin;
multilayer extrusion composite comprising extruded fluororesin/base film and extruded resin
Fluorine resin-based film/extrusion resin/fluorine resin-based film;
the above extruded resin or extruded fluororesin may be a single-layer or multi-layer coextrusion, the base film may be a single-layer or multi-layer film, paper, extruded resin, metal thin, or the like, and the fluororesin is a modified or unmodified resin.
The preparation method of the extrusion composite fluorine film comprises the following steps:
s1, using 1 or more extruders and a T-shaped die head, extruding one or more thermoplastic resins into a flat die after melting in the extruder.
S2, casting and coating the film on the surface of another substrate through a T-type die, and pressing the composite film in a hot-sticking state.
S3, single-sided one-time coating composite type, which is a basic constitution device of an extrusion compounding machine, is most used in the field of flexible packaging, and mainly consists of two parts in production:
(1) the melt-casting film-making device of the resin comprises an extruder, a connector, a lower die head, an extruder moving device, an extruder accessory device, a heating and temperature control device and the like;
(2) the coating compounding device comprises an unreeling device, a base coating drying device, a preheating or corona treatment device, a coating compounding device, a powder spraying device, a reeling device and the like, and can realize three-layer interlayer compounding by configuring a second base material unreeling device.
S4, single-sided twice coating composite type, in production, the composite type film consists of two coating composite devices and two extruders, wherein the two continuous coating can be carried out on the same side of a base material, and the base material is compounded by high-temperature molten resin of a first extruder and then is compounded by a second extruder, so that a three-layer, four-layer or five-layer composite film can be produced at one time.
The single-sided twice-coating composite extrusion compounding machine has the following advantages:
A. in the same process, two resins may be applied;
B. the temperature of the same or different resins can be changed;
C. the coating thickness of the same kind or different kinds of resin can be freely combined, and the upper layer and the lower layer of different colors can be realized by adding the coloring master batch;
D. the processing speed and the extrusion coating thickness can be effectively considered;
E. by arranging the second base material and the third base material to unwind, multi-layer compounding can be realized.
Example 2:
embodiments of the present invention provide a multilayer composite fluorine film/laminated composite fluorine film, in which a composite film formed of two or more layers of the multilayer composite fluorine film/laminated composite fluorine film is not separable as one film. The single-layer or multi-layer unmodified fluororesin film is compounded with a base film through an adhesive (the adhesive can be Polyurethane (PU) or UV light curing), the adhesive is cured through chemical reaction in the adhesive bonding process, the adhesive on the surface of the base material is mainly a physical process, only a small part of the adhesive is a chemical process, at the moment, the components of the adhesive and the components in the plastic film are drilled together and are further cured, and the fluororesin (unmodified or modified) film and the base film are subjected to multi-layer compounding through a multi-layer compounding machine or a lamination compounding machine to prepare a multi-layer composite fluororesin film or a laminated composite fluororesin film structure of the fluororesin;
the material structure types of the multilayer composite fluorine film/laminated composite fluorine film are as follows:
bilayer composites, including fluororesin film/base film;
three layers of composite including a fluororesin film/a base film/a fluororesin film;
a multilayer composite comprising a fluororesin film/base film, a fluororesin film/base film/fluororesin film;
the above extruded resin or extruded fluororesin may be a single-layer or multi-layer coextrusion, the base film may be a single-layer or multi-layer film, paper, extruded resin, metal thin, or the like, and the fluororesin is a modified or unmodified resin.
The preparation method of the multilayer composite fluorine film/laminated composite fluorine film comprises the following steps:
s1, coating an adhesive on the surface of a substrate by a compounding machine by adopting a dry compounding method, and laminating the adhesive on other films by a heating roller to form the adhesive;
s2, adopting wet compounding, coating a water-soluble adhesive, a water-dispersible adhesive and the like on the surface of the substrate, compounding with other materials in a wet state, and then using a press roller to press and dry.
The adhesive is environment-friendly adhesive, such as polyurethane or hot melt adhesive, the base material is PE, PP, PET and other low-cost materials, the temperature of the heating roller is 60-150 ℃, the aqueous adhesive is gelatin, starch and other water-dispersible adhesive is vinyl acetate emulsion and other materials, and the drying temperature is 60-150 ℃.
Example 3:
the embodiment of the invention provides a multilayer coextrusion composite fluorine film, which is prepared by adopting multilayer coextrusion casting/blow molding equipment, and can be applied to separation films, isolation films, release films, barrier films, building films, agricultural films, rubber plug medical corrosion resistant films, solar panel front and back plate protective films, adjacent space aerostats, high-altitude balloons, medium-low-altitude balloons and the like by utilizing the advantages of a multilayer structure.
The preparation method of the multilayer coextrusion casting composite fluorine film comprises the following steps:
s1, respectively feeding raw materials into hoppers of a multilayer co-extrusion extruder according to a certain proportion, wherein the extruder is provided with a plurality of extruder screws, and a heating device is started to preheat a die and the extruder by 50 min;
s2, after the process temperature is reached, co-casting and extruding the melt obtained by different raw materials under the action of pressure through a die orifice of an extruder, draining the melt onto a cooling roller through a traction roller, rapidly quenching, and simultaneously performing auxiliary cooling and compaction through an air knife to form a film with a flat surface;
s3, monitoring the thickness of the film in real time through an infrared film thickness gauge, performing high-voltage electric shock treatment on the surface layer through a corona device to form a corona layer, and forming a coiled material through the traction action of a winding roller after cutting corners and trimming to obtain the multilayer co-extrusion casting composite fluorine film.
Wherein the preheating temperature is 200 ℃, the process temperature is 280 ℃, the method further comprises the step of printing or compounding operation on the surface of the formed corona layer, the flatness error of the flattened film is not more than +/-3%, and the traction force of the winding roller is 30N/m 2 The thickness of the multilayer coextrusion casting film is: 12.5 μm, 25 μm, 50 μm, 100 μm, 150 μm, 200 μm, etc., the multilayer co-extrusion casting film reduces the cost of the pure monolayer fluororesin and increases the mechanical strength.
The preparation method of the multilayer coextrusion blow molding composite fluorine film comprises the following steps:
s1, introducing raw materials into a screw extruder through an existing device, then enabling the temperature to reach 150-350 ℃, heating to enable the materials to be in a molten state, introducing required materials into the screw extruder through a multilayer co-extrusion process of special equipment and special raw materials, and carrying out screw melting plasticization;
s2, starting a screw extruder, enabling the screw extruder to work, and then extruding a polymer material;
s3, longitudinally stretching the melted resin under the action of mechanical force of extrusion blow molding in an extruder, transversely stretching the resin simultaneously or later by blowing with compressed air to enable the multilayer composite film to be blown into a film, co-extruding the film by a plurality of extruders of the multilayer film extruder, extruding the film on a machine head, cooling the multilayer film in a cooling line by a fan of the extruder, and finally obtaining a rectangular fluororesin film;
s4, after the shaping is carried out by a multi-roll shaft pair of the multi-layer film extruder, carrying out high-voltage electric shock treatment on the surface layer by a corona device, rolling the film forming the corona layer, cutting edges of the shaped film by a multi-layer film extruder self-carrying trimming device, or carrying out unilateral slitting, and carrying out flattening rolling on the cut edges by a flattening machine;
s5, cutting samples with the length of about 5m respectively before and after the multi-layer composite film is rolled, checking, taking a film on the samples to test the surface energy, mechanical strength, high and low temperature shrinkage, ultraviolet resistance and the like of the film, judging whether the production of the fluororesin film meets the standard or not, and then reprocessing the fluororesin film which does not meet the standard;
s6, finally, the multilayer composite film which meets the related requirements after inspection and the multilayer composite film which does not meet the related requirements are pasted with a sample, and the film which meets the related requirements is packaged and enters a finished product raw material area.
Wherein the preheating temperature is 200 ℃, the process temperature is 320 ℃, the air ring adopts an inner air ring, an outer air ring or a double air ring, and the printing or the compound operation is carried out on the surface of the formed corona layer, the flatness error of the flat film is not more than +/-5%, and the traction force of the winding roller is 30N/m 2 The thickness of the multilayer coextrusion casting film is: 12.5 μm, 25 μm, 50 μm, 100 μm, 150 μm, 200 μm, etc., the multilayer co-extrusion blown film reduces the cost of a pure monolayer of the fluororesin, etc.
The outermost layer of fluororesin (unmodified or modified, the modifier comprises an inorganic modifier and an organic modifier) has low surface tension self-cleaning property, high toughness, high ductility, impact resistance, high and low temperature resistance, ultraviolet aging resistance, friction resistance, corrosion resistance and water blocking; the adhesive layer adopts adhesive fluororesin (anhydride modified and the like) to connect the outermost layer fluororesin and the middle layer, so that good adhesive performance is achieved; nylon (including PA6, PA66, PA6/12, PA11, PA12, etc.) as intermediate layer material is connected with bondable fluorine tree; and obtaining the organic uniformly prepared multilayer composite film.
The outermost layer of fluororesin (unmodified or modified, the modifier comprises an inorganic modifier and an organic modifier) has low surface tension self-cleaning property, high toughness, high ductility, impact resistance, high and low temperature resistance, ultraviolet aging resistance, friction resistance, corrosion resistance and water blocking; the bonding layer is formed by connecting the outermost layer of fluororesin (anhydride modified and the like) with the intermediate layer by adopting bondable fluororesin, so that good bonding performance is achieved; the middle layer is made of polyolefin materials (including PE, LDPE, HDPE, LLDPE, mLLDPE, POE, PP, EVA, MMA and the like which are not modified or modified), and the polyolefin materials effectively reduce the cost of the fluororesin materials and expand the market application on the basis of ensuring the due comprehensive performance of the fluororesin.
The outermost fluorine resin (modified or unmodified) is resistant to high and low temperature, ultraviolet ageing, friction, corrosion and water; the adhesive layer adopts a barrier material nylon (comprising PA6, PA66, PA6/12, PA11, PA12 and the like) to link the fluororesin and the high barrier layer, so that good adhesive performance is achieved; the high barrier layer adopts a high-performance unmodified or modified barrier material (comprising EVOH, PVA, PA, PVDC and the like); and obtaining the organic uniformly prepared multilayer composite film.
The outermost fluorine resin (modified or unmodified) is resistant to high and low temperature, ultraviolet ageing, friction, corrosion and water; the adhesive layer adopts a barrier material nylon (including PA6, PA66, PA6/12, PA11, PA12 and the like) or a polyolefin material (including PE, LDPE, HDPE, LLDPE, mLLDPE, POE, PP, EVA, MMA and the like which are not modified or modified), and the nylon or the polyolefin material effectively reduces the cost of the fluororesin material and expands the market application on the basis of ensuring the due comprehensive performance of the fluororesin.
The multilayer coextrusion composite fluorine film is a symmetrical double-sided multilayer coextrusion composite fluorine film or an asymmetrical single-sided multilayer coextrusion composite fluorine film, as shown in figures 1 and 2, 1 and 5 layers are single-layer or multilayer fluorine resin (modified or unmodified); 2. the 4 layers are adhesive layer (modified or unmodified) single-layer or multi-layer; 3 is an intermediate layer nylon or polyolefin (modified or unmodified) or a base film monolayer or multilayer.
The multilayer coextrusion composite fluorine film is a multilayer composite fluorine film, as shown in figure 3, and 1 layer is a single layer or multiple layers of fluorine resin (modified or unmodified); the 2 layers are adhesive layers (modified or unmodified)/base film single layer or multiple layers.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (9)

1. The multilayer composite fluorine resin film is characterized in that the multilayer composite fluorine film is prepared by adopting an extrusion compounding machine, the extrusion resin is a single layer or a plurality of layers of fluorine resin (modified or unmodified), molten flaky fluorine resin melt is uniformly and flatly coated on a substrate film, or conversely, resin melt of the extrusion resin (PE, PP, nylon, EVA, EVOH and the like) is uniformly and flatly coated on the fluorine resin substrate film to form the composite fluorine film;
the material structure types of the extruded composite fluorine film are as follows:
single-sided one-shot extrusion composite, comprising extrusion of fluororesin/base film, extrusion of resin/fluororesin-based film;
single-sided multiple extrusion composite, including extrusion of fluororesin/base film, extrusion of resin/fluororesin-based film;
sandwich composite comprising extruded fluororesin/base film/extruded fluororesin;
multilayer extrusion composite including extrusion of fluororesin/base film, extrusion of resin/fluororesin-based film/extrusion of resin/fluororesin-based film;
the above extruded resin or extruded fluororesin may be a single-layer or multi-layer coextrusion, the base film may be a single-layer or multi-layer film, paper, extruded resin, metal thin, or the like, and the fluororesin is a modified or unmodified resin.
The multilayer composite fluorine film/laminated composite fluorine film is formed of two or more layers so that the composite film is not separable as one film. The single-layer or multi-layer unmodified fluororesin film is compounded with a base film through an adhesive (the adhesive can be Polyurethane (PU) or UV light curing), the adhesive is cured through chemical reaction in the adhesive bonding process, the adhesive on the surface of the base material is mainly a physical process, only a small part of the adhesive is a chemical process, at the moment, the components of the adhesive and the components in the plastic film are drilled together and are further cured, and the fluororesin (unmodified or modified) film and the base film are subjected to multi-layer compounding through a multi-layer compounding machine or a lamination compounding machine to prepare a multi-layer composite fluororesin film or a laminated composite fluororesin film structure of the fluororesin;
the material structure types of the multilayer composite fluorine film/laminated composite fluorine film are as follows:
bilayer composites, including fluororesin film/base film;
three layers of composite including a fluororesin film/a base film/a fluororesin film;
a multilayer composite comprising a fluororesin film/base film, a fluororesin film/base film/fluororesin film;
the above extruded resin or extruded fluororesin may be a single-layer or multi-layer coextrusion, the base film may be a single-layer or multi-layer film, paper, extruded resin, metal thin, or the like, and the fluororesin is a modified or unmodified resin.
The multilayer coextrusion composite fluorine film adopts multilayer coextrusion casting/blow molding equipment to prepare the high-performance multilayer coextrusion casting/blow molding composite fluorine film, and the multilayer composite fluorine film utilizes the advantages of a multilayer structure, so that the cost is effectively reduced, the comprehensive performance is improved, and the multilayer coextrusion casting/blow molding composite fluorine film can be applied to separation films, isolation films, release films, barrier films, building films, agricultural films, rubber plug medical anti-corrosion films, solar panel positive backboard protective films, adjacent space aerostats, high-altitude balloons, medium-low-altitude balloons and the like.
2. The method for producing a low-cost multilayer composite fluororesin film according to claim 1, characterized in that said method for producing an extruded composite fluororesin film comprises the steps of:
s1, using 1 or more extruders and a T-shaped die head, extruding one or more thermoplastic resins into a flat die after melting in the extruder.
S2, casting and coating the film on the surface of another substrate through a T-type die, and pressing the composite film in a hot-sticking state.
S3, single-sided one-time coating composite type, which is a basic constitution device of an extrusion compounding machine, is most used in the field of flexible packaging, and mainly consists of two parts in production:
(1) the melt-casting film-making device of the resin comprises an extruder, a connector, a lower die head, an extruder moving device, an extruder accessory device, a heating and temperature control device and the like;
(2) the coating compounding device comprises an unreeling device, a base coating drying device, a preheating or corona treatment device, a coating compounding device, a powder spraying device, a reeling device and the like, and can realize three-layer interlayer compounding by configuring a second base material unreeling device.
S4, single-sided twice coating composite type, in production, the composite type film consists of two coating composite devices and two extruders, wherein the two continuous coating can be carried out on the same side of a base material, and the base material is compounded by high-temperature molten resin of a first extruder and then is compounded by a second extruder, so that a three-layer, four-layer or five-layer composite film can be produced at one time.
3. The method for preparing a low-cost multilayer composite fluororesin film according to claim 2, wherein said single-sided two-coating composite extrusion compounding machine has the following advantages:
A. in the same process, two resins may be applied;
B. the temperature of the same or different resins can be changed;
C. the coating thickness of the same kind or different kinds of resin can be freely combined, and the upper layer and the lower layer of different colors can be realized by adding the coloring master batch;
D. the processing speed and the extrusion coating thickness can be effectively considered;
E. by arranging the second base material and the third base material to unwind, multi-layer compounding can be realized.
4. The method for producing a low-cost multilayer composite fluororesin film according to claim 1, characterized in that said method for producing a multilayer composite fluororesin film/laminated composite fluororesin film comprises the steps of:
s1, coating an adhesive on the surface of a substrate by a compounding machine by adopting a dry compounding method, and laminating the adhesive on other films by a heating roller to form the adhesive;
s2, adopting wet compounding, coating a water-soluble adhesive, a water-dispersible adhesive and the like on the surface of the substrate, compounding with other materials in a wet state, and then using a press roller to press and dry.
5. The method according to claim 4, wherein the adhesive is an environment-friendly adhesive, such as polyurethane or hot melt adhesives, the base material is a low-cost material such as PE, PP, PET, the heating roller temperature is 25-280 ℃, the aqueous adhesive is gelatin, starch, etc., the water-dispersible adhesive is vinyl acetate emulsion, etc., and the drying temperature is 25-280 ℃.
6. The method for preparing a low-cost multilayer composite fluororesin film according to claim 1, characterized in that said method for preparing a multilayer co-extrusion casting composite fluororesin film comprises the steps of:
s1, respectively putting the raw materials into hoppers of a multilayer co-extrusion extruder according to a certain proportion, wherein the extruder is provided with a plurality of extruder screws, and starting a heating device to preheat a die and the extruder for 30-60 min;
s2, after the process temperature is reached, co-casting and extruding the melt obtained by different raw materials under the action of pressure through a die orifice of an extruder, draining the melt onto a cooling roller through a traction roller, rapidly quenching, and simultaneously performing auxiliary cooling and compaction through an air knife to form a film with a flat surface;
s3, monitoring the thickness of the film in real time through an infrared film thickness gauge, performing high-voltage electric shock treatment on the surface layer through a corona device to form a corona layer, and forming a coiled material through the traction action of a winding roller after cutting corners and trimming to obtain the multilayer co-extrusion casting composite fluorine film.
7. The method for producing a low-cost multilayer composite fluororesin film according to claim 6, wherein said preheating temperature is 150 to 350 ℃, said process temperature is 150 to 350 ℃, further comprising the step of performing printing or laminating operation on the surface of the formed corona layer, said flattening film being flatThe surface error is not more than +/-3%, and the traction force of the winding roller is 20N/m 2 ～40N/m 2 The thickness of the multilayer coextrusion casting film is as follows: the multi-layer co-extrusion casting film reduces the cost of the pure single-layer fluororesin and increases the mechanical strength of the single-layer fluororesin.
8. The method for producing a low-cost multilayer composite fluororesin film according to claim 1, characterized in that said method for producing a multilayer co-extrusion blow molded composite fluororesin film comprises the steps of:
s1, introducing raw materials into a screw extruder through an existing device, then enabling the temperature to reach 150-350 ℃, heating to enable the materials to be in a molten state, introducing required materials into the screw extruder through a multilayer co-extrusion process of special equipment and special raw materials, and carrying out screw melting plasticization;
s2, starting a screw extruder, enabling the screw extruder to work, and then extruding a polymer material;
s3, longitudinally stretching the melted resin under the action of mechanical force of extrusion blow molding in an extruder, transversely stretching the resin simultaneously or later by blowing with compressed air to enable the multilayer composite film to be blown into a film, co-extruding the film by a plurality of extruders of the multilayer film extruder, extruding the film on a machine head, cooling the multilayer film in a cooling line by a fan of the extruder, and finally obtaining a rectangular fluororesin film;
s4, after the shaping is carried out by a multi-roll shaft pair of the multi-layer film extruder, carrying out high-voltage electric shock treatment on the surface layer by a corona device, rolling the film forming the corona layer, cutting edges of the shaped film by a multi-layer film extruder self-carrying trimming device, or carrying out unilateral slitting, and carrying out flattening rolling on the cut edges by a flattening machine;
s5, cutting samples with the length of about 5m respectively before and after the multi-layer composite film is rolled, checking, taking a film on the samples to test the surface energy, mechanical strength, high and low temperature shrinkage, ultraviolet resistance and the like of the film, judging whether the production of the fluororesin film meets the standard or not, and then reprocessing the fluororesin film which does not meet the standard;
s6, finally, the multilayer composite film which meets the related requirements after inspection and the multilayer composite film which does not meet the related requirements are pasted with a sample, and the film which meets the related requirements is packaged and enters a finished product raw material area.
9. The method for preparing a low-cost multilayer composite fluororesin film according to claim 8, wherein the preheating temperature is 150 to 350 ℃, the process temperature is 150 to 350 ℃, the air ring is an inner air ring, an outer air ring or a double air ring, and the printing or the composite operation is performed on the surface of the formed corona layer, the flatness error of the flat film is not more than + -5%, and the traction force of the winding roller is 20N/m 2 ～40N/m 2 The thickness of the multilayer coextrusion casting film is as follows: 5-300 mu m, the multi-layer co-extrusion blow molding film reduces the cost of pure single-layer fluororesin and the like.
CN202310199107.2A 2023-03-03 2023-03-03 Low-cost multilayer composite fluororesin film and preparation method thereof Pending CN116423945A (en)

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