A corrosion-resistant metal composite waterproof board and preparation method thereof

Abstract

The present invention relates to the technical field of waterproof boards, and proposes a corrosion-resistant metal composite waterproof board and a preparation method thereof. The corrosion-resistant metal composite waterproof board comprises a weather-resistant layer, an organic film layer, an adhesive layer, a metal plate, and a corrosion-resistant layer from top to bottom; the components of the weather-resistant layer include epoxy resin and a curing agent; the adhesive layer includes the following components in parts by weight: 100 parts of polyolefin, 3 to 6 parts of plasticizer, and 1 to 5 parts of antioxidant; the corrosion-resistant layer includes the following components in parts by weight: 60 to 80 parts of polyethylene, 35 to 45 parts of modified copolymer, 15 to 25 parts of filler, 5 to 8 parts of plasticizer, and 1 to 4 parts of antioxidant; the modified copolymer includes styrene-propylene alcohol copolymer resin, ethylene-vinyl acetate copolymer, and polymethylpentene copolymer. Through the above technical scheme, the problems of low peel strength and poor corrosion resistance of the metal composite waterproof board in the related art are solved.

Description

Technical Field

[0001] The present invention relates to the technical field of waterproof boards, and in particular to a corrosion-resistant metal composite waterproof board and a preparation method thereof. Background Art

[0002] Waterproof sheets can be divided into polymer-based waterproof sheets, metal waterproof sheets, etc., and are prepared through pre-pressing, co-extrusion, coating and other processes. Polymer-based waterproof sheets have the advantages of good flexibility and strong waterproof performance. Metal waterproof sheets are made of metal materials such as aluminum, zinc, and copper, and have good strength.

[0003] Metal composite waterproof board, as a new type of waterproof material, has received extensive attention in its research and development. This composite waterproof board combines the high strength of metal and the flexibility of polymer-based materials, making it have potential application value in many fields such as construction, transportation, subway, tunnel, engineering construction, etc. However, the existing metal composite waterproof board still has the defect of poor interlayer bonding. Especially in some corrosive environments, the external medium is easy to corrode the polymer substrate layer, which seriously reduces the service life of the waterproof board. Therefore, the development of a metal composite waterproof board with excellent interlayer peeling strength and high corrosion resistance will be of great significance to improving the safety and service life of the project, reducing maintenance costs, and broadening the application field of metal composite waterproof boards. Summary of the invention

[0004] The present invention provides a corrosion-resistant metal composite waterproof board and a preparation method thereof, which solves the problems of low peeling strength and poor corrosion resistance of the metal composite waterproof board in the related art.

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

[0006] The present invention provides a corrosion-resistant metal composite waterproof board, which comprises a weather-resistant layer, an organic film layer, an adhesive layer, a metal plate, and a corrosion-resistant layer in order from top to bottom;

[0007] The components of the weather-resistant layer include epoxy resin and curing agent;

[0008] The adhesive layer comprises the following components in parts by weight: 100 parts of polyolefin, 3 to 6 parts of plasticizer, and 1 to 5 parts of antioxidant;

[0009] The corrosion-resistant layer comprises the following components in parts by weight: 60-80 parts of polyethylene, 35-45 parts of modified copolymer, 15-25 parts of filler, 5-8 parts of plasticizer, and 1-4 parts of antioxidant;

[0010] The modified copolymer includes styrene-acryl alcohol copolymer resin, ethylene-vinyl acetate copolymer and polymethylpentene copolymer.

[0011] As a further technical solution, the organic film layer includes one of a PVC film layer, a TPO film layer, an EPDM film layer, a TPR film layer, an asphalt-based film layer, and a fluorocarbon film layer; the metal plate includes one of a stainless steel plate, a stainless iron plate, an aluminum alloy plate, and a galvanized steel plate; the filler includes one or more of white carbon black, mica powder, and talcum powder; the polyolefin includes one or more of polyethylene, polypropylene, polyvinyl chloride, and polytetrafluoroethylene; the plasticizer includes a phthalate plasticizer or a phosphate plasticizer; the antioxidant includes a hindered phenol antioxidant and / or a phosphite antioxidant; and the antioxidant includes a heterocyclic antioxidant.

[0012] As a further technical solution, the thickness of the weather-resistant layer is 0.1~0.2mm, the thickness of the organic film layer is 0.1~0.15mm, the thickness of the bonding layer is 0.05~0.1mm, the thickness of the metal plate is 0.5~1mm, and the thickness of the corrosion-resistant layer is 0.1~0.2mm.

[0013] As a further technical solution, the weather-resistant layer specifically comprises the following components in parts by weight: 100 parts of epoxy resin and 6 to 8 parts of curing agent.

[0014] As a further technical solution, the mass ratio of the styrene-propylene alcohol copolymer resin, the ethylene-vinyl acetate copolymer, and the polymethylpentene copolymer is (4-6):(3-5):1.

[0015] In the present invention, the mass ratio of styrene-propylene alcohol copolymer resin, ethylene-vinyl acetate copolymer and polymethylpentene copolymer is limited to (4-6):(3-5):1, which further improves the peel strength and corrosion resistance of the metal composite waterproof board.

[0016] As a further technical solution, the molar content of vinyl acetate in the ethylene-vinyl acetate copolymer is 18% to 26%.

[0017] As a further technical solution, the filler is a TPU modified filler.

[0018] In the present invention, TPU is used to modify the filler, thereby improving the dispersion of the filler and the bonding of the substrate, and further improving the peeling strength and corrosion resistance of the metal composite waterproof board.

[0019] As a further technical solution, in the TPU modified filler, TPU is a mixture of TPU-1160D and TPU-1198A.

[0020] In the present invention, when different types of TPU-1160D and TPU-1198ATPU are used together to modify the filler, the peeling strength and corrosion resistance of the metal composite waterproof board are further improved.

[0021] As a further technical solution, the mass ratio of TPU-1160D to TPU-1198A is 1:3~4:1.

[0022] As a further technical solution, the preparation method of the TPU modified filler comprises the following steps: mixing TPU and filler to obtain the TPU modified filler.

[0023] As a further technical solution, the mass ratio of the TPU to the filler is 1:11-14.

[0024] The present invention also provides a method for preparing the corrosion-resistant metal composite waterproof board, comprising the following steps:

[0025] After mixing the components of the weather-resistant layer, the organic film layer, the bonding layer and the corrosion-resistant layer respectively, the components of the organic film layer and the bonding layer are extruded on the upper surface of the metal plate from top to bottom, and the components of the corrosion-resistant layer are extruded to the lower surface of the metal plate. Then, the components of the weather-resistant layer are coated on the upper surface of the organic film layer, and hot-pressed to obtain a corrosion-resistant metal composite waterproof board.

[0026] The working principle and beneficial effects of the present invention are:

[0027] In the present invention, the metal composite waterproof board is provided with a weather-resistant layer, an organic film layer, an adhesive layer, a metal plate, and a corrosion-resistant layer in sequence from top to bottom, and a modified copolymer containing styrene-propylene alcohol copolymer resin, ethylene-vinyl acetate copolymer, and polymethylpentene copolymer is added to the corrosion-resistant layer, thereby significantly improving the peel strength and corrosion resistance of the metal composite waterproof board. DETAILED DESCRIPTION

[0028] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0029] In the following embodiments and comparative examples, the model of epoxy resin is E51; the model of polytetrafluoroethylene is FR104; the model of polyethylene is 1I60A; the model of styrene-acrylonitrile copolymer resin is SAA-100; the models of ethylene-vinyl acetate copolymers with molar contents of 16%, 33%, 18% and 26% are UE630, VA810, 7350M and 7470M respectively; the model of polymethylpentene copolymer is MX001.

[0030] Example 1

[0031] The corrosion-resistant metal composite waterproof board includes, from top to bottom, a weather-resistant layer, an organic film layer, an adhesive layer, a stainless steel plate, and a corrosion-resistant layer;

[0032] The thickness of the weather-resistant layer is 0.1mm, the thickness of the organic film layer is 0.15mm, the thickness of the bonding layer is 0.1mm, the thickness of the metal plate is 1mm, and the thickness of the corrosion-resistant layer is 0.2mm; the organic film layer is a PVC film; the metal plate is a stainless steel plate;

[0033] The weather-resistant layer comprises the following components in parts by weight: 100 parts of epoxy resin and 6 parts of diethylenetriamine;

[0034] The bonding layer includes the following components in parts by weight: 100 parts of polytetrafluoroethylene, 3 parts of dioctyl phthalate, and 1 part of antioxidant 1010;

[0035] The corrosion-resistant layer includes the following components in parts by weight: 60 parts of polyethylene, 35 parts of modified copolymer, 15 parts of mica powder, 5 parts of dioctyl phthalate, and 1 part of antioxidant MMBZ;

[0036] The modified copolymer is a styrene-propylene alcohol copolymer resin, an ethylene-vinyl acetate copolymer, and a polymethylpentene copolymer in a mass ratio of 4:5:2; the molar content of vinyl acetate in the ethylene-vinyl acetate copolymer is 16%;

[0037] The preparation method of the corrosion-resistant metal composite waterproof board comprises the following steps:

[0038] After mixing the components of the weather-resistant layer, the organic film layer, the bonding layer and the corrosion-resistant layer respectively, the components of the organic film layer and the bonding layer are extruded on the upper surface of the stainless steel plate from top to bottom, and the components of the corrosion-resistant layer are extruded to the lower surface of the stainless steel plate. Then, the components of the weather-resistant layer are coated on the upper surface of the organic film layer, and hot-pressed to obtain a corrosion-resistant metal composite waterproof board.

[0039] Example 2

[0040] The corrosion-resistant metal composite waterproof board includes, from top to bottom, a weather-resistant layer, an organic film layer, an adhesive layer, an aluminum alloy plate, and a corrosion-resistant layer;

[0041] The thickness of the weather-resistant layer is 0.2mm, the thickness of the organic film layer is 0.1mm, the thickness of the bonding layer is 0.05mm, the thickness of the metal plate is 0.5mm, and the thickness of the corrosion-resistant layer is 0.1mm; the organic film layer is a PVC film; the metal plate is a stainless steel plate;

[0042] The weather-resistant layer comprises the following components in parts by weight: 100 parts of epoxy resin and 7 parts of diethylenetriamine;

[0043] The adhesive layer includes the following components in parts by weight: 100 parts of polyethylene, 6 parts of dioctyl phthalate, and 10105 parts of antioxidant;

[0044] The corrosion-resistant layer includes the following components in parts by weight: 80 parts of polyethylene, 45 parts of modified copolymer, 25 parts of mica powder, 8 parts of dioctyl phthalate, and 4 parts of antioxidant MMBZ;

[0045] The modified copolymer is a styrene-propylene alcohol copolymer resin, an ethylene-vinyl acetate copolymer, and a polymethylpentene copolymer in a mass ratio of 4:5:2; the molar content of vinyl acetate in the ethylene-vinyl acetate copolymer is 16%;

[0046] The preparation method of the corrosion-resistant metal composite waterproof board comprises the following steps:

[0047] After the components of the weather-resistant layer, the organic film layer, the bonding layer and the corrosion-resistant layer are mixed respectively, the components of the organic film layer and the bonding layer are extruded on the upper surface of the aluminum alloy plate from top to bottom, and the components of the corrosion-resistant layer are extruded to the lower surface of the aluminum alloy plate. Then, the components of the weather-resistant layer are coated on the upper surface of the organic film layer, and hot-pressed to obtain a corrosion-resistant metal composite waterproof board.

[0048] Example 3

[0049] The corrosion-resistant metal composite waterproof board includes, from top to bottom, a weather-resistant layer, an organic film layer, an adhesive layer, a stainless steel plate, and a corrosion-resistant layer;

[0050] The thickness of the weather-resistant layer is 0.1mm, the thickness of the organic film layer is 0.15mm, the thickness of the bonding layer is 0.1mm, the thickness of the metal plate is 1mm, and the thickness of the corrosion-resistant layer is 0.2mm; the organic film layer is a PVC film; the metal plate is a stainless steel plate;

[0051] The weather-resistant layer comprises the following components in parts by weight: 100 parts of epoxy resin and 8 parts of diethylenetriamine;

[0052] The adhesive layer includes the following components in parts by weight: 100 parts of polyethylene, 5 parts of dioctyl phthalate, and 10103 parts of antioxidant;

[0053] The corrosion-resistant layer comprises the following components in parts by weight: 70 parts of polyethylene, 40 parts of modified copolymer, 20 parts of white carbon black, 7 parts of dioctyl phthalate, and 3 parts of antioxidant MMBZ;

[0054] The modified copolymer is a styrene-propylene alcohol copolymer resin, an ethylene-vinyl acetate copolymer, and a polymethylpentene copolymer in a mass ratio of 4:5:2; the molar content of vinyl acetate in the ethylene-vinyl acetate copolymer is 16%;

[0055] The preparation method of the corrosion-resistant metal composite waterproof board comprises the following steps:

[0056] After mixing the components of the weather-resistant layer, the organic film layer, the bonding layer and the corrosion-resistant layer respectively, the components of the organic film layer and the bonding layer are extruded on the upper surface of the stainless steel plate from top to bottom, and the components of the corrosion-resistant layer are extruded to the lower surface of the stainless steel plate. Then, the components of the weather-resistant layer are coated on the upper surface of the organic film layer, and hot-pressed to obtain a corrosion-resistant metal composite waterproof board.

[0057] Example 4

[0058] The only difference between this embodiment and embodiment 3 is that the modified copolymer is a styrene-propylene alcohol copolymer resin, an ethylene-vinyl acetate copolymer, and a polymethylpentene copolymer in a mass ratio of 6:2:1.

[0059] Example 5

[0060] The only difference between this embodiment and embodiment 3 is that the modified copolymer is a styrene-propylene alcohol copolymer resin, an ethylene-vinyl acetate copolymer, and a polymethylpentene copolymer in a mass ratio of 4:5:1.

[0061] Example 6

[0062] The only difference between this embodiment and embodiment 3 is that the modified copolymer is a styrene-propylene alcohol copolymer resin, an ethylene-vinyl acetate copolymer, and a polymethylpentene copolymer in a mass ratio of 6:3:1.

[0063] Example 7

[0064] The only difference between this embodiment and embodiment 6 is that the molar content of vinyl acetate in the ethylene-vinyl acetate copolymer is 33%.

[0065] Example 8

[0066] The only difference between this embodiment and embodiment 6 is that the molar content of vinyl acetate in the ethylene-vinyl acetate copolymer is 18%.

[0067] Example 9

[0068] The only difference between this embodiment and embodiment 6 is that the molar content of vinyl acetate in the ethylene-vinyl acetate copolymer is 26%.

[0069] Example 10

[0070] The only difference between this embodiment and embodiment 9 is that white carbon black is replaced by TPU modified white carbon black. The preparation method of TPU modified white carbon black comprises the following steps: after dissolving 1 g of TPU-1160D in 80 mL of cyclohexanone, 12 g of white carbon black is added, mixed, and dried to obtain TPU modified white carbon black.

[0071] Embodiment 11

[0072] The only difference between this embodiment and Embodiment 9 is that TPU-1160D is replaced by TPU-1198A.

[0073] Example 12

[0074] The only difference between this example and Example 9 is that 1 g of TPU-1160D is replaced by 0.25 g of TPU-1160D and 0.75 g of TPU-1198A.

[0075] Embodiment 13

[0076] The only difference between this example and Example 9 is that 1 g of TPU-1160D is replaced by 0.8 g of TPU-1160D and 0.2 g of TPU-1198A.

[0077] Comparative Example 1

[0078] The difference between this comparative example and Example 3 is that the modified copolymer is a styrene-propylene alcohol copolymer resin and an ethylene-vinyl acetate copolymer in a mass ratio of 4:5.

[0079] Comparative Example 2

[0080] The difference between this comparative example and Example 3 is that the modified copolymer is a styrene-acryl alcohol copolymer resin and a polymethylpentene copolymer in a mass ratio of 4:2.

[0081] Comparative Example 3

[0082] The difference between this comparative example and Example 3 is that the modified copolymer is an ethylene-vinyl acetate copolymer and a polymethylpentene copolymer in a mass ratio of 5:2.

[0083] The metal composite waterproof sheet samples prepared in Examples 1 to 13 and Comparative Examples 1 to 3 were respectively subjected to peel strength and corrosion resistance tests:

[0084] Peel strength: tested in accordance with standard T-CBMCA 017-2020 "Film-coated steel sheets for construction";

[0085] Corrosion resistance: After the sample is immersed in a 10% hydrochloric acid solution for 24 hours, the peel strength test after corrosion is carried out according to the standard T-CBMCA017-2020 "Film-coated steel sheets for construction", and the peel strength change rate is calculated. The peel strength change rate = [(peel strength before corrosion - peel strength after corrosion) / peel strength before corrosion] × 100%;

[0086] The results are shown in Table 1.

[0087] Table 1 Performance test results

[0088]

[0089] By comparing the data of Examples 1 to 13 and Comparative Examples 1 to 3, it is found that compared with Comparative Examples 1 to 3, the interlayer peeling strength of the corrosion-resistant layer and the metal plate of the metal composite waterproof board prepared in Examples 1 to 13 is higher, and the peeling strength change rate after corrosion immersion is smaller, indicating that the metal composite waterproof board is sequentially provided with a weather-resistant layer, an organic film layer, an adhesive layer, a metal plate, and a corrosion-resistant layer from top to bottom, and a modified copolymer containing styrene-propylene alcohol copolymer resin, ethylene-vinyl acetate copolymer, and polymethylpentene copolymer is added to the corrosion-resistant layer, thereby significantly improving the peeling strength and corrosion resistance of the metal composite waterproof board.

[0090] By comparing the data of Examples 3 to 6, it is found that compared with Examples 3 to 4, the interlayer peeling strength between the corrosion-resistant layer and the metal plate of the metal composite waterproof board prepared in Examples 5 to 6 is higher, indicating that the mass ratio of styrene-propylene alcohol copolymer resin, ethylene-vinyl acetate copolymer, and polymethylpentene copolymer is limited to (4 to 6): (3 to 5): 1, which further improves the peeling strength and corrosion resistance of the metal composite waterproof board.

[0091] By comparing the data of Examples 6 to 9, it is found that compared with Examples 6 to 7, the interlayer peeling strength between the corrosion-resistant layer and the metal plate of the metal composite waterproof board prepared in Examples 8 to 9 is higher, indicating that the use of TPU to modify the filler improves the dispersion of the filler and the bonding with the substrate, further improving the peeling strength and corrosion resistance of the metal composite waterproof board.

[0092] By comparing the data of Examples 10 to 13, it is found that compared with Examples 10 to 11, the interlayer peeling strength of the corrosion-resistant layer and the metal plate of the metal composite waterproof board prepared in Examples 12 to 13 is higher, indicating that when different types of TPU-1160D and TPU-1198ATPU are used together to modify the filler, the peeling strength and corrosion resistance of the metal composite waterproof board are further improved.

[0093] The above are only 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 in the protection scope of the present invention.

Claims

1. A corrosion-resistant metal composite waterproof board, characterized in that: From top to bottom, it includes a weather-resistant layer, an organic film layer, an adhesive layer, a metal plate, and a corrosion-resistant layer; The components of the weather-resistant layer include epoxy resin and curing agent; The adhesive layer comprises the following components in parts by weight: 100 parts of polyolefin, 3 to 6 parts of plasticizer, and 1 to 5 parts of antioxidant; The corrosion-resistant layer comprises the following components in parts by weight: 60-80 parts of polyethylene, 35-45 parts of modified copolymer, 15-25 parts of filler, 5-8 parts of plasticizer, and 1-4 parts of antioxidant; The modified copolymer includes styrene-acrylic alcohol copolymer resin, ethylene-vinyl acetate copolymer, and polymethylpentene copolymer; The organic film layer includes one of a PVC film layer, a TPO film layer, an EPDM film layer, a TPR film layer, an asphalt-based film layer, and a fluorocarbon film layer; The mass ratio of the styrene-propylene alcohol copolymer resin, the ethylene-vinyl acetate copolymer and the polymethylpentene copolymer is (4-6):(3-5):

1.

2. The corrosion-resistant metal composite waterproof board according to claim 1, characterized in that: The metal plate includes one of a stainless steel plate, a stainless iron plate, an aluminum alloy plate, and a galvanized steel plate; the filler includes one or more of white carbon black, mica powder, and talcum powder; the polyolefin includes one or more of polyethylene, polypropylene, polyvinyl chloride, and polytetrafluoroethylene; the plasticizer includes a phthalate plasticizer or a phosphate plasticizer; the antioxidant includes a hindered phenol antioxidant and / or a phosphite antioxidant; and the antioxidant includes a heterocyclic antioxidant.

3. The corrosion-resistant metal composite waterproof board according to claim 1, characterized in that: The molar content of vinyl acetate in the ethylene-vinyl acetate copolymer is 18% to 26%.

4. The corrosion-resistant metal composite waterproof board according to claim 1, characterized in that: The filler is a TPU modified filler.

5. The corrosion-resistant metal composite waterproof board according to claim 4, characterized in that: In the TPU modified filler, TPU is a mixture of TPU-1160D and TPU-1198A.

6. The corrosion-resistant metal composite waterproof board according to claim 5, characterized in that: The mass ratio of the TPU-1160D to TPU-1198A is 1:3~4:

1.

7. The corrosion-resistant metal composite waterproof board according to claim 4, characterized in that: The preparation method of the TPU modified filler comprises the following steps: mixing TPU and white carbon black to obtain the TPU modified filler.

8. The corrosion-resistant metal composite waterproof board according to claim 7, characterized in that: The mass ratio of the TPU to white carbon black is 1:11-14.

9. The method for preparing a corrosion-resistant metal composite waterproof board according to any one of claims 1 to 8, characterized in that: The following steps are involved: After mixing the components of the weather-resistant layer, the organic film layer, the bonding layer and the corrosion-resistant layer respectively, the components of the organic film layer and the bonding layer are extruded on the upper surface of the metal plate from top to bottom, and the components of the corrosion-resistant layer are extruded to the lower surface of the metal plate. Then, the components of the weather-resistant layer are coated on the upper surface of the organic film layer, and hot-pressed to obtain a corrosion-resistant metal composite waterproof board.

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