PVC composite layer, film-coated metal plate and preparation method and application of PVC composite layer and film-coated metal plate

Abstract

The invention relates to the field of chemical materials, in particular to a PVC composite layer, a film-coated metal plate and a preparation method and application of the PVC composite layer and the film-coated metal plate. The PVC composite layer comprises a PVC surface layer, a PVC middle layer, a glass fiber layer and a PVC bottom layer which are arranged in sequence, wherein the average polymerization degree of the polyvinyl chloride resin is 800 to 1500. The film-coated metal plate prepared from the PVC composite layer provided by the invention is excellent in comprehensive capacity.

Description

Technical Field

[0001] This invention relates to the field of chemical materials, and in particular to a PVC composite layer, a coated metal plate, its preparation method and application. Background Technology

[0002] Coated metal sheets are building materials made by combining metal sheets with polymer films or other types of coating materials. This material is widely used in the construction industry, especially in exterior wall decoration, roofing, and interior finishing. The coating provides an additional protective layer, enhancing the material's durability, aesthetics, and corrosion resistance.

[0003] Because coated metal sheets are expensive, repairs are complex once the coating is damaged, sometimes requiring the entire sheet to be replaced rather than simply patching or recoating. Furthermore, the coating itself may age, peel, or fade due to prolonged exposure to extreme weather conditions.

[0004] Although some coated metal sheets exist in the existing technology, such as CN109648949A, CN102995840A, and CN112060734A, their overall performance still needs to be further improved. Summary of the Invention

[0005] This invention provides a PVC composite layer, a coated metal sheet, its preparation method, and its application, in order to solve the problem that the overall performance of existing coated metal sheets needs to be improved.

[0006] In a first aspect, the present invention provides a PVC composite layer, the PVC composite layer comprising a PVC top layer, a PVC middle layer, a glass fiber layer and a PVC bottom layer arranged sequentially;

[0007] By weight, the PVC surface layer is made of at least the following components: 90-110 parts of polyvinyl chloride resin, 45-60 parts of plasticizer, 0.3-0.8 parts of lubricant, 2-4 parts of stabilizer, 10-20 parts of titanium dioxide, 5-30 parts of filler, 0.1-2 parts of antioxidant, and 0.1-2 parts of UV resistant agent;

[0008] By weight, the PVC middle layer is made of at least the following components: 90-110 parts of polyvinyl chloride resin, 45-60 parts of plasticizer, 0.3-0.8 parts of lubricant, 2-4 parts of stabilizer, 5-15 parts of titanium dioxide, 5-30 parts of filler, 0.1-2 parts of antioxidant, and 0.1-2 parts of UV resistant agent.

[0009] By weight, the PVC underlayer is made of at least the following components: 90-110 parts of polyvinyl chloride resin, 45-60 parts of plasticizer, 0.3-0.8 parts of lubricant, 2-4 parts of stabilizer, 5-30 parts of filler, 0.1-2 parts of antioxidant, and 0-1 part of UV protection agent.

[0010] The polyvinyl chloride resin has an average degree of polymerization of 800-1500. In the PVC composite layer provided by this invention, to maintain the flexibility and weldability of the PVC composite layer, the plasticizer content is not less than 45 parts; to ensure sufficient mechanical properties of the PVC composite layer, the plasticizer content is not more than 60 parts; to improve the solar reflectivity and weather resistance of the surface layer, a certain amount of titanium dioxide is added; to improve the processing convenience, appearance, and overall weather resistance of the PVC sheet, a polyvinyl chloride resin with an average degree of polymerization between 800-1500 is selected. This is because resins with a high average degree of polymerization produce harder sheets, requiring more stringent production conditions and higher hot air welding temperatures, which are detrimental to construction. Resins with a low degree of polymerization produce sheets with poor mechanical properties, making them less suitable for construction and use. In different embodiments, the average degree of polymerization of the polyvinyl chloride resin can be 800, 1000, 1200, 1300, 1350, 1400, 1500, etc.

[0011] The VC composite layer provides superior weather resistance on the surface, while the PVC underlayer provides adhesion to the adhesive film layer. To reduce costs and improve the bond strength between the PVC composite layer and the glass fiber layer, the proportion of titanium dioxide in the PVC intermediate layer is appropriately reduced. Furthermore, because the light aging requirements for the PVC intermediate layer are significantly reduced, titanium dioxide is eliminated, and the content of UV-resistant additives is reduced. The surface and intermediate layer formulations maintain the properties of non-delamination after extrusion and surface interfacial hot-air weldability.

[0012] In this invention, the MFR (melt flow rate or melt index) of each component of the PVC composite layer, measured at 190°C and 5 kg, is no greater than 12.0 g / 10 min.

[0013] The PVC composite layer provided by this invention provides waterproofing, corrosion resistance, weather resistance, and medium-heat weldability for the integrally manufactured coated metal sheet, and the resulting coated metal sheet has excellent overall performance.

[0014] Glass fiber mat can be used as a reinforcing layer in PVC composite layers to improve the dimensional change rate of PVC composite layers during heat treatment, thereby reducing the risk of creep damage caused by the inconsistency of linear expansion coefficients when PVC composite layers and metal sheets are used together. At the same time, glass fiber mat can effectively reduce the migration range of interlayer plasticizers in PVC composite layers during long-term use, ensuring the adhesion strength between the PVC composite layer and the polymer adhesive film layer.

[0015] In some embodiments, the PVC surface layer is made of at least the following components by weight: 95-105 parts of polyvinyl chloride resin, 50-60 parts of plasticizer, 0.3-0.6 parts of lubricant, 2-3 parts of stabilizer, 10-20 parts of titanium dioxide, 5-20 parts of filler, 1-2 parts of antioxidant, and 1-2 parts of UV resistant agent.

[0016] By weight, the PVC middle layer is made of at least the following components: 95-105 parts of polyvinyl chloride resin, 50-60 parts of plasticizer, 0.3-0.6 parts of lubricant, 2-3 parts of stabilizer, 8-10 parts of titanium dioxide, 15-20 parts of filler, 1-2 parts of antioxidant, and 1-2 parts of UV protection agent.

[0017] By weight, the PVC underlayer is made of at least the following components: 95-105 parts polyvinyl chloride resin, 50-60 parts plasticizer, 0.3-0.6 parts lubricant, 2-3 parts stabilizer, 15-20 parts filler, 1-2 parts antioxidant, and 0.1-1 parts UV resistant agent.

[0018] In some embodiments, the glass fiber layer is made of glass fiber mat. Optionally, the basis weight of the glass fiber mat is 25-60 g / m². 2 Specifically, in some embodiments, the basis weight of the fiberglass mat is 45-60 g / m². 2 In some embodiments, the basis weight of the fiberglass mat is 50-60 g / m². 2 ;etc.

[0019] In some embodiments, the thickness of the PVC composite layer is 0.8-2.0 mm. Optionally, the thickness of the PVC composite layer is 1.0-2.0 mm. Preferably, the thickness of the PVC composite layer is not less than 1.2 mm, meeting the waterproofing requirements of the national standard "General Specification for Waterproofing of Building and Municipal Engineering", thus enabling wider application. More preferably, the thickness of the PVC composite layer is 1.5-2.0 mm.

[0020] Optionally, the glass fiber layer is located in the portion of the PVC composite layer that is 30%-70% of its thickness. Preferably, the glass fiber layer is located in the portion between 40%-60% of the thickness of the PVC composite layer. Typically, the glass fiber layer is located in the portion where the thickness of the PVC composite layer is halfway down. That is, the glass fiber layer is usually located in the middle of the PVC composite layer.

[0021] In some embodiments, optionally, the thickness of the PVC surface layer is not less than 0.25 mm; optionally, the thickness of the PVC middle layer is not less than 0.34 mm or the thickness of the PVC middle layer and the glass fiber layer is not less than 0.35 mm; optionally, the thickness of the PVC bottom layer is not less than 0.55 mm.

[0022] The PVC composite layer comprises a PVC top layer, a PVC middle layer, a fiberglass layer, and a PVC bottom layer arranged sequentially. Optionally, the thickness of the PVC top layer is not less than 0.25 mm. As described above, optionally, the fiberglass layer is located in the portion of the PVC composite layer with a thickness of 30%-70%. Preferably, the fiberglass layer is located in the portion between 40%-60% of the thickness of the PVC composite layer. Typically, the fiberglass layer is located in the portion of half the thickness of the PVC composite layer. Optionally, the thickness of the PVC middle layer is not less than 0.34 mm, or the thickness of the PVC middle layer and the fiberglass layer is not less than 0.35 mm. Optionally, the thickness of the PVC bottom layer is not less than 0.55 mm.

[0023] In some possible embodiments, the PVC composite layer comprises a PVC surface layer, a PVC middle layer, a fiberglass layer, and a PVC bottom layer arranged sequentially. The thickness of the PVC surface layer is 0.25 mm, the thickness of the PVC middle layer is 0.34 mm, and the thickness of the PVC bottom layer is 0.55-0.80 mm, such as 0.55 mm, 0.60 mm, 0.70 mm, 0.80 mm, etc. In some possible embodiments, the PVC composite layer comprises a PVC surface layer, a PVC middle layer, a fiberglass layer, and a PVC bottom layer arranged sequentially. The thickness of the PVC surface layer is 0.40 mm, the thickness of the PVC middle layer is 0.40 mm, and the thickness of the PVC bottom layer is 0.55-1.20 mm, such as 0.55 mm, 0.60 mm, 0.65 mm, 0.70 mm, 0.80 mm, 0.90 mm, 1.00 mm, 1.10 mm, 1.20 mm, etc. In some possible implementations, the PVC composite layer includes a PVC top layer, a PVC middle layer, a fiberglass layer, and a PVC bottom layer arranged sequentially. The thickness of the PVC top layer is 0.50 mm, the thickness of the PVC middle layer is 0.35 mm, and the thickness of the PVC bottom layer is 0.55-1.15 mm. For example, the thickness of the PVC bottom layer can be 0.55 mm, 0.60 mm, 0.65 mm, 0.70 mm, 0.75 mm, 0.80 mm, 0.90 mm, 1.00 mm, 1.10 mm, 1.15 mm, etc.

[0024] In some embodiments, the components are at least one of the following:

[0025] The plasticizer includes DINP (diisononyl phthalate);

[0026] The lubricant includes stearic acid (C 18 H 36 O2);

[0027] The stabilizer includes calcium stearate (C 36 H 70 CaO4);

[0028] The titanium dioxide includes rutile titanium dioxide (TiO2);

[0029] The filler includes one or more of calcium carbonate, flame retardant, and colorant;

[0030] The antioxidants include phosphites (C 69 H 135 O 15 P);

[0031] The UV-protecting additive includes UV-9 ((2-hydroxy-4-methoxyphenyl)phenyl ketone).

[0032] Furthermore, the average particle size of the calcium carbonate is 800-2000 mesh; the flame retardant comprises Sb2O3 and Mg(OH)2, and the mass ratio of Sb2O3 to Mg(OH)2 is 1:3±0.3.

[0033] In some embodiments, the average particle size of calcium carbonate is 800 mesh, 1000 mesh, 1200 mesh, 1300 mesh, 1350 mesh, 1500 mesh, 1600 mesh, 1700 mesh, 1800 mesh, 2000 mesh, etc. In some embodiments, the average particle size of the calcium carbonate is 1300-1500 mesh.

[0034] Optionally, the filler may vary in different PVC composite layers.

[0035] Preferably, the filler in the PVC surface layer contains at least calcium carbonate. If a high flame retardancy requirement is placed on the coated metal sheet, a flame retardant is added to the PVC surface layer of the PVC composite layer. Optionally, the PVC surface layer contains the calcium carbonate and the flame retardant. Optionally, the mass ratio of the calcium carbonate to the flame retardant is 2 ± 0.2:1.

[0036] Secondly, the present invention provides a method for preparing the above-mentioned PVC composite layer, wherein the components of the PVC composite layer are mixed and granulated to obtain PVC particles, and then the PVC particles are extruded through a single-screw sheet extruder to obtain sheets of different layers; or the components of the PVC composite layer are mixed and formed in one step through a twin-screw sheet extruder to obtain sheets of different layers.

[0037] Then, the different layers of sheet and the glass fiber layer are laminated together in sequence.

[0038] The method for preparing a PVC composite layer provided by this invention ultimately involves extrusion calendering using a screw extruder. That is, following conventional methods, the components of the PVC layer are first granulated using a twin-screw granulator according to a specified mass ratio, and then the granulated PVC particles are extruded using a single-screw sheet extruder to obtain sheets with different layers. To reduce the loss of antioxidants and other additives in the PVC layer during processing and to improve the weather resistance imparted by PVC to metal-coated panels, a preferred preparation method is to directly extrude the components of the PVC layer according to a specified mass ratio using a twin-screw sheet extruder in a single step to obtain sheets with different layers. Then, the sheets with different layers are sequentially laminated with the glass fiber layer.

[0039] The process involves arranging the PVC composite layers in the following order: PVC top layer, PVC middle layer, fiberglass layer, and PVC bottom layer, and then laminating them using a mold.

[0040] The PVC composite layer provided by this invention is formed by multi-layer co-extrusion of composite sheets. The surface layer of the PVC composite layer provides superior weather resistance, while the PVC underlayer provides adhesion to the adhesive film layer. The formulations of the PVC surface layer and the PVC underlayer maintain the properties of not delaminating after extrusion and being able to be hot-air welded to each other. In a third aspect, this invention provides a coated metal sheet, comprising the above-mentioned PVC composite layer and a metal sheet layer, wherein an adhesive film layer is disposed between the PVC composite layer and the metal sheet layer.

[0041] Furthermore, the adhesive film layer includes a first adhesive layer, a second adhesive layer, and a third adhesive layer arranged in sequence, wherein the first adhesive layer is in contact with the PVC composite layer, and the third adhesive layer is in contact with the metal plate;

[0042] By weight:

[0043] The first adhesive layer comprises 80-95 parts of polyolefin elastomer, 10-15 parts of polyolefin plasmon, and 10 parts of polyolefin oligomer.

[0044] The second adhesive layer comprises 90-95 parts of maleic anhydride-grafted EVA, 60-95 parts of maleic anhydride-grafted polyolefin plasmon, 10-50 parts of maleic anhydride-grafted polyolefin elastomer, 20-30 parts of maleic anhydride-grafted polystyrene elastomer, 10-20 parts of tackifying petroleum resin, and 20-35 parts of polystyrene elastomer.

[0045] The third adhesive layer comprises 40-75 parts of polyolefin elastomer, 40-75 parts of polyolefin plastisol, and 20-50 parts of maleic anhydride graft.

[0046] In some implementations, for example, by weight:

[0047] The first adhesive layer comprises 80-90 parts of polyolefin elastomer, 10-12 parts of polyolefin plasmon, and 10 parts of polyolefin oligomer;

[0048] The second adhesive layer comprises 90-95 parts of maleic anhydride-grafted EVA, 75-85 parts of maleic anhydride-grafted polyolefin plasmon, 30-40 parts of maleic anhydride-grafted polyolefin elastomer, 20-30 parts of maleic anhydride-grafted polystyrene elastomer, 10-15 parts of tackifying petroleum resin, and 25-35 parts of polystyrene elastomer.

[0049] The third adhesive layer comprises 60-70 parts of polyolefin elastomer, 55-65 parts of polyolefin plastisol, and 40-50 parts of maleic anhydride graft.

[0050] The raw materials and proportions used in the adhesive film layer of this invention have been disclosed in 202410523916.9. The raw materials and proportions used in the adhesive film layer in 202410523916.9 are incorporated herein by reference and will not be described in detail here.

[0051] In some embodiments, the polyolefin elastomer can be 84 parts by weight, 87 parts by weight, 89 parts by weight, etc.; the polyolefin plastic elastomer can be 10 parts by weight, 12 parts by weight, 15 parts by weight, etc.; the maleic anhydride-grafted EVA can be 92 parts by weight, 93 parts by weight, 94 parts by weight, etc.; the maleic anhydride-grafted polyolefin plastic elastomer can be 60 parts by weight, 70 parts by weight, 75 parts by weight, 80 parts by weight, 85 parts by weight, 90 parts by weight, etc.; the maleic anhydride-grafted polyolefin elastomer can be 10 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 33 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, etc.; and the maleic anhydride-grafted polystyrene elastomer can be 20 parts by weight, 22 parts by weight, 25 parts by weight, 26 parts by weight. 28 parts by weight, 30 parts by weight, etc.; tackifying petroleum resin can be 10 parts by weight, 12 parts by weight, 15 parts by weight, 16 parts by weight, 18 parts by weight, 20 parts by weight, etc.; polystyrene elastomer can be 20 parts by weight, 22 parts by weight, 25 parts by weight, 26 parts by weight, 30 parts by weight, 35 parts by weight, etc.; polyolefin elastomer can be 40 parts by weight, 50 parts by weight, 60 parts by weight, 65 parts by weight, 70 parts by weight, 75 parts by weight, etc.; polyolefin plastomer can be 40 parts by weight, 50 parts by weight, 58 parts by weight, 60 parts by weight, 65 parts by weight, 70 parts by weight, 75 parts by weight, etc.; maleic anhydride graft can be 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 44 parts by weight, 50 parts by weight, etc.

[0052] Preferably, the thickness of the adhesive film layer is 0.10±0.05mm.

[0053] Optionally, the first adhesive layer is 31±10μm, the second adhesive layer is 33±10μm, and the third adhesive layer is 33±10μm.

[0054] In some embodiments, the metal plate used for the metal plate layer is selected from galvanized steel plate, aluminized zinc plate, aluminized zinc-magnesium plate, or aluminized zinc-magnesium-manganese plate. Optionally, the thickness of the metal plate is 0.5mm-0.8mm.

[0055] Fourthly, the present invention provides a method for preparing the above-mentioned coated metal plate, comprising the following steps:

[0056] The PVC composite layer, the adhesive film layer, and the metal plate layer are provided;

[0057] The PVC composite layer, the adhesive film layer, and the metal plate layer are hot-pressed in a stacking order, so that the PVC composite layer is bonded to the metal plate layer through the adhesive film layer.

[0058] The PVC composite layer comprises a PVC top layer, a PVC middle layer, a glass fiber layer, and a PVC bottom layer arranged in sequence.

[0059] Fifthly, the present invention provides a building material containing the above-mentioned PVC composite layer or the above-mentioned coated metal plate.

[0060] Optionally, the building material is a roof or wall panel.

[0061] Compared with the prior art, the present invention has at least the following advantages:

[0062] (1) The PVC composite layer of the present invention adds glass fiber mat. The coated metal plate made from the PVC composite layer has moderate strength with the film glass without treatment. After heat treatment, the peel strength retention rate with the film is the largest, and the long-term aging during exposure has the least impact on the adhesive ability of the film.

[0063] (2) By selecting a PVC composite layer with a specific formulation, the PVC composite layer is bonded to a metal plate through an adhesive film layer. The resulting coated metal plate has significantly better tensile strength, elongation at break, right-angle tear strength, seam peel strength, MFR, and strength retention rate with the adhesive film glass after heat treatment than the control group. Furthermore, the dimensional change rate after heat treatment is significantly lower than that of the control group.

[0064] The above description is merely an overview of the technical solution of the present invention. In order to better understand the technical means of the present invention, it can be implemented according to the contents of the specification. Furthermore, in order to make the above and other objects, features and advantages of the present invention more apparent and understandable, specific embodiments of the present invention are described below. Detailed Implementation

[0065] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be considered as specific limitations thereof. Furthermore, the following related technologies are optional solutions and can be arbitrarily combined with the technical solutions of the embodiments of the present invention, all of which fall within the protection scope of the present invention.

[0066] Unless otherwise specified, the experimental methods used in the following examples are conventional methods. Unless otherwise specified, the materials and reagents used in the following examples are commercially available. In this invention, unless otherwise stated, the technical terms, reagents, experimental equipment, and experimental methods used herein have the meanings commonly understood by those skilled in the art.

[0067] Example 1

[0068] Using the same main material formula, waterproof PVC composite layers with different product structures were made and heat-aged in a 90℃ oven for 7 days to test the retention rate of the film peel strength of the material.

[0069] The specific steps are as follows:

[0070] The specific formula of the PVC main material is shown in Table 1.

[0071] Table 1 Specific formulation of PVC main material

[0072]

[0073]

[0074] Based on the formulations of each layer of the main material shown in Table 1, different sheets for P-type PVC waterproof membrane, G-type PVC waterproof membrane, and H-type PVC waterproof membrane were prepared using a multi-layer co-extrusion twin-screw extruder. Then, the different sheets were compounded through a die to obtain P-type PVC waterproof membrane, G-type PVC waterproof membrane, and H-type PVC waterproof membrane. Among them, Class G PVC waterproof membrane has a three-layer resin structure, with the top and middle layers directly bonded together, and fiberglass mat (60g / ㎡) between the middle and bottom layers. The thickness of the top layer is 0.25mm, the middle layer is 0.50mm, and the bottom layer is 0.75mm. Class P PVC waterproof membrane has a three-layer resin structure, with the top and middle layers directly bonded together, and a mesh fabric (1000DX1000D(9X9) specification) between the middle and bottom layers. The thickness of the top layer is 0.25mm, the middle layer is 0.50mm, and the bottom layer is 0.75mm. Class H PVC waterproof membrane has a two-layer resin structure, with the top and middle layers directly bonded together. The thickness of the top layer is 0.25mm and the thickness of the middle layer is 1.25mm. The parameters of the multi-layer co-extrusion twin-screw extruder are as follows: barrel temperature 160℃-175℃, die temperature 180℃-190℃, feed rate 12kg / h, screw speed 120RPM, die width 1.3mm, and sample thickness 1.5mm.

[0075] Table 2 Formulation of film materials

[0076]

[0077] Table 2 shows the formulation of a 0.1mm thick adhesive film composited with PVC material. The specific product models of the raw materials used are the same as those used in Example 1 of Chinese Patent Application (Application No.: 202410523916.9, Publication No.: CN118082315A, Invention Title: Coated Metal Plate, Preparation Method, and Roofing). After granulation of the raw materials, a 0.1mm thick adhesive film is produced by blown film at 180℃. The H-type, G-type, and P-type PVC waterproof membranes are bonded to other layers using the 0.1mm adhesive film, with one side of the adhesive film layer bonded to a 0.6mm thick aluminized zinc-coated steel plate and the other side bonded to the PVC membrane. The entire assembly is then pressurized at 150℃-180℃ to produce PMP material, resulting in PMP2115 G-type, PMP2115 P-type, and PMP2115 H-type coated metal plates, respectively.

[0078] The peel strength of different PMP materials was tested as follows: Different PMP materials were placed in a 90℃ oven for 7 days of heat aging. After 7 days, they were removed and left at room temperature for 1 day. The peel strength of the adhesive film after heat aging was then tested, and the peel strength retention rate was calculated. The results are shown in Table 3.

[0079] Table 3 Test Results

[0080]

[0081] As can be seen from Table 3, when using Class G PVC waterproof membrane to bond with aluminized zinc steel plate, the peel strength retention rate of the membrane after heat treatment is the highest, and the long-term aging during exposure has the least impact on the adhesion of the membrane. Therefore, Class G PVC waterproof membrane is selected as the main waterproof material to be composited with steel plate.

[0082] Example 2

[0083] Five sets of three-layer PVC-G type waterproof membrane composite layers with fiberglass mat in the middle were prepared, using fiberglass mat with a specification of 60g / ㎡. The specific formulations of each layer of the PVC composite layer are shown in Table 4.

[0084] Table 4. Specific formulations for each layer of the PVC composite layer.

[0085]

[0086]

[0087] Different PVC composite layers were prepared according to the formulations shown in Table 4 of this embodiment. The PVC composite layers were prepared in the order of top layer, middle layer, glass fiber mat and bottom layer, according to the method of Example 1.

[0088] The adhesive film layer and metal plate used in this embodiment are the same as in Example 1. Then, the PVC composite layers obtained from different groups are hot-pressed with the metal plate using the adhesive film layer in the same way as in Example 1 to obtain the coated metal plate.

[0089] The prepared PVC waterproof sheet was tested according to the following specifications in GB 12952-2011: 6.5 Tensile properties, 6.6 Dimensional change rate after heat treatment, 6.11 Seam peel strength, and 6.12 Right-angle tear strength. The coated metal sheet was tested according to the following specifications in Q / 320584PBT053-2024: 6.8 Peel strength and 6.9 Peel strength after heat aging. The test results are shown in Table 5.

[0090] Table 5 Test Results

[0091]

[0092] As can be seen from Table 5, the coated metal sheet made from the PVC composite layer provided by the present invention has superior performance in all aspects.

[0093] Comparative Example 1

[0094] According to the formulation provided in this comparative example (Table 6), H-type PVC waterproof membrane was prepared as a PVC composite layer (without glass fiber mat in the middle) according to the method in Example 1. The PVC composite layer includes a PVC surface layer and a PVC middle layer, and the formulations of the PVC surface layer and the PVC middle layer are shown in Table 6.

[0095] Table 6 Formula

[0096] Surface formulation Comparison Group 1 Comparison Group 2 Comparison Group 3 Comparison Group 4 Comparison Group 5 Polyvinyl chloride resin 100 100 100 105 95 Plasticizer DINP 56 50 50 55 55 Lubricant stearic acid 0.3 0.3 0.4 0.5 0.6 Stabilizer calcium stearate 2 3 3 2 2 Titanium dioxide 20 20 20 10 15 Calcium carbonate filler 5 15 20 15 20 Antioxidant phosphite 1 1 1 2 2 UV9 anti-ultraviolet additive 2 1 2 1 1 Middle layer formula Comparison Group 1 Comparison Group 2 Comparison Group 3 Comparison Group 4 Comparison Group 5 Polyvinyl chloride resin 100 100 100 105 95 Plasticizer DINP 56 50 50 55 55 Lubricant stearic acid 0.3 0.3 0.4 0.5 0.6 Stabilizer calcium stearate 2 3 3 2 2 Titanium dioxide 10 9 10 10 10 Calcium carbonate filler 20 15 20 15 20 Antioxidant phosphite 1 1 1 2 2 UV9 anti-ultraviolet additive 1 1 2 1 1

[0097] The surface layer has a thickness of 0.25 mm, and the middle layer has a thickness of 1.25 mm.

[0098] The adhesive film layer and metal plate used in this embodiment are the same as in Example 1. Then, the PVC composite layers obtained from different groups are hot-pressed with the metal plate using the adhesive film layer in the same way as in Example 1 to obtain the coated metal plate.

[0099] The prepared coated metal sheet was tested according to the testing method in Example 2. The test results are shown in Table 7.

[0100] Table 7 Test Results

[0101]

[0102]

[0103] Comparing Examples 1 and 2 with Comparative Group 1, it can be seen that when using the same or similar formulations, the PVC-G structure exhibits significant differences compared to the PVC-H structure in terms of right-angle tear strength, seam peel strength, dimensional change rate after heat treatment, and retention rate of peel strength after 30 days of heat treatment at 80℃. Comparing Example 2 with Comparative Groups 2-5, it can be seen that the PVC-G structure performs far better than the PVC-H structure in terms of dimensional change rate after heat treatment and retention rate of peel strength after 30 days of heat treatment at 80℃. This indicates that the addition of glass fiber mat greatly improves the dimensional stability of the PVC roll material and effectively prevents plasticizer migration, ensuring high-temperature bonding performance. Comparing Example 2 with Comparative Groups 2-5, it can be seen that the PVC-G structure performs far better than the PVC-H structure in terms of right-angle tear strength and seam peel strength. This indicates that the PVC is treated in upper and lower layers, and the materials of the upper and lower PVC layers in contact with the glass fiber mat are adjusted differently to improve the composite strength of the materials.

[0104] Comparative Example 2

[0105] A coated metal sheet was prepared using PVC-G type waterproof membrane with glass fiber mat in the middle, which was selected from five groups of preferred formulation ratios. The glass fiber mat used was 60g / ㎡.

[0106] The following are the specific formulations for each layer of the PVC in the comparative example.

[0107] Table 8 Specific Formulas for Each Layer of PVC

[0108]

[0109]

[0110] Different PVC composite layers were prepared according to the formulation shown in Table 8 of this embodiment. The thicknesses of the PVC surface layer, middle layer and bottom layer were 0.25 mm, 0.5 mm and 0.75 mm respectively. Then, the PVC composite layers were prepared according to the hot pressing method of Example 2 in the order of surface layer, middle layer, glass fiber mat (same as in Example 2) and bottom layer.

[0111] The adhesive film layer and metal plate used in this embodiment are the same as those in Example 2. Different groups prepared PVC composite layers according to the method of Example 1, and then hot-pressed the adhesive film layer and metal plate according to the same method as in Example 2 to obtain coated metal plates.

[0112] The prepared coated metal sheet was tested according to the testing method in Example 2. The test results are shown in Table 9.

[0113] Table 9 Test Results

[0114]

[0115]

[0116] As can be seen from the comparison between Example 2 and Comparative Groups 6-10, when the formula ratio is outside the preferred range, under the same structural conditions, the performance of the obtained coated metal plate is lower than that of the examples with the preferred ratio.

[0117] In addition, in the above embodiments and comparative examples of the present invention, the average degree of polymerization of the polyvinyl chloride resin used was 1350; and the calcium carbonate used was light calcium carbonate (1250 mesh).

[0118] In the description of this specification, references to terms such as "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. Moreover, without contradiction, those skilled in the art can combine and integrate the different embodiments or examples described in this specification, as well as the features of those different embodiments or examples.

[0119] Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one of that feature. In the description of this invention, "a plurality of" means two or more, unless otherwise explicitly specified.

[0120] The above description is merely an exemplary embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any person skilled in the art can easily conceive of various variations or substitutions within the technical scope described in the present invention, and these should all be covered within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A PVC composite layer, characterized in that, The PVC composite layer comprises a PVC top layer, a PVC middle layer, a glass fiber layer, and a PVC bottom layer arranged in sequence. By weight, the PVC surface layer is made of at least the following components: 90-110 parts of polyvinyl chloride resin, 45-60 parts of plasticizer, 0.3-0.8 parts of lubricant, 2-4 parts of stabilizer, 10-20 parts of titanium dioxide, 5-30 parts of filler, 0.1-2 parts of antioxidant, and 0.1-2 parts of UV resistant agent. By weight, the PVC middle layer is made of at least the following components: 90-110 parts of polyvinyl chloride resin, 45-60 parts of plasticizer, 0.3-0.8 parts of lubricant, 2-4 parts of stabilizer, 5-15 parts of titanium dioxide, 5-30 parts of filler, 0.1-2 parts of antioxidant, and 0.1-2 parts of UV resistant agent. By weight, the PVC underlayer is made of at least the following components: 90-110 parts of polyvinyl chloride resin, 45-60 parts of plasticizer, 0.3-0.8 parts of lubricant, 2-4 parts of stabilizer, 5-30 parts of filler, 0.1-2 parts of antioxidant, and 0-1 part of UV protection agent. The polyvinyl chloride resin has an average degree of polymerization of 800-1500.

2. The PVC composite layer according to claim 1, characterized in that, The glass fiber layer is made of glass fiber mat; optionally, the basis weight of the glass fiber mat is 25-60 g / m². 2 Preferably 50-60g / m 2 Optionally, the thickness of the PVC composite layer is 0.8-2.0 mm; preferably, the thickness of the PVC composite layer is not less than 1.2 mm; more preferably, the thickness of the PVC composite layer is 1.5-2.0 mm; optionally, the glass fiber layer is located in the portion of the PVC composite layer with a thickness of 30%-70%, preferably in the portion with a thickness of 40%-60%.

3. The PVC composite layer according to claim 2, characterized in that, The thickness of the PVC surface layer is not less than 0.25 mm; the thickness of the PVC middle layer is not less than 0.34 mm, or the thickness of the PVC middle layer and the glass fiber layer is not less than 0.35 mm; optionally, the thickness of the PVC bottom layer is not less than 0.55 mm.

4. The PVC composite layer according to any one of claims 1-3, characterized in that, By weight, the PVC surface layer is made of at least the following components: 95-105 parts of polyvinyl chloride resin, 50-60 parts of plasticizer, 0.3-0.6 parts of lubricant, 2-3 parts of stabilizer, 10-20 parts of titanium dioxide, 5-20 parts of filler, 1-2 parts of antioxidant, and 1-2 parts of UV resistant agent. By weight, the PVC middle layer is made of at least the following components: 95-105 parts of polyvinyl chloride resin, 50-60 parts of plasticizer, 0.3-0.6 parts of lubricant, 2-3 parts of stabilizer, 8-10 parts of titanium dioxide, 15-20 parts of filler, 1-2 parts of antioxidant, and 1-2 parts of UV protection agent. By weight, the PVC underlayer is made of at least the following components: 95-105 parts of polyvinyl chloride resin, 50-60 parts of plasticizer, 0.3-0.6 parts of lubricant, 2-3 parts of stabilizer, 15-20 parts of filler, 1-2 parts of antioxidant, and 0.1-1 parts of UV protection agent. Preferably, the components are at least one of the following: The plasticizer includes DINP; The lubricant includes stearic acid; The stabilizer includes calcium stearate; The titanium dioxide includes rutile titanium dioxide; The filler includes one or more of calcium carbonate, flame retardant, and colorant; The antioxidants include phosphites; The UV-protective additive includes UV-9.

5. The PVC composite layer according to claim 4, characterized in that, The average particle size of the calcium carbonate is 800-2000 mesh, preferably 1300-1500 mesh; the flame retardant comprises Sb2O3 and Mg(OH)2, wherein the mass ratio of Sb2O3 to Mg(OH)2 is 1:3±0.3; optionally, the filler is different in different PVC composite layers; preferably, the filler in the PVC surface layer contains at least calcium carbonate; optionally, the PVC surface layer contains the calcium carbonate and the flame retardant; optionally, the mass ratio of the calcium carbonate to the flame retardant is 2±0.2:

1.

6. A method for preparing the PVC composite layer according to any one of claims 1-5, characterized in that, The components of the PVC composite layer are mixed and granulated to obtain PVC particles, which are then extruded through a single-screw sheet extruder to produce sheets of different layers; or the components of the PVC composite layer are mixed and formed in one step through a twin-screw sheet extruder to produce sheets of different layers. Then, the different layers of sheet and the glass fiber layer are laminated together in sequence.

7. A coated metal plate, characterized in that, The invention comprises a PVC composite layer and a metal plate layer as described in any one of claims 1-5, wherein an adhesive film layer is disposed between the PVC composite layer and the metal plate layer; optionally, the adhesive film layer comprises a first adhesive layer, a second adhesive layer and a third adhesive layer arranged in sequence, wherein the first adhesive layer is in contact with the PVC composite layer and the third adhesive layer is in contact with the metal plate. By weight: The first adhesive layer comprises 80-95 parts of polyolefin elastomer, 10-15 parts of polyolefin plasmon, and 10 parts of polyolefin oligomer. The second adhesive layer comprises 90-95 parts of maleic anhydride-grafted EVA, 60-95 parts of maleic anhydride-grafted polyolefin plasmon, 10-50 parts of maleic anhydride-grafted polyolefin elastomer, 20-30 parts of maleic anhydride-grafted polystyrene elastomer, 10-20 parts of tackifying petroleum resin, and 20-35 parts of polystyrene elastomer. The third adhesive layer comprises 40-75 parts of polyolefin elastomer, 40-75 parts of polyolefin plastisol, and 20-50 parts of maleic anhydride graft. Preferably, the thickness of the adhesive film layer is 0.10±0.05mm; Optionally, the first adhesive layer is 31±10μm, the second adhesive layer is 33±10μm, and the third adhesive layer is 33±10μm.

8. The coated metal plate according to claim 7, characterized in that, The metal plate used in the metal plate layer is selected from galvanized plate, aluminized zinc plate, aluminized zinc-magnesium plate or aluminized zinc-magnesium-manganese plate; optionally, the thickness of the metal plate is 0.5mm-0.8mm.

9. A method for preparing a coated metal plate according to any one of claims 7-8, characterized in that, Includes the following steps: The PVC composite layer, the adhesive film layer, and the metal plate layer are provided; The PVC composite layer, the adhesive film layer, and the metal plate layer are hot-pressed in a stacking order, so that the PVC composite layer is bonded to the metal plate layer through the adhesive film layer.

10. A building material containing a PVC composite layer as described in any one of claims 1-5 or a film-coated metal sheet as described in any one of claims 7-8, wherein the building material is optionally a roofing or wall panel.

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