CN115352165A - Three-layer co-extrusion polyester alloy film with lasting adhesion and preparation method thereof - Google Patents

Three-layer co-extrusion polyester alloy film with lasting adhesion and preparation method thereof Download PDF

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CN115352165A
CN115352165A CN202210813009.9A CN202210813009A CN115352165A CN 115352165 A CN115352165 A CN 115352165A CN 202210813009 A CN202210813009 A CN 202210813009A CN 115352165 A CN115352165 A CN 115352165A
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layer
alloy film
agent
pet
polyester alloy
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CN115352165B (en
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陈洪
茹正伟
周旭
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Changzhou Bbetter Film Technologies Co ltd
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Changzhou Bbetter Film Technologies 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
    • C08L23/0869—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen with unsaturated acids, e.g. [meth]acrylic acid; with unsaturated esters, e.g. [meth]acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)

Abstract

The invention belongs to the technical field of thin films, and particularly relates to a three-layer co-extrusion polyester alloy film with lasting adhesion and a preparation method thereof, wherein the three-layer co-extrusion polyester alloy film comprises the following steps: the layer A, the layer B and the layer C are arranged in sequence; wherein the layer A comprises 1 to 10 weight percent of anti-UV agent, 0.1 to 0.5 weight percent of anti-sticking agent and the balance of PET; the C layer comprises 48.5-77.6 wt% of EBA, 19.4-48.5 wt% of PET and the balance of a cross-linking agent and an anti-sticking agent to form an alloy layer; the layer B comprises 80-90wt% of PET and 10-20wt% of on-line trimming recycled materials; the polyester alloy film greatly reduces the proportion of the addition amount by adding the main alloy raw materials and the functional master batch into the C layer positioned on the surface layer, and the formula of the polyester alloy film is uniquely utilized to realize the addition of the cross-linking agent in the co-extrusion process, so that the alloy layer in the C layer and the EVA form a durable high-adhesion bonding layer.

Description

Three-layer co-extrusion polyester alloy film with lasting adhesion and preparation method thereof
Technical Field
The invention belongs to the technical field of thin films, and particularly relates to a three-layer co-extrusion polyester alloy film with lasting adhesion and a preparation method thereof.
Background
The PET film can be subjected to surface treatment by using a corona device in the production process so as to enhance the surface tension of the film and improve the printing performance and the composite adhesive capacity of the film; however, in the case where a high adhesive force and a strong adhesive durability are required, for example, when a long-life material is produced by adhering a PET film to another material with an adhesive resin such as an acid anhydride-modified copolymer such as PE or PP or an ethylene-vinyl acetate copolymer (EVA), the surface of the PET film is extremely poor in permanent adhesion even if the surface is subjected to corona treatment because of its surface inertness.
Therefore, in order to solve the above technical problems, an effective method is required to be found so that the PET film can overcome the defect in the application.
Disclosure of Invention
The invention provides a modified biaxially oriented polyester alloy film with high adhesion and a preparation method thereof, and aims to solve the problem that the durable adhesion of a PET (polyethylene terephthalate) film and EVA (ethylene-vinyl acetate) in a long-life material is insufficient.
In order to solve the above technical problems, the present invention provides a polyester alloy film comprising: the layer A, the layer B and the layer C are arranged in sequence; wherein the layer A comprises 1 to 10 weight percent of anti-UV agent, 0.1 to 0.5 weight percent of anti-sticking agent and the balance of PET; the C layer comprises 48.5-77.6 wt% of EBA, 19.4-48.5 wt% of PET and the balance of a cross-linking agent and an anti-sticking agent to form an alloy layer; the layer B comprises 80-90wt% of PET and 10-20wt% of on-line edge cutting regrind.
In another aspect, the present invention further provides a method for preparing a polyester alloy film, comprising the following steps: preparing a C-layer premix, namely uniformly mixing the C-layer premix, extruding, granulating and drying; uniformly mixing the raw and auxiliary materials of each layer, and drying and pre-crystallizing; adding the materials of each layer into a corresponding extruder for extrusion; co-extruding three layers of die heads; casting a sheet; longitudinal stretching; transversely stretching; and (5) post-treating and winding the film.
The polyester alloy film has the beneficial effects that the main alloy raw materials and the functional master batch are added into the layer C positioned on the surface layer, so that the addition ratio is greatly reduced, the formula of the polyester alloy film is uniquely utilized to realize the addition of the ester exchange crosslinking catalyst in the co-extrusion process, and in the reaction extrusion process, ester groups on the main chain of a PET molecule and ester groups on the side chain of the EBA undergo ester exchange reaction to carry out grafting and crosslinking, so that a graft copolymer and a crosslinked copolymer are formed; in addition, the B layer positioned in the middle layer utilizes the characteristic of online edge material recovery of a biaxial stretching process, so that the alloy crosslinking degree between the B layer and the C layer is realized, and the interlayer bonding strength is further improved.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by the practice of the invention.
In order to make the aforementioned and other objects, features and advantages of the present invention comprehensible, preferred embodiments accompanied with figures are described in detail below.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a structural view of a polyester alloy film of the present invention;
FIG. 2 is a schematic representation of the use of the polyester alloy film of the present invention;
in the figure:
the adhesive comprises a layer A1, a layer B2, a layer C3, EVA4 and an adhesive layer 5;
Detailed Description
To make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings, and it is apparent that the described embodiments are some, but not all embodiments of the present invention. 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.
As shown in fig. 1, the present invention provides a polyester alloy film comprising: the layer A, the layer B and the layer C are arranged in sequence; wherein the layer A comprises 1 to 10 weight percent of anti-UV agent, 0.1 to 0.5 weight percent of anti-sticking agent and the balance of PET; the C layer comprises 48.5-77.6 wt% of EBA, 19.4-48.5 wt% of PET and the balance of a cross-linking agent and an anti-sticking agent to form an alloy layer; the layer B comprises 80-90wt% of PET and 13wt% of on-line trimming regrind.
Specifically, the ratio of the EBA raw material of the C layer to the sum of the EBA and the PET in the layer is 50-80%, and if the content of the EBA in the C layer is less than 50wt%, the adhesive performance of the C layer relative to EVA, PE and PP anhydride modified adhesive resin is unsatisfactory; if the EBA content in the C layer is more than 80wt%, the corresponding PET content in the C layer is too low (less than 20 wt%), which tends to result in unsatisfactory fusion bonding between B, C layers.
Specifically, the EBA and the PET macromolecules in the layer C are subjected to ester exchange crosslinking reaction, and ester groups on a main chain of a PET molecule and ester groups on an EBA side chain are subjected to ester exchange reaction for grafting and crosslinking by adding an ester exchange crosslinking catalyst in the reaction extrusion process to form a graft copolymer and a crosslinked copolymer; the interface of C, B layer is also subject to partial ester exchange crosslinking reaction under the action of the crosslinking agent contained in layer C, so that EBA and PET in layer C are enhanced to be fused with each other and C, B layer interface.
Specifically, the A, B layer has high PET content (more than 80%) together, so that the interlayer fusion is good; B. the C layer ensures no delamination through interlayer fusion and ester exchange crosslinking; as shown in fig. 2, since the layer C contains a high content of EBA, the polyester alloy film can be fused with a binder resin such as EVA to form a high-adhesion adhesive layer because EBA and EVA are the same type of modified polyethylene binder resin.
In this example, in particular, the EBA has a thermal decomposition temperature higher than 300 ℃, i.e. a temperature resistance higher than that of EVA, and a melt index (2.16 kg/260 ℃) (measured according to DIN EN IOS 1133) ranging from 0.5 to 20g/10min; the mass ratio of butyl acrylate in the EBA is 10-20%; the processing temperature of the EBA is matched with the melting processing temperature of the PET of 270-285 ℃, the extrusion processing temperature of the ethylene-butyl acrylate copolymer (EBA) of the preferred embodiment of the invention can reach 300 ℃, and the requirements are met.
Optionally, the butyl acrylate in the EBA may be replaced by a compound selected from the group consisting of: ethyl methacrylate, methyl acrylate, methyl methacrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, t-butyl acrylate, t-butyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, n-octyl acrylate, n-octyl methacrylate, 2-octyl acrylate, 2-octyl methacrylate, undecyl acrylate, undecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, dodecyl acrylate, dodecyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate.
In this embodiment, the PET is specifically polyethylene terephthalate, and the intrinsic viscosity IV is greater than 0.62, preferably 0.68 to 0.76.
In this embodiment, optionally, in order to produce opaque alloy film, a certain proportion of color modifier may be added to each layer A, B, C, and in the production of white opaque alloy film, titanium dioxide may be added to each layer, and the addition proportion is 5-20 wt%, preferably 10-15 wt%, of the total mass of each layer.
In this embodiment, optionally, in order to prevent adhesion between alloy film layers, prevent opening, and stabilize lamination during use, an anti-sticking agent is added to the film layer surface to control a suitable surface friction coefficient, and inorganic particles are added to the A, C layer as an anti-sticking agent, and if the alloy film is required to be a transparent film, a silica anti-sticking agent is generally selected, and the particle size of the silica anti-sticking agent is 1-5 μm.
In this embodiment, specifically, the total thickness of the polyester alloy film is 0.050 to 0.350mm; the thickness of the layer A is 5-20% of the total thickness; the thickness of the B layer is 60-90% of the total thickness; the thickness of the C layer is 5-20% of the total thickness.
In this embodiment, specifically, the layer C contains a main alloy functional material, so that the alloy film of the present invention has the characteristics of high adhesion with the EVA film, good fusion between layers, and no delamination.
In this embodiment, to ensure the durable adhesion of the alloy film, the alloy film should have aging resistance, and since the aging factor of the polymer film is mainly degradation embrittlement caused by photo-thermal oxidation, the polymer film should be added with a light stabilizer, and the light stabilizer of the present invention is added with two types of ultraviolet absorbers or UV inhibitors, such as alpha-hydroxybenzophenone, salicylates, benzotriazole, etc., according to whether the transparency of the alloy film is required; if the alloy film does not require transparency, a second light stabilizer, namely a light shielding agent, can be added into the high polymer, wherein the second light stabilizer has the functions of absorbing light and converting the light into heat or reflected light so that the heat or reflected light cannot enter the high polymer, such as carbon black, stepless or organic pigments, zinc oxide, titanium oxide, metal powder and the like, preferably titanium dioxide, and the opaque light stabilizer is also used as a color-changing filler for the film material.
In this embodiment, optionally, the transparent alloy film is made of a UV-resistant agent, and the A, C layer is made of a mixture containing one or two of α -hydroxybenzophenone, salicylates, and benzotriazole. anti-UV agents, preferably containing salicylates; wherein the UV inhibitor is added into the layer CIn an amount of 1% to 10%, preferably 5%, of the total mass of the layer; as the anti-UV agent is added into the inner layer and the outer layer of the alloy film, the aging resistance of the alloy film is enhanced, the lasting adhesive force between the alloy film layers and the adhesive resin is ensured, and the alloy film has the thickness of 120kwh.m -2 The surface yellowing value delta b after ultraviolet irradiation is less than or equal to 2.5.
In this embodiment, specifically, the preparation of the C-layer premix includes uniformly mixing the PET, the EBA, and the anti-UV agent in a certain proportion, performing twin-screw mixing granulation to obtain premix slices, and performing drying treatment to control the moisture content of the material to be less than 50 PPM.
In this embodiment, it is specific that three-layer is crowded altogether includes that required raw and auxiliary materials of each layer mix respectively after the drying, is extruded corresponding material by each layer extruder, and wherein C layer material adds the esterification crosslinking catalyst in extrusion process and reacts and extrudes, and each layer fuse-element passes through filter, measuring pump, distributor, flat membrane die head coextrusion. The main process control parameters are as follows: the temperature of an extruder on the layer A is 250-285 ℃, the temperature of an extruder on the layer B is 250-285 ℃, and the temperature of an extruder on the layer C is 240-275 ℃; the temperature of the filter is 275-280 ℃; the temperature of the melt line A, B is 275-280 ℃, and the temperature of the melt line C is 270-275 ℃.
In this embodiment, the crosslinking agent is a transesterification catalytic crosslinking agent, preferably tetrabutyl titanate Ti (OBu) 4 And tetrabutyl stannate Sn (OBu) 4 (ii) a The cross-linking agent is injected by a micro pump according to the mass ratio of 0.1-1 wt% of the layer C.
In this embodiment, specifically, the die temperature of the cast sheet is 270 to 275 ℃; the temperature of the cooling rotary drum is 20-40 ℃.
In this embodiment, specifically, the longitudinal stretching includes preheating the sheet and stretching at a temperature of 70-95 ℃, after the longitudinal stretching, the sheet needs to be cooled at a temperature of less than or equal to 60 ℃, the cooling process needs to be performed with appropriate longitudinal relaxation, which is realized by controlling an appropriate rate to decrease progressively, and the relaxation rate after the longitudinal stretching is generally 1-5%; the longitudinal stretching ratio of the alloy film ranges from 2.8 to 4.0.
In this embodiment, specifically, the transverse stretching includes that the longitudinally stretched sheet enters a transverse stretcher, and is drawn into a film through four stages of preheating, stretching, heat treatment and cooling. The preheating temperature range is 80-105 ℃, the transverse stretching temperature is 100-150 ℃, the heat treatment temperature is 190-240 ℃, and the temperature after cooling is less than or equal to 60 ℃; the film relaxation rate of the heat treatment rear section and the cooling zone after transverse stretching is 1-5%; the transverse draw ratio is usually in the range of 3.0 to 4.0.
In this embodiment, specifically, the film post-treatment and rolling includes stretching the alloy film in the transverse direction, in order to increase the surface wet tension or surface free energy of the C layer and enhance the adhesive force with the adhesive resin, corona or flame treatment is generally performed, and the treated C layer wet Zhang Li dyn/cm is controlled.
Specifically, the alloy film biaxial stretching production line is complex, the automation degree is high, besides the strict control of the main process indexes, a plurality of process parameters need to be correspondingly and meticulously controlled, such as the quality control of raw and auxiliary materials, the thickness tolerance control of the film, the reasonable and stable proportion of the raw and auxiliary materials of each layer, the proper and stable magnitude of the film winding tension and the like, which are necessary factors for obtaining the high-quality alloy film of the invention.
Specific examples and comparative examples:
examples 1, 2, 3 test layer a UV inhibitor ratio;
examples 4, 5, 6 test the EBA ratio of the C layer;
examples 1, 7, 8 test the ratio of transesterification crosslinking catalyst in layer C;
example 9 testing the limit high EBA ratio of layer C;
compared with the prior art, the single-layer or three-layer co-extruded pure PET film facilitates comparison of various performance detection parameters of the embodiment and the comparative example.
And EVA peel strength test method: the samples of examples and comparative examples were cut into 5 pieces each having a width (10. + -. 0.5) mm and a length of 250 to 300mm as specified in GB/T2790-1995, pressed on ground glass using EVA for sealing, laminated at 148 ℃ for 10 minutes, and then tested for 180 ℃ peel force between the piece and the EVA by a tensile tester at a peel speed of 100mm/min.
UV resistance (UV treatment and test): according to IEC61215.2005 10.10, 3 100mmx100mm samples were cut out, and the temperature used was (60. + -.5). The following UV A wavelength was applied: 320 nm-400 nm, radiation at 120kwh.m -2 And operating, testing the yellow index b of the sample, calculating delta b, and taking a median value of the result.
Mechanical property testing (tensile strength, elongation at break): according to the specification of GB/T13542.2-2009, a sample is 200mm long, has a width of (15 +/-1) mm, is taken 5 in each of the transverse direction and the longitudinal direction, two marking lines are marked in the sample at a distance of at least 50mm, and a load is applied at a speed of 100mm/min until the single component of the sample is destroyed as an end point. The result was the median of 5 test values.
Testing the thermal shrinkage rate: according to the regulation of GB/T13542.2-2009, a sample is hung and placed in a constant-temperature oven, the heating temperature is (150 +/-2) DEG C, the heating time is 30min, and the longitudinal and transverse thermal shrinkage rates of the sample are averaged.
Testing the water vapor transmission rate: the test method comprises an electrolytic sensor method and an infrared sensor method, wherein the electrolytic sensor method is preferably selected, and the test conditions are as follows according to the regulation of GB/T21529-2008: the temperature (38 +/-2) DEG C and the relative humidity (90 +/-2)%, the sample is detected, and the median value is taken.
Boiling water treatment: according to the standard GB/31034-2014 of the solar cell back panel, a sample prepared by laminating a film sample and EVA (according to the method for preparing the sample by using the EVA peel strength) (100 mmx300 mm) is placed in a constant-temperature boiling water bath at the temperature of (98 +/-2) DEG for treatment for 24 (48) hours, the peel strength is taken out for testing, and the median value is taken for comparison.
Coefficient of friction: according to ASTM D1894 or GB10006 test method, 5 pairs of samples are cut along the longitudinal direction of the film, the size of the sample is 200mmx85mm, and the action and static friction coefficient are measured by using a film surface roughness tester.
Example 1
In the alloy film of the present embodiment, the a layer includes: 94.7wt% of PET resin, 0.3wt% of silica anti-sticking agent and 5wt% of anti-UV agent; the B layer includes: 87wt% of PET resin and 13wt% of online trimming recycled material; the C layer comprises 40.2wt% of PET resin, 58.5wt% of EBA, 0.3wt% of silica antisticking agent and 1wt% of cross-linking agent; the alloy film is an ABC three-layer co-extrusion structure, and the total thickness of the alloy film is 300um.
Example 2
In the alloy film of the embodiment, the layer a includes: 91.7wt% of PET resin, 0.3wt% of silica anti-sticking agent and 8wt% of anti-UV agent; the B layer includes: 87wt% of PET resin and 13wt% of online trimming recycled material; the C layer comprises 40.2wt% of PET, 58.5wt% of EBA, 1wt% of cross-linking agent and 0.3wt% of silica antisticking agent. The alloy film is an ABC three-layer co-extrusion structure, and the total thickness of the alloy film is 300um.
Example 3
In the alloy film of the present embodiment, the a layer includes: 99.7wt% of PET resin and 0.3wt% of silica anti-sticking agent; the B layer includes: 87wt% of PET resin and 13wt% of online trimming recycled material; the C layer comprises PETG 40.2wt%, EBA 58.5wt%, cross-linking agent 1wt% and silica anti-sticking agent 0.3wt%. The alloy film is an ABC three-layer co-extrusion structure, and the total thickness of the alloy film is 300um.
Example 4
In the alloy film of the present embodiment, the a layer includes: 94.7wt% of PET resin, 5wt% of anti-UV agent and 0.3wt% of silica anti-sticking agent; the B layer includes: 87wt% of PET resin and 13wt% of online trimming recycled material; the C layer comprises 25.2wt% of PET resin, 73.5wt% of EBA, 1wt% of cross-linking agent and 0.3wt% of silica antisticking agent. The alloy film is an ABC three-layer co-extrusion structure, and the total thickness of the alloy film is 300um.
Example 5
In the alloy film of the embodiment, the layer a includes: 94.7wt% of PET resin, 5wt% of anti-UV agent and 0.3wt% of silica anti-sticking agent; the B layer includes: 87wt% of PET resin and 13wt% of online trimming recycled material; the C layer comprises 50.2wt% of PET resin, 48.5wt% of EBA, 1wt% of cross-linking agent and 0.3wt% of silica antisticking agent. The alloy film is an ABC three-layer co-extrusion structure, and the total thickness of the alloy film is 300 mu m.
Example 6
In the alloy film of the present embodiment, the a layer includes: 94.7wt% of PET resin, 5wt% of anti-UV agent and 0.3wt% of silica anti-sticking agent; the B layer includes: 87wt% of PET resin and 13wt% of online trimming recycled material; the C layer comprises 85.2wt% of PET resin, 13.5wt% of EBA, 1wt% of cross-linking agent and 0.3wt% of silica antisticking agent. The alloy film is an ABC three-layer co-extrusion structure, and the total thickness of the alloy film is 300um.
Example 7
In the alloy film of the embodiment, the layer a includes: 94.7wt% of PET resin, 0.3wt% of silica anti-sticking agent and 5wt% of anti-UV agent; the B layer includes: 87wt% of PET resin and 13wt% of online trimming recycled material; the C layer comprises 40.2wt% of PET, 59wt% of EBA, 0.5wt% of cross-linking agent and 0.3wt% of silica antisticking agent. The alloy film is an ABC three-layer co-extrusion structure, and the total thickness of the alloy film is 300um.
Example 8
In the alloy film of the present embodiment, the a layer includes: 94.7wt% of PET resin, 0.3wt% of silica anti-sticking agent and 5wt% of anti-UV agent; the B layer includes: 87wt% of PET resin and 13wt% of online trimming recycled material; the C layer comprises 50.7wt% of PET resin, 49wt% of EBA and 0.3wt% of silica antisticking agent. The alloy film is an ABC three-layer co-extrusion structure, and the total thickness of the alloy film is 300um.
Example 9
In the alloy film of the present embodiment, the a layer includes: 94.7wt% of PET resin, 0.3wt% of silica anti-sticking agent and 5wt% of anti-UV agent; the B layer includes: 87wt% of PET resin and 13wt% of online trimming recycled material; the C layer comprises 16.7wt% of PET resin, 82wt% of EBA, 1wt% of cross-linking agent and 0.3wt% of silica antisticking agent. The alloy film is an ABC three-layer co-extrusion structure, and the total thickness of the alloy film is 300 mu m.
Comparative example
100% pure PET, obtaining a PET film through a biaxial stretching process, wherein the PET film is a single layer or three layers, and comprises: 100wt% of PET resin. The thickness is 300um.
TABLE 1 comparison of Performance parameters of examples 1-9 with comparative examples
Figure BDA0003739985450000101
Figure BDA0003739985450000111
The examples and comparative examples illustrate:
example 3: the layer A is not added with an anti-UV agent, the delta b is high, and the weather resistance of the alloy film is poor;
example 5: the EBA content in the C layer is low, and the peel strength between the C layer and EVA after boiling water treatment is less than or equal to 80N/10mm, so that the high peel strength requirement cannot be met;
example 6: the EBA proportion in the C layer is low, and the peel strength of the C layer and EVA after boiling water treatment is less than 60N/10mm, which does not meet the requirement;
example 8: the layer C is free of a crosslinking agent, and the peel strength of the layer C and EVA after boiling water treatment is less than or equal to 80N/10mm, so that the requirement is not met;
example 9: the EBA proportion in the layer C is too high, the content of corresponding PET in the layer C is too low, and the layer C and the layer B are easily delaminated and disqualified after boiling water treatment;
the comparative example was a pure PET film;
the following sections in Table 1"C layer and EVA Peel Strength" after boiling Water treatment C layer and EVA Peel Strength "show that: the adhesive strength of the C layer and the EVA adhesive resin is greatly influenced by the EBA content and the content of the cross-linking agent in the C layer, generally in a proportional relationship, and considering the loss of the peel strength after aging and the requirement of B, C interlayer PET fusion, the mass ratio of the EBA in the alloy film C layer is preferably 48.5-77.6%; the mass fraction of the added cross-linking agent is 0.5-1%.
Ultraviolet aging resistance and durability: to ensure 120kwh.m -2 After ultraviolet treatment, the yellowing value delta b is less than 2.5, and the mass fraction of the added UV resistant agent in the layer A is more than or equal to 1wt%;
the adhesive property modification of the alloy film is concentrated on the layer C, and the thickness of the layer C accounts for only 10-20% of the total thickness, so that the influence on the integral tensile strength, elongation at break and thermal shrinkage rate of the alloy film is small, and the characteristics of good mechanical property and low thermal shrinkage rate of PET are basically kept.
Analyzing the influence of the water vapor transmission rate of the samples in table 1, it can be seen that the equal proportion of the EBA and PET of the C layer and the high content of the cross-linking agent improve the degree of cross-linking, which is helpful for improving the water vapor transmission rate.
From the above analysis, it can be seen that examples 1, 2, 4 and 7 are preferred alloy film examples.
In this embodiment, optionally, the alloy film prepared by the above method is a transparent alloy film with a lasting high adhesive force on one side, and if a double-sided lasting alloy film with a high adhesive force needs to be prepared, the layer a can be produced by the same formula and process as the layer C; the prepared alloy film is a unidirectional light anti-ultraviolet aging alloy film, if a bidirectional light anti-ultraviolet alloy film is needed, more than 5% of anti-UV agent is added into the layer C to prepare the bidirectional light anti-ultraviolet alloy film; if opaque alloy films need to be produced, pigment color master batches with different proportions can be added into raw materials of each layer of the alloy film according to the requirement of light transmittance, inorganic pigment fillers with light stabilization effect (such as titanium dioxide, barium sulfate, calcium carbonate, carbon black and the like) can be used in combination with an anti-UV agent, the weather resistance and the ageing resistance are better, and the anti-UV agent can be reduced or not used.
In conclusion, the polyester alloy film greatly reduces the proportion of the addition amount by adding the main alloy raw materials and the functional master batch into the layer C positioned on the surface layer, and the formula of the invention is exclusively utilized to realize the addition of the ester exchange crosslinking catalyst in the co-extrusion process, and the ester group on the main chain of the PET molecule and the ester group on the side chain of the EBA generate ester exchange reaction for grafting and crosslinking in the reaction extrusion process to form the graft copolymer and the crosslinking copolymer; in addition, a small amount of alloy crosslinking degree is formed between the layers B and C located in the intermediate layer, and the interlayer adhesion strength is further improved.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.

Claims (10)

1. A polyester alloy film, comprising:
the layer A, the layer B and the layer C are arranged in sequence; wherein
The layer A comprises 1 to 10 weight percent of anti-UV agent, 0.1 to 0.5 weight percent of anti-sticking agent and the balance of PET;
the C layer comprises 48.5-77.6 wt% of EBA, 19.4-48.5 wt% of PET and the balance of a cross-linking agent and an anti-sticking agent to form an alloy layer;
the layer B comprises 80-90wt% of PET and 10-20wt% of on-line trimming recycled materials.
2. The polyester alloy film according to claim 1,
the thermal decomposition temperature of the EBA is higher than 300 ℃, and the range of the melt index is 0.5-20 g/10min;
the mass ratio of butyl acrylate in the EBA is 10-20%.
3. The polyester alloy film according to claim 1,
the PET is polyethylene terephthalate, and the intrinsic viscosity IV is 0.68-0.76.
4. The polyester alloy film according to claim 1,
the anti-sticking agent is silicon dioxide anti-sticking agent;
the particle size of the silicon dioxide anti-sticking agent is 1-5 mu m.
5. The polyester alloy film according to claim 1,
the total thickness of the polyester alloy film is 0.050-0.350 mm;
the thickness of the layer A is 5-20% of the total thickness;
the thickness of the B layer is 60-90% of the total thickness;
the thickness of the C layer is 5-20% of the total thickness.
6. The polyester alloy film according to claim 5,
the layer B contains 10-20wt% of on-line trimming recycled materials, and the on-line trimming recycled materials comprise 5-20 wt% of C-layer alloy recycled materials.
7. The preparation method of the polyester alloy film is characterized by comprising the following steps:
preparing a C-layer premix, namely uniformly mixing the C-layer premix, extruding, granulating and drying;
uniformly mixing the raw and auxiliary materials of each layer, and drying and pre-crystallizing;
adding the materials of each layer into a corresponding extruder for extrusion;
co-extruding three layers of the die head;
casting a sheet;
longitudinal stretching;
transversely stretching;
and (5) post-treating and winding the film.
8. The process for producing a polyester alloy film according to claim 7,
the preparation of the C-layer premix comprises the steps of uniformly mixing PET, EBA and an anti-sticking agent in proportion, carrying out double-screw mixing granulation to obtain premix slices, and drying, wherein the water content of the material is controlled below 50 PPM.
9. The process for producing a polyester alloy film according to claim 8,
the three-layer co-extrusion comprises the step of adding a cross-linking agent into a compression section or a feeding section in the extrusion process of the layer C material.
10. The process for producing a polyester alloy film according to claim 9,
the crosslinking agent is ester exchange reaction catalytic crosslinking agent, preferably Ti (OBu) 4 And Sn (OBu) 4 ；
The cross-linking agent is injected by a micro pump according to the mass ratio of 0.1-1 wt% of the layer C.
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