CN117659894A - Composite release film, preparation method and application thereof - Google Patents
Composite release film, preparation method and application thereof Download PDFInfo
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- CN117659894A CN117659894A CN202311370331.XA CN202311370331A CN117659894A CN 117659894 A CN117659894 A CN 117659894A CN 202311370331 A CN202311370331 A CN 202311370331A CN 117659894 A CN117659894 A CN 117659894A
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- 230000001070 adhesive effect Effects 0.000 claims description 40
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
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- 229910000831 Steel Inorganic materials 0.000 description 2
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 description 2
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention provides a composite release film, a preparation method and application thereof. The composite release film comprises a release layer adhesive layer and a substrate layer which are sequentially laminated, wherein the release layer is a PVDF layer, the adhesive layer is an epoxy acrylate layer, and the substrate layer is a PET layer. The composite release film has the advantages that the release layer and the substrate layer can be well bonded due to the existence of the adhesive layer, the tensile strength of the obtained composite release film is 130-135 MPa, the elongation at break is 75-87%, the thermal shrinkage at 160 ℃ is less than 1%, the thickness of the release layer is 1-4 mu m, the water contact angle is 76-79 degrees, and the peeling force between the release layer and the proton exchange film is 9-13 gf. After the resin is applied to a proton exchange membrane tape casting film coating process, the perfluorinated sulfonic acid resin solution on the resin can well form a film, can be peeled off easily, and can not cause the transfer of a release agent.
Description
Technical Field
The invention relates to the field of fuel cells, in particular to a composite release film, a preparation method and application thereof.
Background
Release films, also known as release films, separation films, and the like. The common release film product is to coat silicone oil, fluorine or non-silicon release agent on the surface of a plastic film such as PET, PI, PP, so that the release film has extremely light and stable release force. The release film has the advantages of non-adhesiveness, isolation, protection and the like, so that the release film is widely applied to the fields of packaging, printing, silk screen printing, electronics and the like.
The proton exchange membrane is used as a core component of a proton exchange membrane fuel cell, plays roles of conducting protons, serving as an electrode reaction medium and a catalyst carrier and isolating cathode and anode reactants, and the preparation process is a hot spot of research in the current industry field. The preparation process of the proton exchange membrane is divided into a casting coating process and a melt extrusion process, wherein the casting coating process is generally selected due to low equipment requirements. In the casting coating process, core parameters such as contact angle of the release film and the perfluorinated sulfonic acid resin solution, temperature resistance of the release film, stripping force, transfer amount of the release agent and the like have important influence on the performance of the obtained proton exchange film. The silicone oil type or fluorine type release film commonly used in the market can cause the perfluorinated sulfonic acid resin solution to be incapable of forming a film or transferring silicon, and the peeling force of the non-silicon release film commonly used in China is larger.
In this case, polyvinylidene fluoride (hereinafter referred to as PVDF) has advantages of temperature resistance, self-lubricity, chemical stability, and the like as a good release agent material, and can be used as a release coating layer on a high temperature resistant PET film in order to reduce its release force. However, the surface energy of the PVDF and the PET is low, and when the PVDF is used as a coating, the adhesion force between the PVDF and the PET film is not strong, and a composite film with strong consistency and stability cannot be formed.
CN114292554a (upper seawater cubic new material limited company) discloses a modified nano silica reinforced water-based PVDF coating and a preparation method, wherein the water-based PVDF/fluorine-containing acrylic composite emulsion reacts with fluorine-containing polysiloxane components, and nano silica with surface modification is added, so that compatibility among the components is improved, when film forming property is ensured, adhesion between a coating and metals is increased, moisture and heat resistance is excellent, the coating has excellent hydrophobic property, hydrolysis resistance and acid and alkali resistance are excellent, the coating can be effectively adhered to the surfaces of various metal substrates, film forming is stable, and the coating has excellent practicability. However, the incorporation of the epoxy acrylic component in this patent does not provide good peel force, while the silicone and silica components can lead to silicon transfer.
Based on this, there is a need in the art to provide a novel release film for proton exchange membranes, which solves the problems of poor temperature resistance, large stripping force and release agent transfer existing in the existing release films for proton exchange membranes.
Disclosure of Invention
The invention mainly aims to provide a composite release film, a preparation method and application thereof, and aims to solve the problems of poor temperature resistance, large stripping force and release agent transfer existing in the release film for the existing proton exchange film.
In order to achieve the above purpose, the invention provides a composite release film, which comprises a release layer, an adhesive layer and a substrate layer which are sequentially laminated, wherein the release layer is a PVDF layer, the adhesive layer is an epoxy acrylate layer, and the substrate layer is a PET layer.
Further, the thickness of the release layer is 1-4 μm, the thickness of the adhesive layer is 1-5 μm, and the thickness of the base material layer is 75-175 μm.
The invention also provides a preparation method of the composite release film, which comprises the following steps:
step S1, providing a substrate layer with a first surface and a second surface which are opposite;
step S2, providing epoxy acrylate paint as adhesive slurry, and preparing PVDF resin into release slurry;
step S3, coating the adhesive slurry on the first surface of the substrate layer, and drying to form an adhesive layer on the first surface;
and S4, coating release slurry on the surface of the adhesive layer far away from the substrate layer, and drying to form a release layer, thereby obtaining the composite release film.
Further, in the step S2, the epoxy acrylate paint is selected from one or more of polyurethane modified epoxy acrylate, bisphenol A epoxy acrylate and anhydride modified epoxy acrylate.
Further, the thickness of the wet film coated with the binder slurry in step S3 is 10 to 50 μm.
Further, in the drying process for forming the adhesive layer in the step S3, the temperature is 80-150 ℃ and the time is 1-3 min.
Further, the preparation method of the release slurry in the step S2 comprises the following steps:
s2-1, dispersing PVDF resin into a solvent to obtain a mixed solution;
step S2-2, heating the mixed solution to 40-80 ℃, and stirring for 1-4 hours to obtain release slurry;
preferably, the solvent is a mixed solvent of N, N-dimethylformamide and ethyl acetate, and the mass ratio of the N, N-dimethylformamide to the ethyl acetate is (1-4): 1, a step of; preferably, the solid content of PVDF resin in the mixed solution is 4-10%.
Further, the thickness of the coating wet film of the release slurry in the step S4 is 30-100 mu m, the temperature in the drying process is 120-160 ℃, and the time is 3-5 min.
Further, prior to applying the binder slurry, corona treatment of the first surface of the substrate layer is also included.
The invention also provides an application of the composite release film in a proton exchange film casting film coating process.
The composite release film prepared by the invention can be well bonded with a substrate layer due to the existence of the adhesive layer, the tensile strength of the composite release film is 130-135 MPa, the elongation at break is 75-87%, the thermal shrinkage is less than 1% at 160 ℃, the thickness of the release layer is 1-4 mu m, the water contact angle is 76-79 DEG, the peeling force between the release layer and the proton exchange film is 9-13 gf, and meanwhile, the release layer cannot be transferred. After the resin is applied to a proton exchange membrane tape casting film coating process, the perfluorinated sulfonic acid resin solution on the resin can well form a film, can be peeled off easily, and can not cause the transfer of a release agent.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. In the drawings:
FIG. 1 is a schematic structural diagram of a composite release film according to the present application;
wherein, each reference numeral represents the following:
10. a release layer; 20. an adhesive layer; 30. a substrate layer.
Detailed Description
It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be combined with each other. The present invention will be described in detail with reference to examples.
As described in the background art, the existing release film for the proton exchange membrane has the problems of poor temperature resistance, large high-temperature stripping force and release agent transfer. In order to solve the above technical problem, the present application provides a composite release film, as shown in fig. 1, which includes a release layer 10, an adhesive layer 20 and a substrate layer 30 that are sequentially stacked, wherein the release layer 10 is a PVDF layer, the adhesive layer 20 is an epoxy acrylate layer, and the substrate layer 30 is a PET layer.
The invention utilizes the PVDF layer to obtain excellent release effect, uses high-temperature resistant PET as a substrate layer to enable the release film to have good temperature resistance and tensile strength, uses the epoxy acrylate layer as an adhesive layer, and enhances the adhesive force between the PET substrate layer and the release layer. The adhesive layer is an epoxy acrylate layer, and compared with other adhesives with the same adhesive effect, the epoxy acrylate adhesive has better adhesive performance, and particularly has excellent adhesive capability for materials with PVDF (polyvinylidene fluoride) hydrophobic surfaces; meanwhile, the composite release film also has high weather resistance, water resistance and chemical resistance, so that the integral stability of the composite release film can be kept in the application process. The inventor has found through a great deal of repeated experiments that compared with other binders such as organosilicon, polyurethane, acrylic acid and polyacrylic acid base coat (obtained by dissolving resin particles) and the like, wherein the organosilicon base coat cannot be adhered to a PVDF layer, the polyurethane, the acrylic acid and the polyacrylic acid can be swelled by a solvent of PVDF, and the epoxy acrylate disclosed by the invention can exert better adhesive property; meanwhile, the composite release film prepared by the method and taking the epoxy acrylate layer as the adhesive layer has better structural stability in the preparation process of the proton exchange film. The obtained composite release film has good mechanical strength, temperature resistance and excellent release effect, and the release layer can not be transferred.
In order to ensure that the surface of the composite release film, which is contacted with the proton exchange film, has good release performance, and simultaneously, the release layer 10 has better coordination compatibility with other layer components in the composite release film, and the thickness of the layer is controlled to be 1-4 mu m; the thickness of the adhesive layer 20 is controlled to be 1-5 μm to obtain a better adhesive effect and to allow the resulting composite film to have better continuity in structure; in order to make the substrate layer better support in the composite release film and provide better physical and mechanical properties, so that the subsequently obtained composite release film has better mechanical properties and temperature resistance, the thickness of the substrate layer 30 is defined to be 75-175 μm.
The invention also provides a preparation method of the composite release film, which comprises the following steps:
step S1, providing a substrate layer 30 with a first surface and a second surface opposite to each other;
step S2, providing epoxy acrylate paint as adhesive slurry, and preparing PVDF resin into release slurry;
step S3, coating the adhesive slurry on the first surface of the substrate layer 30, and drying to form an adhesive layer 20 on the first surface;
in step S4, the release slurry is coated on the surface of the adhesive layer 20 away from the substrate layer 30, and dried to form the release layer 10, thereby obtaining the composite release film.
The preparation method of the composite release film provided by the invention can simply obtain the composite release film which is easy to peel, good in temperature resistance and mechanical property and free from release agent transfer through conventional equipment. Specifically, in the step S1, a high-temperature-resistant PET film is used as a base material, so that the obtained composite release film has good temperature resistance and tensile strength; in the step S2, epoxy acrylate paint is used as adhesive slurry so that an adhesive layer with good cohesiveness, good compatibility and weather resistance is formed after the adhesive slurry is dried, and PVDF resin is used as coating slurry of a release layer so as to obtain excellent release effect; in the preparation process provided by the application, the two materials are firstly prepared into slurry, and then the slurry is sequentially coated and dried, so that compared with the processes of coextrusion and the like, the compatibility among components of each layer can be effectively improved, the heat resistance of the material is not damaged, and meanwhile, the multilayer structure with special functions can be realized under the conditions of simple operation and simple equipment; and after the composite release film is obtained, testing the roughness of the release film by a white light interferometer, so as to ensure the flatness of the release film.
In order to improve the adhesion between the substrate layer 30 and the release layer 10 to achieve a composite release film with more stable structure and more excellent performance, the epoxy acrylate paint used in the present invention is one or more selected from polyurethane modified epoxy acrylate, bisphenol a epoxy acrylate and anhydride modified epoxy acrylate, and compared with other adhesive materials such as silicone elastomer, styrene-butadiene-styrene copolymer, etc., the epoxy acrylate paint used in the present invention is usually a low viscosity liquid, and is more convenient to use in the experimental process, reduces the difficulty of the process used in the experimental process, can also achieve rapid drying at a lower temperature, does not need a pressurizing step, has strong medium, drug and atmospheric aging resistance, and more important, has good adhesion, and has more excellent adhesive strength to the polymer film. And the epoxy resin is modified, so that the adhesive force, the water resistance and the flexibility of the acrylate adhesive are further improved, the defect that the acrylate adhesive is easy to be sticky at a low temperature Shi Yi is overcome, and the mechanical property and the weather resistance of the obtained composite release film are finally improved, so that the composite release film can be applied to various experimental environments.
On the basis of the above, the thickness of the wet film coated with the adhesive slurry is controlled to be 10-50 μm so that it can exert the adhesive effect better while maintaining the integrity and consistency of the resulting composite film structure to a greater extent.
In a preferred embodiment, the temperature of the adhesive layer 20 during the drying process is 80-150 ℃ for 1-3 min, and the drying temperature and time are controlled within this range so as to control the solvent evaporation rate, thereby reducing the adhesive loss or embrittlement phenomenon and effectively shortening the production cycle.
The preparation of the release slurry comprises the steps of dispersing PVDF resin into a solvent to obtain a mixed solution, heating the mixed solution to 40-80 ℃, and stirring for 1-4 h to obtain uniform release slurry. In a typical embodiment, the solvent used for dispersion is a mixed solvent of N, N-Dimethylformamide (DMF) and Ethyl Acetate (EA), and the mass ratio of N, N-dimethylformamide to ethyl acetate is (1-4): 1, selecting the two solvents and controlling the mass ratio of the two solvents to be (1-4): in the range of 1, a solvent having a polarity more similar to that of the PVDF resin is obtained, which contributes to obtaining a better dissolution effect, so that a wet film having a uniform composition is obtained after coating and can be completely volatilized upon drying. The solid content of PVDF resin in the mixed solution is preferably 4-10%, and the solid content of PVDF resin is controlled within the range, so that the PVDF resin can better show release performance, and meanwhile, the leveling property of the PVDF resin in the coating process is improved, and the apparent performance of the PVDF resin is improved.
The thickness of the coating wet film is controlled to be 30-100 mu m in the coating process of the release slurry so as to obtain a release layer with better release performance and mechanical comprehensive performance; the drying temperature and the drying time are controlled to be 120-160 ℃ and 3-5min respectively so as to improve the apparent quality of the composite release film and effectively shorten the production period.
In a typical embodiment, prior to applying the adhesive slurry, corona treatment is also included on the first surface of the substrate layer 30 to increase the roughness of the PET film surface to enhance its compounding with the adhesive layer 20, allowing better adhesion of the layers.
The invention also provides an application of the composite release film in a proton exchange film casting film coating process. In the tape-casting film coating process based on the composite release film, the perfluorinated sulfonic acid resin solution can be well formed into a film and can be peeled off easily, and meanwhile, the transfer of the release agent can not happen, so that the large-scale mass production can be carried out under the condition of ensuring the performance of the proton exchange film.
The present application is described in further detail below in conjunction with specific embodiments, which should not be construed as limiting the scope of the claims.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Example 1
Preparation of a composite release film:
s1, single-sided corona treatment of a PET film: high temperature resistant PET film with thickness of 100 μm, single-sided corona treatment.
S2, preparing a release agent: DMF and EA were proportioned to 2.33:1 preparing a mixed solvent, adding PVDF into a mixed solvent of DMF and EA with a solid content of 10%, heating to 60 ℃ in an oil bath, and stirring for 2h.
S3, preparing an adhesive layer: the polyurethane modified epoxy acrylate adhesive is coated on the corona surface of the PET film, the thickness of the wet film is 30 mu m, the wet film is heated for 1-2min at the temperature of 100 ℃ to prepare an adhesive layer, and the thickness of the dried adhesive layer is 2 mu m.
S4, preparing a release layer: PVDF solution with the solid content of 10% is coated on the bottom coating surface of the PET film, the wet film thickness is 40 mu m, and the PVDF release film layer is prepared by heating for 3-5min at the temperature of 150 ℃, and the structure schematic diagram is shown in figure 1.
Example 2
Preparation of a composite release film:
s1, single-sided corona treatment of a PET film: high temperature resistant PET film with thickness of 100 μm, single-sided corona treatment.
S2, preparing a release agent: DMF and EA were proportioned to 2.33:1 preparing a mixed solvent, adding PVDF into a mixed solvent of DMF and EA with a solid content of 6%, heating to 60 ℃ in an oil bath, and stirring for 2h.
S3, preparing an adhesive layer: the polyurethane modified epoxy acrylate adhesive is coated on the corona surface of the PET film, the thickness of the wet film is 10 mu m, the wet film is heated for 1-2min at the temperature of 100 ℃ to prepare an adhesive layer, and the thickness of the dried adhesive layer is 1 mu m.
S4, preparing a release layer: and (3) coating PVDF solution with the solid content of 6% on the bottom coating surface of the PET film, heating the film at 150 ℃ for 3-5min, wherein the wet film thickness is 30 mu m, and preparing the PVDF release film layer.
Example 3
Preparation of a composite release film:
s1, single-sided corona treatment of a PET film: high temperature resistant PET film with thickness of 100 μm, single-sided corona treatment.
S2, preparing a release agent: DMF and EA were proportioned to 2.33:1 preparing a mixed solvent, adding PVDF into a mixed solvent of DMF and EA with a solid content of 4%, heating to 60 ℃ in an oil bath, and stirring for 2h.
S3, preparing an adhesive layer: the polyurethane modified epoxy acrylate adhesive is coated on the corona surface of the PET film, the thickness of the wet film is 10 mu m, the wet film is heated for 1-2min at the temperature of 100 ℃ to prepare an adhesive layer, and the thickness of the dried adhesive layer is 1 mu m.
S4, preparing a release layer: and (3) coating PVDF solution with the solid content of 4% on the bottom coating surface of the PET film, heating the film with the wet film thickness of 40 mu m at the temperature of 150 ℃ for 3-5min, and preparing the PVDF release film layer.
Example 4
Preparation of a composite release film:
s1, single-sided corona treatment of a PET film: high temperature resistant PET film with thickness of 100 μm, single-sided corona treatment.
S2, preparing a release agent: DMF and EA were proportioned to 2.33:1 preparing a mixed solvent, adding PVDF into a mixed solvent of DMF and EA with a solid content of 10%, heating to 60 ℃ in an oil bath, and stirring for 2h.
S3, preparing an adhesive layer: the polyurethane modified epoxy acrylate adhesive is coated on the corona surface of the PET film, the thickness of the wet film is 60 mu m, and the wet film is heated for 1-2min at the temperature of 100 ℃ to prepare an adhesive layer, and the thickness of the dried adhesive layer is 6 mu m.
S4, preparing a release layer: and (3) coating PVDF solution with the solid content of 10% on the bottom coating surface of the PET film, heating the film with the wet film thickness of 40 mu m at the temperature of 150 ℃ for 3-5min, and preparing the PVDF release film layer.
Namely, the difference from example 1 is: the adhesive layer had a thickness of 6. Mu.m.
Example 5
Preparation of a composite release film:
s1, single-sided corona treatment of a PET film: high temperature resistant PET film with thickness of 100 μm, single-sided corona treatment.
S2, preparing a release agent: DMF and EA were proportioned to 2.33:1 preparing a mixed solvent, adding PVDF into a mixed solvent of DMF and EA with a solid content of 10%, heating to 60 ℃ in an oil bath, and stirring for 2h.
S3, preparing an adhesive layer: the polyurethane modified epoxy acrylate adhesive is coated on the corona surface of the PET film, the thickness of the wet film is 5 mu m, the wet film is heated for 1-2min at the temperature of 100 ℃ to prepare an adhesive layer, and the thickness of the dried adhesive layer is 0.5 mu m.
S4, preparing a release layer: and (3) coating PVDF solution with the solid content of 10% on the bottom coating surface of the PET film, heating the film with the wet film thickness of 40 mu m at the temperature of 150 ℃ for 3-5min, and preparing the PVDF release film layer.
Namely, the difference from example 1 is: the adhesive layer thickness was 0.5 μm.
Example 6
Preparation of a composite release film:
s1, single-sided corona treatment of a PET film: high temperature resistant PET film with thickness of 100 μm, single-sided corona treatment.
S2, preparing a release agent: DMF and EA were proportioned to 2.33:1 preparing a mixed solvent, adding PVDF into a mixed solvent of DMF and EA with a solid content of 10%, heating to 60 ℃ in an oil bath, and stirring for 2h.
S3, preparing an adhesive layer: the polyurethane modified epoxy acrylate adhesive is coated on the corona surface of the PET film, the thickness of the wet film is 30 mu m, the wet film is heated for 1-2min at 170 ℃ to prepare an adhesive layer, and the thickness of the dried adhesive layer is 2 mu m.
S4, preparing a release layer: and (3) coating PVDF solution with the solid content of 10% on the bottom coating surface of the PET film, heating the film with the wet film thickness of 40 mu m at the temperature of 150 ℃ for 3-5min, and preparing the PVDF release film layer.
Namely, the difference from example 1 is: the drying temperature of the binder was 170 ℃.
Example 7
Preparation of a composite release film:
s1, single-sided corona treatment of a PET film: high temperature resistant PET film with thickness of 100 μm, single-sided corona treatment.
S2, preparing a release agent: DMF and EA were proportioned to 2.33:1 preparing a mixed solvent, adding PVDF into a mixed solvent of DMF and EA with a solid content of 10%, heating to 60 ℃ in an oil bath, and stirring for 2h.
S3, preparing an adhesive layer: the polyurethane modified epoxy acrylate adhesive is coated on the corona surface of the PET film, the thickness of the wet film is 30 mu m, the wet film is heated for 1-2min at the temperature of 60 ℃ to prepare an adhesive layer, and the thickness of the dried adhesive layer is 2 mu m.
S4, preparing a release layer: and (3) coating PVDF solution with the solid content of 10% on the bottom coating surface of the PET film, heating the film with the wet film thickness of 40 mu m at the temperature of 150 ℃ for 3-5min, and preparing the PVDF release film layer.
Namely, the difference from example 1 is: the drying temperature of the binder was 60 ℃.
Example 8
Preparation of a composite release film:
the differences from example 1 are: the solid content of the PVDF resin in the mixed solution was 2%.
Example 9
Preparation of a composite release film:
the differences from example 1 are: the solid content of the PVDF resin in the mixed solution was 12%.
Example 10
Preparation of a composite release film:
the differences from example 1 are: bisphenol A epoxy acrylate is adopted as the adhesive.
Example 11
Preparation of a composite release film:
the differences from example 1 are: the adhesive adopts anhydride modified epoxy acrylate.
Comparative example 1
Preparation of a composite release film:
the differences from example 1 are: no adhesive layer is provided.
Comparative example 2
Preparation of a composite release film:
the differences from example 1 are: the adhesive is a silicone elastomer such as polydimethylsiloxane.
Comparative example 3
Preparation of a composite release film:
the differences from example 1 are: the adhesive is an olefin copolymer of styrene-butadiene-styrene.
Comparative example 4
Preparation of a composite release film:
the differences from example 1 are: the adhesive adopts an ethylene-vinyl acetate (EVA) hot melt adhesive.
Comparative example 5
Preparation of a composite release film:
the differences from example 1 are: the adhesive slurry and the release agent slurry are mixed and then coated on the substrate layer.
The test methods for each performance with respect to the above examples and comparative examples in the present invention are as follows, in which:
mechanical properties: preparing dumbbell test bars meeting the film tensile test standard by using a punching machine, measuring the thickness of each sample by using a thickness gauge, placing the samples into two clamps of a testing machine, setting the tensile speed (50 mm/min) of a universal tensile testing machine, starting the testing machine for testing, and reading the required performance related parameters after the samples are broken.
Release layer adhesion: reference to "GB/T33049-2016 method for measuring adhesion of polarizer optical film coating", specifically: the sample of 150mm x 100mm was cut, the sample surface was cut vertically with a hundred-blade knife with uniform pressure, the test sample was rotated by 90 °, and the sample surface was cut again to form a lattice pattern. The test tape was applied to the grid in a direction parallel to a set of dicing lines, and the tape was torn off within 5 minutes of the application of the tape, and the cut edge or the cut intersection of the coating surface was observed with a magnifying glass for peeling off, and the ratio of the peeled off area was calculated.
Temperature resistance: a 100mm x 100mm release film sample was taken, its dimensions before heating in the Machine Direction (MD) and Transverse Direction (TD) were tested, then placed in an oven at 160 ℃ for 15min, taken out and cooled, and its heated dimensions were tested. MD heat shrinkage= (MD pre-heating dimension-MD post-heating dimension) ×100%/MD pre-heating dimension; TD heat shrinkage= (TD pre-heating dimension-MD post-heating dimension) ×100%/TD pre-heating dimension. Three times, the average value was taken.
Room temperature peel force: double-sided adhesive tape was adhered along the long side parallel direction of the stainless steel plate, the release film side of the sample strip was adhered thereto, and the sample strip was rolled back and forth twice with a press roll at a speed of about 10 mm/s. And (3) uncovering the proton exchange membrane at one end of the sample strip by about 2cm, and then respectively placing the stainless steel sheet and the uncovered proton exchange membrane into a lower clamp and an upper clamp of a tensile testing machine to ensure that the directions of the steel plate and the sample strip are vertically upwards. The peel test was performed at a speed of 300 mm/min.+ -.10 mm/min, the peeling was stopped until the upper end of the steel sheet, and the peel force F1 in gf of the measured specimen was recorded. The peel force of all the bars was measured sequentially and the average value was 180 ° peel force of the release film.
Contact angle: the sample is spread on a glass slide with the release surface upwards, a small amount of pure water is sucked by a contact angle measuring instrument, 3 mu L-5 mu L of pure water is dripped on the release film surface according to the operation procedure of the contact angle measuring instrument, and the contact angles of the sample at 5s, 10s and 15s are recorded. The operation was repeated 3 times and the contact angle was recorded.
Transferring release agent: the test sample and the reference sample are placed in an SEM metal spraying instrument for chromium (or platinum) spraying treatment. Carrying out element identification and content analysis on the treated sample by SEM+EDS test, and testing voltage: 15KV, current: 0.06mA. The elemental species of the test sample and the reference sample are identified (C, O, F, S), respectively, and are compared to determine whether the contents of the respective elements are close or coincident.
The results of the performance parameter tests of the above examples and comparative examples are shown in tables 1 and 2, respectively.
TABLE 1 physical mechanical Properties of Release films obtained in examples and comparative examples
TABLE 2 Performance parameters of the Release films obtained in examples and comparative examples
From the above description, it can be seen that the embodiment of the invention uses the high temperature resistant PET film as the base material, so that the release film has good temperature resistance and tensile strength, uses the epoxy acrylate as the adhesive, uses the PVDF as the release agent, and makes the PVDF layer and the PET layer achieve good adhesion and release effect by determining proper solid content, coating wet thickness and drying temperature. The prepared high-temperature resistant release film has the tensile strength of 130-135 MPa, the elongation at break of 75-87%, the thermal shrinkage at 160 ℃ of less than 1%, the thickness of the release layer of 1-4 mu m, the water contact angle of 76-79 DEG, the peeling force between the release layer and the proton exchange film of 9 gf-13 gf, and no transfer of the release layer.
It should be noted that the terms "first," "second," and the like in the description and in the claims of the present application are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances such that the embodiments of the application described herein are, for example, capable of operation in sequences other than those described herein.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The utility model provides a compound release film which characterized in that, compound release film is including range upon range of release layer (10), binder layer (20) and substrate layer (30) that set up in proper order, wherein:
the release layer (10) is a PVDF layer, the adhesive layer (20) is an epoxy acrylate layer, and the base material layer (30) is a PET layer.
2. The composite release film according to claim 1, wherein the release layer (10) has a thickness of 1 to 4 μm, the adhesive layer (20) has a thickness of 1 to 5 μm, and the base material layer (30) has a thickness of 75 to 175 μm; preferably, the epoxy acrylate layer is a polyurethane modified epoxy acrylate layer, a bisphenol a epoxy acrylate layer or an anhydride modified epoxy acrylate layer.
3. A method of preparing the composite release film of claim 1 or 2, comprising:
step S1, providing a substrate layer (30) with a first surface and a second surface which are opposite;
step S2, providing epoxy acrylate paint as adhesive slurry, and preparing PVDF resin into release slurry;
step S3, coating the adhesive slurry on the first surface of the substrate layer (30), and forming the adhesive layer (20) on the first surface after drying;
and S4, coating the release slurry on the surface of the adhesive layer (20) away from the substrate layer (30), and drying to form the release layer (10) so as to obtain the composite release film.
4. The method of claim 3, wherein the epoxy acrylate paint in step S2 is one or more selected from the group consisting of polyurethane modified epoxy acrylate, bisphenol a epoxy acrylate and anhydride modified epoxy acrylate paint.
5. The method according to claim 3 or 4, wherein the adhesive slurry in step S3 has a wet film thickness of 10 to 50 μm.
6. The method according to any one of claims 3 to 5, wherein the temperature during the drying to form the adhesive layer (20) in step S3 is 80 to 150 ℃ for 1 to 3min.
7. The method according to claim 3, wherein the preparation method of the release slurry in step S2 comprises:
s2-1, dispersing the PVDF resin into a solvent to obtain a mixed solution;
s2-2, heating the mixed solution to 40-80 ℃, and stirring for 1-4 hours to obtain the release slurry;
preferably, the solvent is a mixed solvent of N, N-dimethylformamide and ethyl acetate, and the mass ratio of the N, N-dimethylformamide to the ethyl acetate is (1-4): 1, a step of;
preferably, the solid content of the PVDF resin in the mixed solution is 4-10%.
8. The method according to claim 3 or 7, wherein the thickness of the wet film coated with the release slurry in step S4 is 30 to 100 μm, and the temperature during the drying process is 120 to 160 ℃ for 3 to 5min.
9. The method of preparation according to any one of claims 3 to 8, characterized in that it further comprises the step of corona treatment of the first surface of the substrate layer (30) before coating the binder slurry.
10. Use of the composite release film according to claim 1 or 2, or according to any one of claims 3 to 9, in a proton exchange membrane cast film coating process.
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