CN115352165B - 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 PDFInfo
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- CN115352165B CN115352165B CN202210813009.9A CN202210813009A CN115352165B CN 115352165 B CN115352165 B CN 115352165B CN 202210813009 A CN202210813009 A CN 202210813009A CN 115352165 B CN115352165 B CN 115352165B
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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
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- 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 other atoms than carbon or hydrogen atoms
- C08L23/0869—Acids or derivatives thereof
-
- 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
Abstract
The invention belongs to the technical field of films, and in particular relates to a three-layer co-extrusion polyester alloy film with lasting adhesion and a preparation method thereof, comprising the following steps: the layer A, the layer B and the layer C are sequentially arranged; wherein the layer A comprises 1 to 10 weight percent of UV resistant agent, 0.1 to 0.5 weight percent of anti-adhesion agent and the balance of PET; the C layer comprises 48.5-77.6wt% of EBA, 19.4-48.5wt% of PET, and the balance of cross-linking agent and anti-adhesion agent to form an alloy layer; the layer B comprises 80-90wt% of PET and 10-20wt% of online trimming recycled material; the polyester alloy film of the invention 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 invention is utilized independently to realize the addition of the cross-linking agent in the coextrusion process, so that the alloy layer in the C layer and EVA form a durable high-adhesion bonding layer.
Description
Technical Field
The invention belongs to the technical field of 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 bonding capability of the film; however, in the case where a long-life material is produced by bonding other materials with an adhesive resin such as an acid anhydride-modified copolymer such as PE or PP and an ethylene-vinyl acetate copolymer (EVA) to a PET film, which is required to have a high adhesive strength and a high adhesion durability, the long-life adhesive strength is extremely poor even if the surface of the PET film is subjected to corona treatment due to the inertness of the surface of the PET film.
Therefore, in order to solve the above technical problems, an effective method is sought to enable the PET film to overcome the defect in this application.
Disclosure of Invention
The invention provides a modified biaxially oriented polyester alloy film with high adhesion and a preparation method thereof, which are used for solving the problem of insufficient permanent adhesion between a PET film and EVA in a long-life material.
In order to solve the technical problems, the present invention provides a polyester alloy film comprising: the layer A, the layer B and the layer C are sequentially arranged; wherein the layer A comprises 1 to 10 weight percent of UV resistant agent, 0.1 to 0.5 weight percent of anti-adhesion agent and the balance of PET; the C layer comprises 48.5-77.6wt% of EBA, 19.4-48.5wt% of PET, and the balance of cross-linking agent and anti-adhesion agent to form an alloy layer; the layer B comprises 80-90wt% of PET and 10-20wt% of online trimming material.
In still another aspect, the present invention also provides a method for preparing a polyester alloy film, comprising the steps of: preparing a layer C premix, wherein the layer C premix is prepared by uniformly mixing, extruding, granulating and drying; mixing the raw materials and the auxiliary materials of each layer uniformly, and drying and pre-crystallizing; adding all the layers of materials into corresponding extruders for extrusion; three layers of the die head are co-extruded; casting the cast sheet; stretching in the longitudinal direction; stretching in the transverse direction; and (5) film post-treatment and rolling.
The polyester alloy film has the beneficial effects that the main alloy raw materials and the functional master batch are added into the C layer positioned on the surface layer, so that the proportion of the addition is greatly reduced, the formula is utilized independently to realize the addition of the transesterification crosslinking catalyst in the coextrusion process, and the grafting and crosslinking are carried out through the transesterification reaction between the ester groups on the PET molecular main chain and the ester groups on the EBA side chains in the reaction extrusion process, so that the grafting copolymer and the crosslinking copolymer are formed; in addition, the B layer positioned in the middle layer realizes the formation of alloy crosslinking degree between the B layer and the C layer by utilizing the characteristic of online recovery of the rim charge by a biaxial stretching process, and further improves the interlayer adhesive strength.
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 practice of the invention.
In order to make the above objects, features and advantages of the present invention more 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 that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a block diagram of a polyester alloy film of the present invention;
FIG. 2 is a schematic illustration of the use of a polyester alloy film of the present invention;
in the figure:
layer A1, layer B2, layer C3, EVA4, adhesive layer 5;
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, 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 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.
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 sequentially arranged; wherein the layer A comprises 1 to 10 weight percent of UV resistant agent, 0.1 to 0.5 weight percent of anti-adhesion agent and the balance of PET; the C layer comprises 48.5-77.6wt% of EBA, 19.4-48.5wt% of PET, and the balance of cross-linking agent and anti-adhesion agent to form an alloy layer; the layer B comprises 80-90wt% of PET and 13wt% of online trimming recycled material.
Specifically, the ratio of the EBA raw material of the layer C to the sum of the mass of the EBA and the mass of the PET of the layer is 50-80%, and if the content of the EBA in the layer C is less than 50wt%, the adhesive property of the layer C 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%) and the fusion adhesion between B, C layers is easy to be unsatisfactory.
Specifically, the EBA and PET macromolecules in the layer C undergo transesterification crosslinking reaction, and ester groups on the main chain of PET molecules and ester groups on side chains of the EBA undergo transesterification reaction to undergo grafting and crosslinking in the reaction extrusion process by adding a transesterification crosslinking catalyst, so that a graft copolymer and a crosslinked copolymer are formed; the interface of C, B layer is also partially transesterified and crosslinked by the crosslinking agent contained in the C layer, so that the fusion of EBA and PET in the C layer with each other and with the C, B layer interface is enhanced.
Specifically, the A, B layers have high PET content (more than 80 percent), so that the interlayer fusion property is good; B. the layer C ensures no layering through interlayer fusion and transesterification crosslinking; as shown in fig. 2, the high-adhesion adhesive layer can be formed by fusing the polyester alloy film with an adhesive resin such as EVA, because the C layer contains a high-content EBA and the EBA and EVA belong to the same class of modified polyethylene adhesive resins.
In this example, the EBA has a thermal decomposition temperature higher than 300 ℃, i.e. a temperature resistance higher than EVA, and a melt index (2.16 kg/260 ℃) in the range of 0.5 to 20g/10min (measured according to DIN EN IOS 1133); the mass ratio of butyl acrylate in the EBA is 10-20%; the EBA processing temperature should match the melt processing temperature of PET 270-285 ℃, and the ethylene-butyl acrylate copolymer (EBA) extrusion processing temperature of the preferred embodiment of the present invention can be as high as 300 ℃, meeting the aforementioned requirements.
Alternatively, 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 methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate.
In this embodiment, specifically, the PET is polyethylene terephthalate, and the intrinsic viscosity IV is greater than 0.62, preferably 0.68 to 0.76.
In this example, optionally, for producing an opaque alloy film, a certain proportion of a coloring material may be added to each layer of A, B, C, and titanium dioxide may be added to each layer in the production of a white opaque alloy film in a proportion of 5 to 20wt%, preferably 10 to 15wt%, based on the total mass of each layer.
In this embodiment, optionally, in order to prevent adhesion between the alloy film layers, not easy to open and stable in lamination paving during use, an anti-adhesion agent is added to the surface of the film layer, so as to control a proper surface friction coefficient, inorganic particles are added to the A, C layer as an anti-adhesion agent, if the alloy film is required to be a transparent film, a silicon dioxide anti-adhesion agent is generally selected, and the particle size of the silicon dioxide anti-adhesion 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 layer B is 60-90% of the total thickness; the thickness of the layer C is 5-20% of the total thickness.
In this embodiment, specifically, the C layer contains a main alloy functional material, so that the alloy film of the present invention has the characteristics of higher adhesion with the EVA film and better interlayer fusion without delamination.
In the embodiment, specifically, to ensure the lasting adhesion of the alloy film, the alloy film itself should have aging resistance, and since the aging factor of the high polymer film is mainly degradation embrittlement caused by photo-thermal oxidation, a light stabilizer should be added into the high polymer, and according to whether the transparency of the alloy film is required, the light stabilizer is respectively added into two types, namely, if the alloy film is required to be a transparent film, a first type of ultraviolet absorber or UV inhibitor, such as alpha-hydroxybenzophenone, salicylates, benzotriazole and the like, is added; if the alloy film does not require transparency, a second type of light stabilizer "light shielding agent" may be added to the polymer, which functions to absorb light and convert it to heat or reflect light so that it cannot enter the polymer, such as carbon black, stepless or organic pigments, zinc oxide, titanium oxide, metal powder, etc., preferably titanium dioxide, while such opaque light stabilizers are also used as color changing fillers for the film material.
In this embodiment, optionally, the transparent alloy film is selected from UV-resistant agents, and the A, C layer is selected from a mixture containing one or two UV-resistant agents selected from α -hydroxybenzophenones, salicylates, and benzotriazoles. Preferably containing salicylate-based anti-UV agents; wherein the addition amount of the UV resistant agent in the layer C is 1-10% of the total mass of the layer, and is preferably 5%; as the anti-UV agent is added into the inner layer and the outer layer of the alloy film, the anti-aging capability of the alloy film is enhanced, and the lasting adhesion force between the layers of the alloy film and the adhesive resin is ensured, wherein the alloy film has 120kwh m -2 The yellowing value delta b of the surface after ultraviolet irradiation is less than or equal to 2.5.
In this embodiment, specifically, the preparation of the layer C premix includes uniformly mixing PET, EBA and an anti-UV agent in proportion, performing twin-screw mixing granulation to obtain premix slices, and performing drying treatment to control the water content of the material below 50 PPM.
In this embodiment, specifically, the three-layer co-extrusion includes mixing the raw materials and auxiliary materials required by each layer uniformly, drying, and extruding the corresponding materials by each layer of extruder, wherein the esterification crosslinking catalyst is added in the extrusion process of the layer C material for reaction extrusion, and the melt of each layer is co-extruded by a filter, a metering pump, a distributor and a flat film die head. The main process control parameters are as follows: the temperature of the extruder of the layer A is 250-285 ℃, the temperature of the extruder of the layer B is 250-285 ℃, and the temperature of the extruder of the layer C is 240-275 ℃; the temperature of the filter is 275-280 ℃; melt line A, B temperature 275-280 ℃ and melt line C temperature 270-275 ℃.
In this embodiment, the crosslinking agent is a transesterification catalyst crosslinking agent, preferably tetrabutyl titanate Ti (OBu) 4 And tetrabutyl stannate Sn (OBu) 4 The method comprises the steps of carrying out a first treatment on the surface of the The cross-linking agent is injected by a micropump, and is injected according to the mass ratio of the layer C of 0.1-1 wt%.
In this embodiment, specifically, the die temperature of the cast sheet is 270-275 ℃; the temperature of the cooling drum is 20-40 ℃.
In this embodiment, specifically, the longitudinal stretching includes preheating the sheet material and stretching at 70-95 ℃, after the longitudinal stretching, the sheet material needs to be cooled at a temperature less than or equal to 60 ℃, the cooling process needs to perform proper longitudinal relaxation, and the proper rate is controlled to decrease, so that 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 sheet after being stretched in the transverse direction is drawn into a film by four stages of preheating, stretching, heat treatment and cooling. The preheating temperature 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 relaxation rate of the thin film after transverse stretching in the heat treatment rear section and the cooling zone is 1-5%; the transverse stretch ratio typically ranges from 3.0 to 4.0.
In this embodiment, specifically, the film post-treatment and winding include alloy films after transverse stretching treatment, in order to improve the surface wet tension or surface free energy of the C layer, to enhance the adhesion with the adhesive resin, corona or flame treatment is generally required, and the wet tension of the C layer after the treatment is controlled to be equal to or greater than 52dyn/cm.
Specifically, the biaxially oriented alloy film production line is complex, the degree of automation is high, besides the main process indexes are strictly controlled, and a plurality of process parameters are required to be carefully controlled correspondingly, such as quality control of raw materials and auxiliary materials, thickness tolerance control of films, reasonable stability of the ratio of raw materials and auxiliary materials of each layer, proper and stable film winding tension and the like, which are all necessary factors for obtaining the high-quality alloy film.
Specific examples and comparative examples:
examples 1, 2, 3 test layer a UV agent ratios;
examples 4, 5, 6 test C layer EBA ratios;
examples 1, 7, 8 test the C layer transesterification crosslinking catalyst ratio;
example 9 test layer C extreme high EBA ratio;
comparative example, single or three layer co-extruded pure PET film, facilitates comparison of examples with comparative examples on various performance test parameters.
Peel strength test with EVA: according to the specification of GB/T2790-1995, samples of examples and comparative examples were cut into pieces of Cheng Kuandu (10.+ -. 0.5) mm and lengths of 250-300 mm, 5 pieces of the pieces were each pressed onto ground glass using EVA for encapsulation, and after lamination at 148 ℃ for 10 minutes, 180 DEG peel force between the pieces and EVA was measured by a tensile tester, and the peel speed was 100mm/min.
UV resistance (UV treatment and test): 3 samples of 100mmx100mm were prepared as specified in IEC61215.2005 at a temperature of (60.+ -. 5) ℃ and applied with UV A wavelength: 320 nm-400 nm, and the irradiation is 120kwh.m -2 And (3) operating, namely testing the yellow index b of the sample, calculating delta b, and taking a median value as a result.
Mechanical property test (tensile strength, elongation at break): according to the specification of GB/T13542.2-2009, a sample is 200mm long and (15+/-1) mm wide, 5 samples are taken transversely and longitudinally, two mark lines which are at least 50mm apart are marked in the sample, and a load is applied at a speed of 100mm/min until the single component of the sample breaks as an end point. The median of the 5 test values was taken as the result.
Heat shrinkage test: according to the specification of GB/T13542.2-2009, placing the sample in a constant temperature oven in a hanging manner, wherein the heating temperature is (150+/-2) DEG C, the heating time is 30min, and the longitudinal and transverse heat shrinkage rates of the sample are averaged.
Water vapor transmission rate test: 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 specified in GB/T21529-2008: the temperature (38.+ -. 2) DEG C and the relative humidity (90.+ -. 2)%, and the sample was measured to obtain the median.
Boiling water treatment: according to solar cell backboard standard GB/31034-2014, a sample (100 mmx300 mm) prepared by laminating a film sample and EVA (according to the method for preparing the sample with EVA peel strength) is placed in a constant-temperature boiling water bath at the temperature of (98+/-2) ℃ for 24 (48) hours, and the test peel strength is taken out for median comparison.
Coefficient of friction: 5 pairs of samples were cut in the machine direction of the film according to ASTM D1894 or GB10006 test methods, 200mmx85mm in size, and the dynamic and static coefficients of friction were measured using a film surface roughness tester.
Example 1
The alloy film of this example, layer a, comprises: 94.7wt% of PET resin, 0.3wt% of silicon dioxide anti-adhesion agent and 5wt% of UV resistant agent; the layer B comprises: 87wt% of PET resin and 13wt% of online trimming recycle material; the layer C comprises 40.2wt% of PET resin, 58.5wt% of EBA, 0.3wt% of silicon dioxide anti-sticking agent and 1wt% of crosslinking agent; the alloy film is of an ABC three-layer co-extrusion structure, and the total thickness of the alloy film is 300um.
Example 2
The alloy film of this example, layer a, comprises: 91.7wt% of PET resin, 0.3wt% of silicon dioxide anti-adhesion agent and 8wt% of UV resistant agent; the layer B comprises: 87wt% of PET resin and 13wt% of online trimming recycle material; the C layer comprises 40.2wt% of PET, 58.5wt% of EBA, 1wt% of cross-linking agent and 0.3wt% of silicon dioxide anti-sticking agent. The alloy film is of an ABC three-layer co-extrusion structure, and the total thickness of the alloy film is 300um.
Example 3
The alloy film of this example, layer a, comprises: 99.7wt% of PET resin and 0.3wt% of silicon dioxide anti-adhesion agent; the layer B comprises: 87wt% of PET resin and 13wt% of online trimming recycle material; the C layer comprises 40.2wt% of PET, 58.5wt% of EBA, 1wt% of cross-linking agent and 0.3wt% of silica anti-sticking agent. The alloy film is of an ABC three-layer co-extrusion structure, and the total thickness of the alloy film is 300um.
Example 4
The alloy film of this example, layer a, comprises: 94.7wt% of PET resin, 5wt% of UV resistant agent and 0.3wt% of silicon dioxide anti-sticking agent; the layer B comprises: 87wt% of PET resin and 13wt% of online trimming recycle material; the layer C comprises 25.2wt% of PET resin, 73.5wt% of EBA, 1wt% of cross-linking agent and 0.3wt% of silicon dioxide anti-adhesion agent. The alloy film is of an ABC three-layer co-extrusion structure, and the total thickness of the alloy film is 300um.
Example 5
The alloy film of this example, layer a, comprises: 94.7wt% of PET resin, 5wt% of UV resistant agent and 0.3wt% of silicon dioxide anti-sticking agent; the layer B comprises: 87wt% of PET resin and 13wt% of online trimming recycle material; the layer C comprises 50.2wt% of PET resin, 48.5wt% of EBA, 1wt% of cross-linking agent and 0.3wt% of silicon dioxide anti-adhesion agent. The alloy film is of an ABC three-layer co-extrusion structure, and the total thickness of the alloy film is 300um.
Example 6
The alloy film of this example, layer a, comprises: 94.7wt% of PET resin, 5wt% of UV resistant agent and 0.3wt% of silicon dioxide anti-sticking agent; the layer B comprises: 87wt% of PET resin and 13wt% of online trimming recycle material; the layer C comprises 85.2wt% of PET resin, 13.5wt% of EBA, 1wt% of cross-linking agent and 0.3wt% of silicon dioxide anti-adhesion agent. The alloy film is of an ABC three-layer co-extrusion structure, and the total thickness of the alloy film is 300um.
Example 7
The alloy film of this example, layer a, comprises: 94.7wt% of PET resin, 0.3wt% of silicon dioxide anti-adhesion agent and 5wt% of UV resistant agent; the layer B comprises: 87wt% of PET resin and 13wt% of online trimming recycle material; the C layer comprises 40.2wt% of PET, 59wt% of EBA, 0.5wt% of cross-linking agent and 0.3wt% of silicon dioxide anti-sticking agent. The alloy film is of an ABC three-layer co-extrusion structure, and the total thickness of the alloy film is 300um.
Example 8
The alloy film of this example, layer a, comprises: 94.7wt% of PET resin, 0.3wt% of silicon dioxide anti-adhesion agent and 5wt% of UV resistant agent; the layer B comprises: 87wt% of PET resin and 13wt% of online trimming recycle material; the C layer comprises 50.7wt% PET resin, 49wt% EBA, and 0.3wt% silica anti-sticking agent. The alloy film is of an ABC three-layer co-extrusion structure, and the total thickness of the alloy film is 300um.
Example 9
The alloy film of this example, layer a, comprises: 94.7wt% of PET resin, 0.3wt% of silicon dioxide anti-adhesion agent and 5wt% of UV resistant agent; the layer B comprises: 87wt% of PET resin and 13wt% of online trimming recycle material; the layer C comprises 16.7wt% of PET resin, 82wt% of EBA, 1wt% of cross-linking agent and 0.3wt% of silicon dioxide anti-adhesion agent. The alloy film is of an ABC three-layer co-extrusion structure, and the total thickness of the alloy film is 300um.
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 the following components: 100wt% of PET resin. The thickness was 300um.
Table 1 comparison of the performance parameters of examples 1-9 and comparative examples
Examples and comparative examples comparison shows:
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 layer C is low, and the peeling strength of the layer C and EVA after boiling water treatment is less than or equal to 80N/10mm, so that the high peeling strength requirement can not be met;
example 6: the EBA proportion in the layer C is low, and the peeling strength of the layer C and EVA after boiling water treatment is less than 60N/10mm and does not meet the requirements;
example 8: the layer C has no cross-linking agent, and the peel strength of the layer C and EVA after boiling water treatment is less than or equal to 80N/10mm, which does not meet the requirements;
example 9: the EBA proportion in the layer C is too high, the PET content of the corresponding layer C is too low, and the layer C and the layer B are easy to delaminate and are unqualified after boiling water treatment;
the comparative example is a pure PET film;
the peel strength of the layer and EVA in Table 1"C and the peel strength of the layer C and EVA after boiling water treatment are shown in the following two columns: the bonding strength of the C layer and the EVA adhesive resin is greatly influenced by the EBA content in the C layer and the content of the cross-linking agent, and the mass ratio of the EBA in the alloy film C layer is preferably 48.5-77.6% in consideration of the peel strength loss after aging and the PET fusion requirement between B, C layers; the adding mass fraction of the cross-linking agent is 0.5-1%.
Durability against ultraviolet aging: to ensure 120kwh.m -2 The yellowing value delta b after ultraviolet treatment is less than 2.5, and the added mass fraction of the layer A UV resistant agent is more than or equal to 1wt%;
the invention concentrates on the C layer in the adhesion modification of the alloy film, and the thickness of the C layer accounts for only 10-20% of the total thickness, so that the influence on the whole tensile strength, elongation at break and thermal shrinkage of the alloy film is small, and the characteristics of good PET mechanical property and low thermal shrinkage are basically maintained.
Analysis of the effect of water vapor transmission in the samples of Table 1 shows that the equivalent ratio of EBA to PET in the C layer and the high crosslinker content improve the degree of crosslinking, contributing to improved water vapor transmission.
From the above analysis, 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 durable high adhesion on one side, and if a double-sided durable high adhesion alloy film is required to be prepared, the layer a can be produced with the formula and process of the layer C; the prepared alloy film is a unidirectional light anti-ultraviolet aging alloy film, and if the alloy film needs to be subjected to bidirectional light anti-ultraviolet aging, the anti-ultraviolet alloy film with bidirectional light can be prepared by adding more than 5% of anti-ultraviolet agent into the layer C; if the opaque alloy film is required to be produced, pigment color master batches with different proportions can be added into the raw materials of each layer of the alloy film according to the light transmittance requirement, and inorganic pigment fillers with light stabilization (such as titanium dioxide, barium sulfate, calcium carbonate, carbon black and the like) can be matched with the UV-resistant agent for use, so that the weather-resistant and ageing-resistant performances are better, and the UV-resistant agent can be reduced or not.
In summary, the polyester alloy film of the invention greatly reduces the proportion of the added amount by adding the main alloy raw material and the functional master batch into the C layer positioned on the surface layer, and the formula of the invention is utilized to realize the addition of the transesterification crosslinking catalyst in the coextrusion process, and the graft copolymer and the crosslinking copolymer are formed by the transesterification reaction between the ester groups on the PET molecular main chain and the ester groups on the EBA side chains in the reaction extrusion process; in addition, a small amount of alloy crosslinking degree is formed between the B layer and the C layer of the intermediate layer, so that the interlayer adhesive strength is further improved.
With the above-described preferred embodiments according to the present invention as an illustration, the above-described descriptions can be used by persons skilled in the relevant art to make various changes and modifications without departing from the scope of the technical idea of the present invention. The technical scope of the present invention is not limited to the description, but must be determined according to the scope of claims.
Claims (8)
1. A polyester alloy film comprising:
the layer A, the layer B and the layer C are sequentially arranged; wherein the method comprises the steps of
The layer A comprises 1 to 10 weight percent of UV resistant agent, 0.1 to 0.5 weight percent of anti-adhesion agent and the balance of PET;
the C layer comprises 48.5-77.6wt% of EBA, 19.4-48.5wt% of PET, and the balance of cross-linking agent and anti-adhesion agent to form an alloy layer;
the layer B comprises 80-90wt% of PET and 10-20wt% of online trimming recycled material;
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 layer B is 60-90% of the total thickness;
the thickness of the layer C is 5-20% of the total thickness;
the cross-linking agent is Ti (OBu) 4 And Sn (OBu) 4 ；
The cross-linking agent is injected by a micropump, and is injected according to the mass ratio of the layer C of 0.1-1 wt%.
2. The polyester alloy film according to claim 1,
the thermal decomposition temperature of the EBA is higher than 300 ℃, and the melt index is 2.16kg/260 ℃ and is in the range of 0.5-20 g/10min;
the mass ratio of the 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-adhesion agent is a silicon dioxide anti-adhesion 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 layer B contains 10-20wt% of online trimming recycled material, and the online trimming recycled material comprises 5-20wt% of C-layer alloy recycled material.
6. A method of making the polyester alloy film of any of claims 1 to 5, comprising the steps of:
preparing a layer C premix, wherein the layer C premix is prepared by uniformly mixing, extruding, granulating and drying;
mixing the raw materials and the auxiliary materials of each layer uniformly, and drying and pre-crystallizing;
adding all the layers of materials into corresponding extruders for extrusion;
three layers of the die head are co-extruded;
casting the cast sheet;
stretching in the longitudinal direction;
stretching in the transverse direction;
and (5) film post-treatment and rolling.
7. The method for producing a polyester alloy film according to claim 6, wherein,
the preparation of the layer C premix comprises the steps of uniformly mixing PET, EBA and an anti-sticking agent according to a proportion, carrying out twin-screw mixing granulation to obtain premix slices, and drying to control the water content of the materials below 50 PPM.
8. The method for producing a polyester alloy film according to claim 7, wherein,
the three-layer coextrusion comprises adding a cross-linking agent into a compression section or a feeding section in the extrusion process of the C layer material.
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