A metal composite waterproof membrane and its preparation method

Abstract

The application relates to the technical field of waterproof building materials, and discloses a metal composite waterproof plate and a preparation method thereof, wherein the metal composite waterproof plate comprises, from top to bottom, a polymer layer, a glue layer and a metal plate; the polymer layer comprises the following components: ethylene-olefin copolymer, hydrogenated styrene-isoprene copolymer, hydroxyl-terminated polybutadiene styrene, high-impact polypropylene, a first antioxidant, a light stabilizer, a filler, titanium white and an antibacterial agent; the glue layer comprises the following components: ethylene-vinyl acetate copolymer, polyurethane elastomer, an adhesion promoter and a second antioxidant; and the adhesion promoter comprises 2-aminonicotinic acid ethyl ester and nano-kaolin. Through the technical scheme, the problem of poor peeling strength of the metal composite waterproof plate in the prior art is solved.

Description

Technical Field

[0001] This invention relates to the field of waterproof building materials technology, specifically to a metal composite waterproof board and its preparation method. Background Technology

[0002] Metal composite waterproof membrane is a commonly used building material with high utilization rate, light weight, convenient and quick installation, good corrosion resistance, and long service life. It can be combined to form a sealed and leak-proof metal roofing system, which is suitable for roof or wall decoration and waterproofing layers in various industrial and civil building projects.

[0003] Currently, the main method for manufacturing metal composite waterproof membranes involves bonding polymer sheets to the surface of metal sheets using adhesives. However, with increasingly harsh operating environments, these membranes are prone to peeling during use, severely impacting their lifespan and potentially posing significant safety hazards. Therefore, there is an urgent need to develop a metal composite waterproof membrane with high peel strength. Summary of the Invention

[0004] This invention proposes a metal composite waterproof membrane and its preparation method, which solves the problem of poor peel strength of metal composite waterproof membranes in related technologies.

[0005] The technical solution of the present invention is as follows:

[0006] This invention proposes a metal composite waterproof membrane, comprising a polymer layer, an adhesive layer, and a metal plate arranged sequentially from top to bottom. The polymer layer comprises the following components in parts by weight: 30-50 parts of ethylene-olefin copolymer, 5-15 parts of hydrogenated styrene-isoprene copolymer, 5-15 parts of hydroxyl-terminated polybutadiene styrene, 10-30 parts of high-impact polypropylene, 0.1-1 part of a first antioxidant, 0.1-1 part of a light stabilizer, 20-30 parts of filler, 1-5 parts of titanium dioxide, and 0.1-0.5 parts of an antibacterial agent.

[0007] The adhesive layer comprises the following components in parts by weight: 30-40 parts of ethylene-vinyl acetate copolymer, 20-30 parts of polyurethane elastomer, 4-6 parts of tackifier, and 1-2 parts of second antioxidant;

[0008] The thickener includes ethyl 2-aminonicotinic acid and nano-kaolin.

[0009] As a further technical solution, the mass ratio of 2-aminonicotinic acid ethyl ester to nano-kaolin is 1:3 to 3:1.

[0010] When the mass ratio of ethyl 2-aminonicotinic acid to nano-kaolin is 1:3 to 3:1, it helps to further improve the peel strength of the metal composite waterproof membrane.

[0011] As a further technical solution, the nano-kaolin is sodium p-hydroxybenzenesulfonate modified nano-kaolin.

[0012] Modifying nano-kaolin with sodium p-hydroxybenzenesulfonate can enhance its dispersion ability and allow it to form hydrogen bonds with the polymer layer and metal plate, which helps to further improve the peel strength of the metal composite waterproof membrane.

[0013] As a further technical solution, the preparation method of the sodium p-hydroxybenzenesulfonate modified nano-kaolin is as follows: dissolve sodium p-hydroxybenzenesulfonate in water, add nano-kaolin, disperse evenly, dehydrate, and obtain the sodium p-hydroxybenzenesulfonate modified nano-kaolin.

[0014] As a further technical solution, the mass ratio of sodium p-hydroxybenzenesulfonate to nano-kaolin is 1:9~19.

[0015] When the mass ratio of sodium p-hydroxybenzenesulfonate to nano-kaolin is 1:9~19, it helps to further improve the peel strength of the metal composite waterproof membrane.

[0016] As a further technical solution, the thickness of the polymer layer is 0.5~2.5mm;

[0017] The thickness of the adhesive layer is 0.01~0.1mm;

[0018] The thickness of the metal plate is 0.5~1.5mm.

[0019] As a further technical solution, the metal plate is a steel plate or an aluminum plate.

[0020] As a further technical solution, the ethylene-olefin copolymer is an ethylene-propylene copolymer and / or an ethylene-octene copolymer.

[0021] As a further technical solution, the first antioxidant and the second antioxidant are each independently one or more of antioxidant 1010, antioxidant 2246, and antioxidant 168;

[0022] The light stabilizer is Tinuvin XT847 or CYASORB B877.

[0023] The filler is one or more of calcium carbonate, talc, and silica.

[0024] The antibacterial agent is a nano-silver ion antibacterial agent.

[0025] The present invention also proposes a method for preparing the aforementioned metal composite waterproof membrane, comprising the following steps:

[0026] S1. The components of the polymer layer are blended and extruded, and then calendered to obtain a polymer layer roll material;

[0027] S2. Mix all components of the adhesive layer evenly, heat and melt to obtain hot melt adhesive;

[0028] S3. The hot melt adhesive is sprayed onto the surface of the metal plate, and then calendered and laminated in the order of polymer layer roll material, hot melt adhesive and metal plate from top to bottom to obtain metal composite waterproof board.

[0029] As a further technical solution, in step S1, during the blending extrusion, the temperature of zone one is 150~160℃, the temperature of zone two is 170~180℃, and the temperature of zone three is 160~170℃.

[0030] As a further technical solution, in step S2, the temperature during heating and melting is 180~190℃.

[0031] This invention also proposes the application of the metal composite waterproof board described above or the metal composite waterproof board prepared by the described preparation method in the construction field.

[0032] The working principle and beneficial effects of this invention are as follows:

[0033] 1. In this invention, the adhesive layer tackifier includes 2-aminonicotinic acid ethyl ester and nano-kaolin. On the one hand, it can improve the adhesion between the adhesive layer and the polymer layer and the metal plate through organic-inorganic synergistic effect, thereby improving the peel strength of the metal composite waterproof board. On the other hand, 2-aminonicotinic acid ethyl ester can form hydrogen bonds with the hydroxyl-terminated polybutadiene styrene in the polymer layer and the polar molecules on the surface of the metal plate, thereby improving the peel strength of the metal composite waterproof board. Detailed Implementation

[0034] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. 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 of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0035] Unless otherwise specified, in the following examples and comparative examples, the ethylene-propylene copolymer is designated as Vistamaxx-8880, the ethylene-octene copolymer as SK-8705L, the hydrogenated styrene-isoprene copolymer as BI-THIN602, the hydroxyl-terminated polybutadiene-styrene as HTBS-D0303, the high-impact polypropylene as PP-K8003, the calcium carbonate as 15μm in particle size, the titanium dioxide as R2219, the antibacterial agent as silver ion antibacterial agent-LD904, the ethylene-vinyl acetate copolymer as UE647-04, the polyurethane elastomer as TPU-385E, and the nano-kaolin as 300nm in particle size.

[0036] Example 1

[0037] A method for preparing a metal composite waterproof membrane includes the following steps:

[0038] S1. By weight, 30 parts of ethylene-propylene copolymer, 5 parts of hydrogenated styrene-isoprene copolymer, 5 parts of hydroxyl-terminated polybutadiene styrene, 10 parts of high-impact polypropylene, 0.1 parts of antioxidant 1010, 0.1 parts of Tinuvin XT847 light stabilizer, 20 parts of calcium carbonate, 1 part of titanium dioxide, and 0.1 parts of antibacterial agent are blended, extruded, and calendered to obtain a polymer layer roll material;

[0039] During the blending and extrusion process, the temperature in zone one is 150℃, the temperature in zone two is 170℃, and the temperature in zone three is 160℃.

[0040] S2. Mix 30 parts of ethylene-vinyl acetate copolymer, 20 parts of polyurethane elastomer, 0.5 parts of 2-aminonicotinic acid ethyl ester and 3.5 parts of nano-kaolin evenly, and heat to 180℃ to melt to obtain hot melt adhesive.

[0041] S3. Apply hot melt adhesive to the surface of 304 stainless steel plate, and perform calendering and lamination in the order of polymer layer roll material, hot melt adhesive and 304 stainless steel plate from top to bottom to obtain metal composite waterproof board.

[0042] The polymer layer of the metal composite waterproof membrane has a thickness of 0.5mm, the adhesive layer has a thickness of 0.01mm, and the 304 stainless steel plate has a thickness of 0.5mm.

[0043] Example 2

[0044] A method for preparing a metal composite waterproof membrane includes the following steps:

[0045] S1. By weight, 40 parts of ethylene-octene copolymer, 10 parts of hydrogenated styrene-isoprene copolymer, 10 parts of hydroxyl-terminated polybutadiene styrene, 20 parts of high-impact polypropylene, 0.5 parts of antioxidant 1010, 0.5 parts of Tinuvin XT847 light stabilizer, 25 parts of calcium carbonate, 3 parts of titanium dioxide, and 0.3 parts of antibacterial agent are blended, extruded, and calendered to obtain a polymer layer roll material;

[0046] During the blending extrusion process, the temperature in zone one is 160℃, the temperature in zone two is 180℃, and the temperature in zone three is 170℃.

[0047] S2. Mix 35 parts of ethylene-vinyl acetate copolymer, 25 parts of polyurethane elastomer, 1 part of 2-aminonicotinic acid ethyl ester and 4 parts of nano-kaolin evenly, and heat to 190℃ to melt to obtain hot melt adhesive.

[0048] S3. Apply hot melt adhesive to the surface of 304 stainless steel plate, and perform calendering and lamination in the order of polymer layer roll material, hot melt adhesive and 304 stainless steel plate from top to bottom to obtain metal composite waterproof board.

[0049] The polymer layer of the metal composite waterproof membrane is 1.5mm thick, the adhesive layer is 0.05mm thick, and the 304 stainless steel plate is 1.0mm thick.

[0050] Example 3

[0051] A method for preparing a metal composite waterproof membrane includes the following steps:

[0052] S1. By weight, 25 parts of ethylene-octene copolymer, 25 parts of ethylene-propylene copolymer, 15 parts of hydrogenated styrene-isoprene copolymer, 15 parts of hydroxyl-terminated polybutadiene styrene, 30 parts of high-impact polypropylene, 1 part of antioxidant 1010, 1 part of Tinuvin XT847 light stabilizer, 30 parts of calcium carbonate, 5 parts of titanium dioxide, and 0.5 parts of antibacterial agent are blended and extruded, then calendered to obtain a polymer layer roll material.

[0053] During the blending extrusion process, the temperature in zone one is 160℃, the temperature in zone two is 180℃, and the temperature in zone three is 170℃.

[0054] S2. Mix 40 parts of ethylene-vinyl acetate copolymer, 30 parts of polyurethane elastomer, 1 part of 2-aminonicotinic acid ethyl ester and 5 parts of nano-kaolin evenly, and heat to 190℃ to melt to obtain hot melt adhesive.

[0055] S3. Apply hot melt adhesive to the surface of 304 stainless steel plate, and perform calendering and lamination in the order of polymer layer roll material, hot melt adhesive and 304 stainless steel plate from top to bottom to obtain metal composite waterproof board.

[0056] The polymer layer of the metal composite waterproof membrane is 2.5mm thick, the adhesive layer is 0.1mm thick, and the 304 stainless steel plate is 1.5mm thick.

[0057] Example 4

[0058] The only difference between this embodiment and Embodiment 3 is that, in this embodiment, the weight parts of 2-aminonicotinic acid ethyl ester are 5 parts, and the weight parts of nano-kaolin are 1 part.

[0059] Example 5

[0060] The only difference between this embodiment and Embodiment 3 is that, in this embodiment, the weight parts of 2-aminonicotinic acid ethyl ester are 1.5 parts, and the weight parts of nano-kaolin are 4.5 parts.

[0061] Example 6

[0062] The only difference between this embodiment and Embodiment 3 is that, in this embodiment, the weight parts of 2-aminonicotinic acid ethyl ester are 4.5 parts and the weight parts of nano-kaolin are 1.5 parts.

[0063] Example 7

[0064] The only difference between this embodiment and Embodiment 5 is that in this embodiment, the nano-kaolin is sodium p-hydroxybenzenesulfonate modified nano-kaolin. The preparation method of sodium p-hydroxybenzenesulfonate modified nano-kaolin is as follows: sodium p-hydroxybenzenesulfonate is dissolved in water, nano-kaolin is added, dispersed evenly, and dehydrated to obtain sodium p-hydroxybenzenesulfonate modified nano-kaolin, wherein the mass ratio of sodium p-hydroxybenzenesulfonate to nano-kaolin is 1:5.

[0065] Example 8

[0066] The only difference between this embodiment and Embodiment 7 is that in this embodiment, the mass ratio of sodium hydroxybenzenesulfonate to nano-kaolin is 1:20.

[0067] Example 9

[0068] The only difference between this embodiment and Embodiment 7 is that in this embodiment, the mass ratio of sodium hydroxybenzenesulfonate to nano-kaolin is 1:9.

[0069] Example 10

[0070] The only difference between this embodiment and Embodiment 7 is that in this embodiment, the mass ratio of sodium hydroxybenzenesulfonate to nano-kaolin is 1:19.

[0071] Comparative Example 1

[0072] The only difference between this comparative example and Example 1 is that ethyl 2-aminonicotinic acid was not added in this comparative example, and the weight of the added nano-kaolin was 4 parts.

[0073] Comparative Example 2

[0074] The only difference between this comparative example and Example 1 is that no nano-kaolin was added in this comparative example, and the weight of ethyl 2-aminonicotinic acid added was 4 parts.

[0075] Comparative Example 3

[0076] The only difference between this comparative example and Example 1 is that ethyl 2-aminonicotinic acid and nano-kaolin were not added in this comparative example.

[0077] The peel strength of the metal composite waterproof membranes prepared in Examples 1-10 and Comparative Examples 1-3 was tested according to T / CBMCA017-2020 "Clad Steel Sheets for Building". After immersing the metal composite waterproof membranes prepared in Examples 1-10 and Comparative Examples 1-3 in water at room temperature for 24 hours, the peel strength after immersion was tested according to T / CBMCA017-2020 "Clad Steel Sheets for Building", and the peel strength retention rate after immersion was calculated. The test results are shown in Table 1 below.

[0078] Table 1 Test Results

[0079]

[0080] A comparison of Examples 1 and Comparative Examples 1-3 shows that the synergistic effect of ethyl 2-aminonicotinic acid and nano-kaolin significantly improves the peel strength of the metal composite waterproof membrane. A comparison of Examples 3-4 and Examples 5-6 shows that a mass ratio of ethyl 2-aminonicotinic acid to nano-kaolin of 1:3 to 3:1 further enhances the peel strength of the metal composite waterproof membrane. A comparison of Examples 5 and Examples 7-10 shows that modification of nano-kaolin with sodium p-hydroxybenzenesulfonate further improves the peel strength of the metal composite waterproof membrane. A comparison of Examples 9-10 and Examples 7-8 shows that a mass ratio of sodium p-hydroxybenzenesulfonate to nano-kaolin of 1:9 to 19 further enhances the peel strength of the metal composite waterproof membrane.

[0081] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A metal composite waterproof board comprising a polymer layer, an adhesive layer and a metal plate arranged in order from top to bottom, characterized in that, The high polymer layer comprises the following components in parts by weight: ethylene-olefin copolymer 30-50 parts, hydrogenated styrene-isoprene copolymer 5-15 parts, hydroxyl-terminated polybutadiene styrene 5-15 parts, high-impact polypropylene 10-30 parts, first antioxidant 0.1-1 part, light stabilizer 0.1-1 part, filler 20-30 parts, titanium white 1-5 parts, antibacterial agent 0.1-0.5 parts; The adhesive layer comprises the following components in parts by weight: ethylene-vinyl acetate copolymer 30-40 parts, polyurethane elastomer 20-30 parts, tackifier 4-6 parts, second antioxidant 1-2 parts; The tackifier comprises ethyl 2-aminonicotinate and nano-kaolin.

2. The metal composite waterproof sheet according to claim 1, wherein The mass ratio of the ethyl 2-aminonicotinate and nano-kaolin is 1:3-3:

1.

3. The metal composite waterproof sheet according to claim 1, wherein The nano-kaolin is sodium p-hydroxybenzenesulfonate-modified nano-kaolin.

4. The metal composite underlayment of claim 3, wherein, The preparation method of the sodium p-hydroxybenzenesulfonate-modified nano-kaolin comprises the following steps: dissolving sodium p-hydroxybenzenesulfonate in water, adding nano-kaolin, uniformly dispersing, and dehydrating to obtain the sodium p-hydroxybenzenesulfonate-modified nano-kaolin.

5. The metal composite underlayment panel of claim 4, wherein, The mass ratio of the sodium p-hydroxybenzenesulfonate and nano-kaolin is 1:9-19.

6. The metal composite underlayment panel of claim 1, wherein, The thickness of the high polymer layer is 0.5-2.5 mm; The thickness of the adhesive layer is 0.01-0.1 mm; The thickness of the metal plate is 0.5-1.5 mm.

7. The metal composite underlayment panel of claim 1, wherein, The ethylene-olefin copolymer is ethylene-propylene copolymer and / or ethylene-octene copolymer.

8. The metal composite underlayment panel of claim 1, wherein, The first antioxidant and the second antioxidant are each independently one or more of antioxidant 1010, antioxidant 2246, and antioxidant 168; The light stabilizer is Tinuvin XT847 light stabilizer or CYASORB B877 light stabilizer; The filler is one or more of calcium carbonate, talcum powder, and white carbon black; The antibacterial agent is a nano-silver ion antibacterial agent.

9. A method of manufacturing the metal composite waterproof sheet according to any one of claims 1 to 8, characterized by, The method comprises the following steps: S1, blending and extruding the components of the high polymer layer, and calendering to obtain a high polymer layer roll; S2, uniformly mixing the components of the adhesive layer, heating and melting to obtain a hot melt adhesive; S3, spraying the hot melt adhesive on the surface of the metal plate, and calendering in the order of the high polymer layer roll, the hot melt adhesive, and the metal plate from top to bottom to obtain a metal composite waterproof board.

10. Application of the metal composite waterproof board according to any one of claims 1-8 or prepared by the preparation method of claim 9 in the field of building.

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