A corrosion-resistant protective film and its preparation method

Abstract

This invention discloses a corrosion-resistant protective film and its preparation method. The film comprises 30-50 parts of a novel film-forming matrix resin, 15-25 parts of recycled modified polymer film powder, 8-15 parts of a crosslinking modifier, 5-12 parts of a zinc ion slow-release antibacterial agent, 3-8 parts of an active antibacterial functional monomer, 6-14 parts of corrosion-resistant filler powder, 1-3 parts of a wetting and dispersing agent, 0.5-2 parts of a defoamer, 15-28 parts of an environmentally friendly solvent, 2-5 parts of a toughening agent, and 1-2 parts of a coupling activator. Utilizing waste plastic scraps as the core raw material, this invention effectively solves the environmental problems of difficult degradation and disposal of waste membrane materials. The activated and modified recycled film powder can uniformly fill the micropores of the resin crosslinking network, further improving the overall density of the membrane layer and enhancing its resistance to aging, salt spray, and acid and alkali corrosion. Based on the synergistic antibacterial system of zinc ion slow release and active groups, it can quickly inhibit and effectively resist harmful bacteria such as Staphylococcus aureus and Escherichia coli, solving the problems of mold growth and bacterial proliferation on the membrane surface in humid environments.

Description

Technical Field

[0001] This invention relates to the field of protective film technology, specifically to a corrosion-resistant protective film and its preparation method. Background Technology

[0002] Currently, most commercially available protective films are made from virgin petroleum-based resin raw materials, resulting in high production costs and resource consumption. Furthermore, discarded protective films are difficult to degrade and recycle, easily causing solid waste pollution, which contradicts the industrial development concept of green, low-carbon, and circular economy. At the same time, traditional protective films have significant performance shortcomings: the substrate structure is loose and the film layer is not dense enough. Under complex working conditions such as acid, alkali, salt spray, humidity, oil, and alternating high and low temperatures, corrosive media can easily penetrate quickly, leading to peeling, bulging, cracking, and detachment within a short period, resulting in a short service life. Moreover, these products lack a dedicated antibacterial structure design, making them prone to the growth of harmful bacteria such as Staphylococcus aureus and Escherichia coli during long-term use, causing problems such as mold growth on the film surface, substrate contamination, and accelerated corrosion, greatly limiting the applicable scenarios of the products.

[0003] Existing recycled protective membrane technologies simply involve directly mixing and crushing waste membrane materials without fine impurity removal, modification, or activation treatment. This results in defects such as poor compatibility of recycled materials, uneven system dispersion, poor membrane mechanical properties, and high porosity. Not only does it fail to improve corrosion resistance, but it also leads to easy membrane damage and protective failure. Furthermore, it lacks long-term antibacterial function and cannot meet the dual requirements of environmentally friendly recycling and high-performance protection. The industry urgently needs a protective membrane preparation technology that can efficiently utilize waste protective membranes and plastic film waste, while also possessing excellent corrosion resistance and long-term broad-spectrum antibacterial properties.

[0004] To address the aforementioned problems, this invention presents a corrosion-resistant protective film and its preparation method. Summary of the Invention

[0005] To address the shortcomings of existing technologies, this invention provides a corrosion-resistant protective film and its preparation method, thereby solving the aforementioned problems.

[0006] To achieve the above objectives, the present invention is implemented through the following technical solution: a corrosion-resistant protective film comprising the following components: 30-50 parts of virgin film-forming matrix resin, 15-25 parts of recycled modified polymer film powder, 8-15 parts of crosslinking modifier, 5-12 parts of zinc ion slow-release antibacterial agent, 3-8 parts of active antibacterial functional monomer, 6-14 parts of corrosion-resistant filler powder, 1-3 parts of wetting and dispersing agent, 0.5-2 parts of defoamer, 15-28 parts of environmentally friendly solvent, 2-5 parts of toughening agent, and 1-2 parts of coupling activator.

[0007] Preferably, the recycled modified polymer membrane powder is obtained from waste PET, PP, and PVC membrane materials through impurity removal, cleaning, ultrafine pulverization, and coupling activation modification.

[0008] Preferably, the coupling activator is any one or more of silane coupling agents, titanate coupling agents, and aluminate coupling agents.

[0009] Preferably, the zinc ion slow-release antibacterial agent is one of mesoporous silica, zeolite molecular sieve, or bentonite loaded with zinc ions, and has a porous slow-release structure; it can achieve uniform and long-term release of zinc ions and avoid short-term precipitation failure.

[0010] Preferably, the active antibacterial functional monomer is an acrylic functional monomer containing quaternary ammonium salt groups, imidazole groups, and pyridine groups, which can undergo copolymerization with the resin matrix to stably graft the antibacterial active groups into the cross-linked network backbone.

[0011] Preferably, the corrosion-resistant filler powder is one or more of nano-silica, talc, mica powder, and heavy calcium carbonate powder, with a particle size of 500-800 mesh. It can synergistically recover membrane powder to fill the micropores of the membrane layer and further improve the resistance to media permeation.

[0012] Preferably, the novel film-forming matrix resin is one or more of acrylic resin, polyurethane resin, and epoxy resin, possessing excellent film-forming properties, adhesion, and weather resistance, and is suitable for composite film-forming systems using recycled modified film powder.

[0013] Preferably, the crosslinking modifier is one or more of isocyanate, epoxy, and amino resin crosslinking agents, with aliphatic hexamethylene diisocyanate being preferred, used to construct a dense multi-level crosslinking network and improve the film density.

[0014] Preferably, the wetting and dispersing agent is one of the following: high molecular block polyether, polyacrylate, or organosilicon dispersant, used to improve the dispersibility of recycled membrane powder and inorganic functional powder, and to prevent agglomeration and sedimentation.

[0015] Preferably, the defoamer is one of polyether, silicone, or mineral oil defoamers, used to eliminate microbubbles in the system and prevent pinholes and shrinkage defects in the protective film.

[0016] Preferably, the environmentally friendly solvent is a benzene-free environmentally friendly solvent system composed of ethyl acetate, butyl acetate, propylene glycol methyl ether acetate, ethanol, and deionized water, which has mild volatility and no toxic residue.

[0017] Preferably, the toughening agent is one of polyester or polyurethane flexible toughening agents, used to offset the rigidity defects caused by recycled membrane powder and improve the flexibility and bending resistance of the membrane.

[0018] A method for preparing a corrosion-resistant protective film, S1: Pretreatment and modification of recycled waste materials: S11: Sorting and impurity removal: Collect waste industrial protective film, household plastic film scraps, and waste PET / PP / PVC film materials. Manually and by air separation, remove non-polymer impurities such as sand, metal, and debris, and screen out intact waste film materials without heavy carbonization. S12: Cleaning and degreasing: Place the sorted waste material in a neutral cleaning solution and ultrasonically clean for 15-25 minutes to remove surface oil, dust, and mold. Then rinse repeatedly with pure water and dry in a 60-80℃ constant temperature oven until constant weight. S13: Ultrafine grinding: The dried waste membrane material is ultrafinely ground by a low-temperature pulverizer to prepare a uniform membrane powder of 800-1200 mesh, and the coarse particles are removed by screening. S14: Activation and modification: Add the membrane powder to a high-speed mixer, spray the coupling activator, stir at high speed for 15-20 minutes, and let it stand at room temperature for 2 hours to activate it, thereby improving the surface activity of the membrane powder and enhancing its cross-linking ability with the resin matrix, and obtaining the final recycled modified polymer membrane powder for later use. S2: Premixing and Activating Recycled Material: The prepared recycled modified polymer membrane powder, environmentally friendly solvent, and wetting and dispersing agent are put into a high-speed stirring tank, stirred at low speed for 10 minutes for initial mixing, and then stirred at high speed for 20 minutes to make the recycled membrane powder uniformly dispersed in the solvent system and avoid agglomeration and sedimentation. S3: Functional slurry grinding: Add corrosion-resistant filler powder and zinc ion slow-release antibacterial agent to the mixing system in sequence, grind and disperse at high speed for 30-50 minutes to refine the powder particles, eliminate micro-agglomeration, and obtain a uniform regenerated antibacterial and corrosion-resistant premixed slurry. S4: Matrix fusion and preparation: Add new film-forming matrix resin and toughening agent to the premixed slurry, stir at a constant temperature of 45-55℃ for 40-60 minutes until the resin is completely dissolved, and the recovered film powder is fully fused with the matrix resin. The system is free of particles and stratification. S5: Functional crosslinking modification: Slowly add crosslinking modifier and active antibacterial functional monomer, control the temperature at 50-60℃ and stir at a uniform speed for 25-40 minutes to promote the synergistic crosslinking polymerization of resin matrix, recycled modified film powder and functional components to form a dense and stable multi-level crosslinking network structure. S6: Additive blending and defoaming: Add defoamer and stir at low speed for 15 minutes to remove bubbles from the system. Filter to remove trace impurities and unactivated coarse particles to obtain corrosion-resistant, antibacterial, and regenerating protective film coating stock solution. S7: Coating and Curing: The original liquid is evenly coated onto the surface of PET, PP, and PVC substrates using a coating machine. A gradient heating drying process of 40℃ pre-baking, 60℃ curing, and 80℃ maturation is adopted. After drying and cooling, the film is rolled up and cut to obtain the finished corrosion-resistant, antibacterial, and regenerable protective film.

[0019] The present invention has the following beneficial effects: The present invention makes extensive use of industrial solid waste such as waste protective film and plastic film scraps as core raw materials, replacing 20%-40% of the new resin raw materials, significantly reducing the use of petroleum-based raw materials, effectively solving the environmental problems of waste film materials being difficult to degrade and handle, reducing solid waste emissions, reducing production costs, and meeting the industrial policy requirements of circular economy and green manufacturing. The activated and modified recycled membrane powder can be uniformly filled in the micropores of the resin cross-linking network, making up for the micropore defects of traditional cross-linking membranes, further improving the overall density of the membrane, and providing double protection against the penetration of corrosive media such as acids, alkalis, salt spray, and water vapor. Its resistance to aging, salt spray, and acid and alkali corrosion is greatly improved, and it can be adapted to complex industrial conditions for a long time. Relying on the zinc ion slow-release and active group synergistic antibacterial system, it can quickly inhibit and resist harmful bacteria such as Staphylococcus aureus and Escherichia coli, solving the problems of mold growth and bacterial growth on the membrane surface in humid environments; and the antibacterial components are uniformly embedded in the regenerated cross-linked network, combined with the dense structure filled with recycled materials, which effectively avoids the loss of antibacterial components and ensures long-term antibacterial stability. Through coupling activation modification, the defects of poor compatibility between recycled waste and new resin, easy delamination, and easy brittleness are completely solved. The film has strong adhesion, good flexibility, wear resistance, and is not easy to fall off. The overall preparation process is simple, and the waste pretreatment is seamlessly connected with the main process. No new large-scale equipment is required, and industrial mass production can be achieved. Attached Figure Description

[0020] Figure 1 This is a schematic diagram of the process flow of the present invention; Detailed Implementation The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0021] Please see Figure 1 The present invention provides a technical solution: A corrosion-resistant protective film comprises the following components: 30-50 parts of virgin film-forming matrix resin, 15-25 parts of recycled modified polymer film powder, 8-15 parts of crosslinking modifier, 5-12 parts of zinc ion slow-release antibacterial agent, 3-8 parts of active antibacterial functional monomer, 6-14 parts of corrosion-resistant filler powder, 1-3 parts of wetting and dispersing agent, 0.5-2 parts of defoamer, 15-28 parts of environmentally friendly solvent, 2-5 parts of toughening agent, and 1-2 parts of coupling activator.

[0022] In this embodiment, preferably, the recycled modified polymer film powder is obtained from waste PET, PP, and PVC film materials through impurity removal, cleaning, ultrafine pulverization, and coupling activation modification.

[0023] In this embodiment, preferably, the coupling activator is any one or more of silane coupling agents, titanate coupling agents, and aluminate coupling agents.

[0024] Preferably, the zinc ion slow-release antibacterial agent is one of the following: zinc ion-loaded mesoporous silica, zeolite molecular sieve, or bentonite, possessing a porous slow-release structure; it can achieve uniform and long-term release of zinc ions, avoiding short-term precipitation failure.

[0025] In this embodiment, preferably, the active antibacterial functional monomer is an acrylic functional monomer containing quaternary ammonium salt groups, imidazole groups, and pyridine groups, which can undergo copolymerization with the resin matrix to stably graft the antibacterial active groups into the crosslinked network backbone.

[0026] In this embodiment, preferably, the corrosion-resistant filler powder is one or more of nano-silica, talc, mica powder, and heavy calcium carbonate powder, with a particle size of 500 mesh. It can synergistically recover membrane powder to fill the micropores of the membrane layer and further improve the resistance to media permeation.

[0027] In this embodiment, preferably, the novel film-forming matrix resin is one or more of acrylic resin, polyurethane resin, and epoxy resin, which has excellent film-forming properties, adhesion and weather resistance, and is suitable for composite film-forming systems of recycled modified film powder.

[0028] In this embodiment, preferably, the crosslinking modifier is one or more of isocyanate, epoxy, and amino resin crosslinking agents, preferably aliphatic hexamethylene diisocyanate, used to construct a dense multi-level crosslinking network and improve the compactness of the film layer.

[0029] In this embodiment, preferably, the wetting and dispersing agent is one of the following: high molecular block polyether, polyacrylate, or organosilicon dispersant, used to improve the dispersibility of the recycled membrane powder and inorganic functional powder, and to prevent agglomeration and sedimentation.

[0030] In this embodiment, preferably, the defoamer is one of polyether, silicone, or mineral oil defoamers, used to eliminate microbubbles in the system and prevent pinholes and shrinkage defects in the protective film.

[0031] In this embodiment, the preferred environmentally friendly solvent is a benzene-free environmentally friendly solvent system composed of ethyl acetate, butyl acetate, propylene glycol methyl ether acetate, ethanol, and deionized water, which has mild volatility and no toxic residue.

[0032] In this embodiment, preferably, the toughening agent is one of polyester or polyurethane flexible toughening agents, used to offset the rigidity defects caused by recycled membrane powder and improve the flexibility and bending resistance of the membrane.

[0033] A method for preparing a corrosion-resistant protective film, S1: Pretreatment and modification of recycled waste materials: S11: Sorting and impurity removal: Collect waste industrial protective film, household plastic film scraps, and waste PET / PP / PVC film materials. Manually and by air separation, remove non-polymer impurities such as sand, metal, and debris, and screen out intact waste film materials without heavy carbonization. S12: Cleaning and degreasing: Place the sorted waste material in a neutral cleaning solution and ultrasonically clean for 15-25 minutes to remove surface oil, dust, and mold. Then rinse repeatedly with pure water and dry in a 60-80℃ constant temperature oven until constant weight. S13: Ultrafine grinding: The dried waste membrane material is ultrafinely ground by a low-temperature pulverizer to prepare a uniform membrane powder of 800-1200 mesh, and the coarse particles are removed by screening. S14: Activation and modification: Add the membrane powder to a high-speed mixer, spray the coupling activator, stir at high speed for 15-20 minutes, and let it stand at room temperature for 2 hours to activate it, thereby improving the surface activity of the membrane powder and enhancing its cross-linking ability with the resin matrix, and obtaining the final recycled modified polymer membrane powder for later use. S2: Premixing and Activating Recycled Material: The prepared recycled modified polymer membrane powder, environmentally friendly solvent, and wetting and dispersing agent are put into a high-speed stirring tank, stirred at low speed for 10 minutes for initial mixing, and then stirred at high speed for 20 minutes to make the recycled membrane powder uniformly dispersed in the solvent system and avoid agglomeration and sedimentation. S3: Functional slurry grinding: Add corrosion-resistant filler powder and zinc ion slow-release antibacterial agent to the mixing system in sequence, grind and disperse at high speed for 30-50 minutes to refine the powder particles, eliminate micro-agglomeration, and obtain a uniform regenerated antibacterial and corrosion-resistant premixed slurry. S4: Matrix fusion and preparation: Add new film-forming matrix resin and toughening agent to the premixed slurry, stir at a constant temperature of 45-55℃ for 40-60 minutes until the resin is completely dissolved, and the recovered film powder is fully fused with the matrix resin. The system is free of particles and stratification. S5: Functional crosslinking modification: Slowly add crosslinking modifier and active antibacterial functional monomer, control the temperature at 50-60℃ and stir at a uniform speed for 25-40 minutes to promote the synergistic crosslinking polymerization of resin matrix, recycled modified film powder and functional components to form a dense and stable multi-level crosslinking network structure. S6: Additive blending and defoaming: Add defoamer and stir at low speed for 15 minutes to remove bubbles from the system. Filter to remove trace impurities and unactivated coarse particles to obtain corrosion-resistant, antibacterial, and regenerating protective film coating stock solution. S7: Coating and Curing: The original liquid is evenly coated onto the surface of PET, PP, and PVC substrates using a coating machine. A gradient heating drying process of 40℃ pre-baking, 60℃ curing, and 80℃ maturation is adopted. After drying and cooling, the film is rolled up and cut to obtain the finished corrosion-resistant, antibacterial, and regenerable protective film.

[0034] The preferred embodiments of the present invention disclosed above are merely illustrative of the invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the invention to the specific implementations described. Clearly, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to better understand and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims

1. A corrosion-resistant protective film, characterized in that: It includes the following components: 30-50 parts of virgin film-forming matrix resin, 15-25 parts of recycled modified polymer film powder, 8-15 parts of crosslinking modifier, 5-12 parts of zinc ion slow-release antibacterial agent, 3-8 parts of active antibacterial functional monomer, 6-14 parts of corrosion-resistant filler powder, 1-3 parts of wetting and dispersing agent, 0.5-2 parts of defoamer, 15-28 parts of environmentally friendly solvent, 2-5 parts of toughening agent, and 1-2 parts of coupling activator.

2. The corrosion-resistant protective film according to claim 1, characterized in that: The recycled modified polymer membrane powder is obtained from waste PET, PP, and PVC membrane materials through impurity removal, cleaning, ultrafine pulverization, and coupling activation modification.

3. The corrosion-resistant protective film according to claim 2, characterized in that: The coupling activator is any one or more of silane coupling agents, titanate coupling agents, and aluminate coupling agents.

4. The corrosion-resistant protective film according to claim 3, characterized in that: The zinc ion slow-release antibacterial agent is one of the following: zinc ion-loaded mesoporous silica, zeolite molecular sieve, or bentonite, and has a porous slow-release structure.

5. The corrosion-resistant protective film according to claim 4, characterized in that: The active antibacterial functional monomer is an acrylic functional monomer containing quaternary ammonium salt groups, imidazole groups, and pyridine groups.

6. The corrosion-resistant protective film according to claim 5, characterized in that: The corrosion-resistant filler powder is one or more of nano-silica, talc, mica powder, and heavy calcium carbonate powder.

7. The corrosion-resistant protective film according to claim 6, characterized in that: The novel film-forming matrix resin is one or more of acrylic resin, polyurethane resin, and epoxy resin.

8. The corrosion-resistant protective film according to claim 1, characterized in that: The crosslinking modifier is one or more of isocyanate, epoxy, and amino resin crosslinking agents; the wetting and dispersing agent is one of polymer block polyether, polyacrylate, and organosilicon dispersing agents.

9. The corrosion-resistant protective film according to claim 1, characterized in that: Preferably, the defoamer is one of polyether, silicone, or mineral oil defoamers; the environmentally friendly solvent is a benzene-free environmentally friendly solvent system composed of ethyl acetate, butyl acetate, propylene glycol methyl ether acetate, ethanol, and deionized water; and the toughening agent is one of polyester or polyurethane flexible toughening agents.

10. A method for preparing a corrosion-resistant protective film as described in any one of claims 1-9, characterized in that: S1: Pretreatment and modification of recycled waste materials: S11: Sorting and impurity removal: Collect waste industrial protective film, household plastic film scraps, and waste PET / PP / PVC film materials. Manually and by air separation, remove non-polymer impurities such as sand, metal, and debris, and screen out intact waste film materials without heavy carbonization. S12: Cleaning and degreasing: Place the sorted waste material in a neutral cleaning solution and ultrasonically clean for 15-25 minutes to remove surface oil, dust, and mold. Then rinse repeatedly with pure water and dry in a 60-80℃ constant temperature oven until constant weight. S13： Ultrafine grinding: The dried waste membrane material is ultrafinely ground by a low-temperature pulverizer to prepare uniform membrane powder of 800-1200 mesh, and coarse particles and lumps are removed by screening. S14: Activation and modification: Add the membrane powder to a high-speed mixer, spray the coupling activator, stir at high speed for 15-20 minutes, and let it stand at room temperature for 2 hours to activate it, thereby improving the surface activity of the membrane powder and enhancing its cross-linking ability with the resin matrix, and obtaining the final recycled modified polymer membrane powder for later use. S2: Premixing and Activating Recycled Material: The prepared recycled modified polymer membrane powder, environmentally friendly solvent, and wetting and dispersing agent are put into a high-speed stirring tank, stirred at low speed for 10 minutes for initial mixing, and then stirred at high speed for 20 minutes to make the recycled membrane powder uniformly dispersed in the solvent system and avoid agglomeration and sedimentation. S3: Functional slurry grinding: Add corrosion-resistant filler powder and zinc ion slow-release antibacterial agent to the mixing system in sequence, grind and disperse at high speed for 30-50 minutes to refine the powder particles, eliminate micro-agglomeration, and obtain a uniform regenerated antibacterial and corrosion-resistant premixed slurry. S4: Matrix fusion and preparation: Add new film-forming matrix resin and toughening agent to the premixed slurry, stir at a constant temperature of 45-55℃ for 40-60 minutes until the resin is completely dissolved, and the recovered film powder is fully fused with the matrix resin. The system is free of particles and stratification. S5: Functional crosslinking modification: Slowly add crosslinking modifier and active antibacterial functional monomer, control the temperature at 50-60℃ and stir at a uniform speed for 25-40 minutes to promote the synergistic crosslinking polymerization of resin matrix, recycled modified film powder and functional components to form a dense and stable multi-level crosslinking network structure. S6: Additive blending and defoaming: Add defoamer and stir at low speed for 15 minutes to remove bubbles from the system. Filter to remove trace impurities and unactivated coarse particles to obtain corrosion-resistant, antibacterial, and regenerating protective film coating stock solution. S7: Coating and Curing: The original liquid is evenly coated onto the surface of PET, PP, and PVC substrates using a coating machine. A gradient heating drying process of 40℃ pre-baking, 60℃ curing, and 80℃ maturation is adopted. After drying and cooling, the film is rolled up and cut to obtain the finished corrosion-resistant, antibacterial, and regenerable protective film.

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