A polyolefin elastomer film self-adhesive bituminous waterproofing membrane, its preparation method and application

Abstract

The present application relates to a kind of polyolefin elastomer film self-adhesive asphalt waterproofing membrane and its preparation method and application, the membrane includes polyolefin elastomer film layer, barrier bonding layer, self-adhesive polymer modified asphalt layer and release film layer arranged in sequence, the raw material of self-adhesive polymer modified asphalt layer includes petroleum asphalt, tackifying resin, modifier, softening oil and filler, the mass ratio of petroleum asphalt, tackifying resin, modifier, softening oil, filler is 40~50:2~10:5~20:5~25:15~35, wherein, filler at least contains modified powder, modified powder is the surface of siliceous powder or quartz powder modified by amine group silane coupling agent.The present application is set by barrier bonding layer, not only can polyolefin elastomer and modified asphalt two materials isolate each other, so that it does not affect each other, improve the long-term stability of waterproofing membrane, polyolefin elastomer film layer and self-adhesive polymer modified asphalt layer can be firmly bonded together simultaneously, avoid film separation, improve the long-term stability and reliability of waterproofing membrane.

Description

Technical Field

[0001] This invention belongs to the field of building waterproofing materials technology, specifically relating to a polyolefin elastomer membrane self-adhesive bitumen waterproof membrane, its preparation method, and its application. Background Technology

[0002] Self-adhesive modified bitumen waterproof membranes without reinforcing material generally use high-molecular films such as HDPE cross-laminated film, PET film, and PET aluminized film as reinforcing materials, and self-adhesive polymer modified bitumen as adhesive. The membrane is lightweight, has good conformability, and is highly adaptable to the substrate and joints, and is widely used in waterproofing projects of buildings and structures.

[0003] However, in existing technologies, the elongation at break of reinforcing membranes for non-woven self-adhesive modified bitumen waterproof membranes is generally low. For example, the elongation at break of PET film is below 100%, and that of HDPE cross-laminated film is below 300%, making it difficult to meet the waterproofing needs of expansion joints, deformation joints, or areas with severe foundation settlement. Furthermore, due to the low elongation at break of PET film or HDPE cross-laminated film, the waterproof membrane shrinks and deforms during rolling, storage, and transportation due to stress changes, resulting in severe wrinkles after unrolling and poor sealing at the overlaps, thus affecting the reliability of the waterproofing system.

[0004] Meanwhile, PET films or HDPE cross-laminated films, due to their relatively hard materials, high molecular chain crystallinity, and low surface energy, have poor adhesion to self-adhesive polymer-modified asphalt, making them prone to film separation during long-term use. Furthermore, current self-adhesive polymer-modified asphalts generally use aromatic oils and ordinary paraffin oils to modify the low-temperature resistance of the asphalt. Aromatic oils and ordinary paraffin oils have high pour points, resulting in insufficient low-temperature resistance of the modified asphalt. At low temperatures, the asphalt tends to become brittle and hard, further exacerbating the film separation problem.

[0005] CN102991073B discloses a polyolefin composite modified bitumen wet-laid waterproof membrane and its production method, which consists of a modified bitumen adhesive layer capable of chemical cross-linking and physical interlocking bonding with concrete, an adhesive release film protective layer, and a polyolefin thermoplastic elastomer material layer; CN110408340B discloses a reactive adhesive wet-laid polymer waterproof membrane and its preparation method, which involves coating a reactive modified bitumen adhesive onto a high-strength and tough polyolefin thermoplastic elastomer base reinforcement layer using an oiling roller, and then covering the modified bitumen reactive adhesive layer with an anti-sticking release film. Although the above patents also involve the technology of preparing waterproof membranes by combining polyolefin thermoplastic elastomers and modified bitumen, the modified bitumen used is a modified bitumen adhesive layer capable of chemical cross-linking and physical interlocking bonding with concrete, which can solve the technical problem of bonding polymer membranes to cement concrete.

[0006] However, the thickness of these polyolefin thermoplastic elastomer (PET) layers ranges from 0.4 to 2.0 mm or 0.5 to 2.0 mm. The relatively large thickness of the PET layer significantly affects the adhesion between the roll material and the substrate. Furthermore, the direct hot-pressing bonding of the PET layer to the modified asphalt without considering the adhesion and compatibility between the PET and the modified asphalt can lead to film separation due to poor adhesion during long-term use, as well as performance degradation of the PET layer due to oil migration from the modified asphalt. Summary of the Invention

[0007] The technical problem to be solved by the present invention is to address the issues of easy separation of the adhesive film and performance degradation of the polyolefin thermoplastic elastomer layer in existing waterproof membranes made of polyolefin thermoplastic elastomer and modified bitumen, and to provide a novel polyolefin elastomer film self-adhesive bitumen waterproof membrane.

[0008] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0009] A polyolefin elastomer membrane self-adhesive bitumen waterproof membrane includes, from top to bottom, a polyolefin elastomer membrane layer, a self-adhesive polymer-modified bitumen layer, and a release membrane layer. The polyolefin elastomer membrane self-adhesive bitumen waterproof membrane further includes a barrier adhesive layer disposed between the polyolefin elastomer membrane layer and the self-adhesive polymer-modified bitumen layer. The raw materials of the self-adhesive polymer-modified bitumen layer include petroleum asphalt, tackifying resin, modifier, softening oil, and filler. The mass ratio of petroleum asphalt, tackifying resin, modifier, softening oil, and filler is 40–50:2–10:5–20:5–25:15–35. The filler contains at least a modified powder, which is silica powder or quartz powder with a surface modified by an aminosilane coupling agent.

[0010] In some embodiments, the aminosilane coupling agent is one or more combinations of γ-aminopropyltriethoxysilane and γ-aminopropyltrimethoxysilane.

[0011] In some specific embodiments, the mass ratio of the modified powder to the filler is 1:3 to 18. Preferably, the mass ratio of the modified powder to the filler is 1:5 to 10.

[0012] In some specific embodiments, the modified powder is silica powder or quartz powder whose surface has been modified with γ-aminopropyltriethoxysilane or γ-aminopropyltrimethoxysilane.

[0013] In some specific embodiments, the filler also includes at least one of talc, heavy calcium carbonate, light calcium carbonate, montmorillonite, and kaolin.

[0014] In some specific embodiments, the softening oil is one or more of low-pour-point naphthenic oil and low-pour-point paraffinic oil. Preferably, the softening oil is a mixture of low-pour-point naphthenic oil and low-pour-point paraffinic oil in a mass ratio of 0.5 to 5:1, wherein the pour point of the low-pour-point naphthenic oil is below -25°C, and the pour point of the low-pour-point paraffinic oil is below -40°C. More preferably, the mass ratio of the low-pour-point naphthenic oil and low-pour-point paraffinic oil is 1 to 3:1.

[0015] In some specific embodiments, the modifier is one or more of styrene-based thermoplastic elastomers and styrene-butadiene rubber. Preferably, the modifier is a combination of styrene-based thermoplastic elastomers and styrene-butadiene rubber in a mass ratio of 0.3 to 1.6:1.

[0016] In some specific embodiments, the styrene-based thermoplastic elastomer is at least one of SBS, SEBS, SIS, and SEPS; and the styrene-butadiene rubber is at least one of emulsion styrene-butadiene rubber and solution styrene-butadiene rubber.

[0017] In some specific embodiments, the petroleum asphalt is at least one of 70#, 90#, and 200# petroleum asphalt;

[0018] In some specific embodiments, the tackifying resin is at least one of C5 petroleum resin, C9 petroleum resin, C5 / C9 copolymer petroleum resin, rosin resin, and hydrogenated rosin resin.

[0019] In some specific embodiments, the mass ratio of the petroleum asphalt, tackifying resin, modifier, softening oil, and filler is 40-50:5-10:8-15:10-20:20-35.

[0020] In some embodiments, the barrier adhesive layer comprises at least a first adhesive layer bonded to the polyolefin elastic film layer, a second adhesive layer bonded to the self-adhesive polymer-modified bitumen layer, and a barrier layer located between the first adhesive layer and the second adhesive layer.

[0021] In some specific embodiments, the first adhesive layer is a maleic anhydride-grafted polypropylene layer (PP-g-MAH), the second adhesive layer is a maleic anhydride-grafted polyethylene layer (PE-g-MAH), and the barrier layer is a polyester layer or a polyamide layer, such as PET, PA, etc.

[0022] In this invention, the maleic anhydride-grafted polypropylene layer contains both polar and non-polar groups, exhibiting excellent adhesion to both non-polar polyolefin elastomer film layers and polar polyester or polyamide layers, further ensuring that the polyolefin elastomer film layer and the barrier adhesive layer will not separate. Furthermore, the maleic anhydride groups in the maleic anhydride-grafted polyethylene layer have hydrogen bonding interactions with the amine groups in the modified powder, which further ensures that the barrier adhesive layer and the self-adhesive polymer-modified asphalt layer will not separate.

[0023] In some specific embodiments, the barrier adhesive layer is prepared by adding the raw materials used in each layer of the barrier adhesive layer into different screw extruders, melting and extruding them, extruding and fusing them in a T-die, and then stretching, pulling, and winding them to obtain the finished product. The extrusion temperature of maleic anhydride-grafted polypropylene is 190-210°C, the extrusion temperature of polyester or polyamide is 220-240°C, and the extrusion temperature of maleic anhydride-grafted polyethylene is 180-200°C.

[0024] In some embodiments, the barrier adhesive layer is a multilayer co-extruded film.

[0025] In some embodiments, the thickness of the barrier adhesive layer is 0.02 to 0.12 mm.

[0026] In some embodiments, the polyolefin elastomer film is a TPO film or a POE film; the thickness of the polyolefin elastomer film is 0.1 to 0.4 mm.

[0027] Compared to existing polyolefin elastomer membrane self-adhesive bitumen waterproofing membranes, this membrane is thinner, more flexible, and has a higher elongation at break. It exhibits strong conformability and adaptability to the substrate, meeting the waterproofing needs of expansion joints, deformation joints, or areas with severe foundation settlement. Furthermore, compared to traditional non-reinforced self-adhesive bitumen waterproofing membranes, this membrane uses a polyolefin elastomer membrane layer instead of the reinforcing membrane, resulting in a smooth appearance, wrinkle-free membrane overall and overlapping edges. The use of self-adhesive bitumen for bonding and overlapping ensures excellent sealing and high reliability of the waterproofing system.

[0028] Preferably, the thickness of the polyolefin elastomer film layer is 0.2 to 0.3 mm.

[0029] In some specific embodiments, the polyolefin elastomer film layer is a homogeneous polyolefin elastomer film, a fiber-reinforced polyolefin elastomer film, or a polyolefin elastomer film with a fiber backing.

[0030] In some embodiments, the thickness of the polyolefin elastomer film self-adhesive bitumen waterproof membrane is 1.5 to 2.2 mm; further, the thickness of the polyolefin elastomer film self-adhesive bitumen waterproof membrane is 1.5 to 2.0 mm.

[0031] In some embodiments, the thickness of the self-adhesive polymer-modified bitumen layer is 1.0 to 1.9 mm.

[0032] The second technical solution adopted by the present invention is: the preparation method of the above-mentioned polyolefin elastomer film self-adhesive bitumen waterproof membrane includes the following steps:

[0033] (1) Preparation of self-adhesive polymer-modified asphalt

[0034] Petroleum asphalt and softening oil are stirred and dehydrated at 140–150°C, then modifiers, tackifying resins and fillers are added, and the mixture is sheared and mixed at 170–180°C to obtain the self-adhesive polymer-modified asphalt.

[0035] (2) Preparation of polyolefin elastomer film / barrier adhesive layer composite film

[0036] A polyolefin elastomer film and a barrier adhesive layer are hot-pressed together at a temperature of 120–150°C to prepare a polyolefin elastomer film / barrier adhesive layer composite film.

[0037] (3) Preparation of polyolefin elastomer film self-adhesive bitumen waterproof membrane

[0038] The self-adhesive polymer-modified bitumen is coated onto the surface of the release membrane at 140-150°C and cooled. After the surface of the self-adhesive polymer-modified bitumen cools to 40-60°C, a polyolefin elastomer film / barrier adhesive layer composite film is applied, extruded and bonded, and then cooled and molded to obtain the polyolefin elastomer film self-adhesive bitumen waterproof membrane.

[0039] The third technical solution adopted by the present invention is: the use of the above-mentioned polyolefin elastomer film self-adhesive bitumen waterproof membrane in the field of waterproofing of buildings or structures.

[0040] Due to the application of the above technical solution, the present invention has the following advantages compared with the prior art:

[0041] The polyolefin elastomer film self-adhesive bitumen waterproof membrane of the present invention features a barrier adhesive layer between the polyolefin elastomer film layer and the self-adhesive polymer-modified bitumen layer. This not only isolates the polyolefin elastomer and modified bitumen materials from each other, preventing them from interfering with each other and solving the problem of mechanical property degradation of the polyolefin elastomer film caused by the migration of low-molecular-weight oils from the modified bitumen, thus improving the long-term stability of the waterproof membrane, but also firmly bonds the polyolefin elastomer film layer and the self-adhesive polymer-modified bitumen layer together, effectively forming an integrated structure, preventing film separation, and improving the long-term stability and reliability of the waterproof membrane. Furthermore, the redesigned formulation of the self-adhesive polymer-modified bitumen layer further prevents film separation. Detailed Implementation

[0042] As described in the background section, existing technologies for preparing waterproof membranes by combining polyolefin thermoplastic elastomers and modified bitumen have problems such as film separation due to poor adhesion between the polyolefin thermoplastic elastomer and self-adhesive bitumen, and performance degradation of the polyolefin thermoplastic elastomer material layer due to oil migration from the modified bitumen during long-term application.

[0043] The main concept of this invention lies in using a barrier adhesive layer as an intermediate material to connect the polyolefin elastomer film layer and the self-adhesive polymer modified bitumen layer. On the one hand, its barrier properties isolate the two materials, polyolefin elastomer and modified bitumen, so that they do not affect each other, solving the problem of the decline in the mechanical properties of polyolefin elastomer film caused by the migration of low molecular weight oil in modified bitumen, and improving the long-term stability of waterproof membrane. On the other hand, the barrier adhesive layer can firmly bond the polyolefin elastomer film layer and the self-adhesive polymer modified bitumen layer together, effectively forming an integrated structure and avoiding the problem of film separation.

[0044] A further aspect of this invention lies in redesigning the formulation of the self-adhesive polymer-modified asphalt layer. Utilizing the hydrogen bonding between the amine and maleic anhydride groups in the modified powder, the problem of film separation is further avoided. In some preferred embodiments, the softener in the raw materials of the self-adhesive polymer-modified asphalt layer uses low-pour-point naphthenic oil and low-pour-point paraffin oil, effectively improving the low-temperature brittleness and low-temperature peeling properties of the self-adhesive polymer-modified asphalt layer. This ensures that the polyolefin elastomer film self-adhesive asphalt waterproof membrane maintains good adhesion even below -20°C, preventing film separation.

[0045] A further aspect of this invention is that the thickness of the polyolefin elastomer membrane layer is set to 0.1–0.4 mm. On the one hand, the membrane layer is thinner, more flexible, and has a higher elongation at break, resulting in better conformability and adaptability to the substrate, which can meet the waterproofing requirements of expansion joints, deformation joints, or areas with severe foundation settlement. On the other hand, the polyolefin elastomer membrane layer replaces the reinforcing membrane on existing non-woven self-adhesive bitumen waterproof membranes, resulting in a smooth appearance, no wrinkles on the membrane as a whole or at the overlapping edges, and good sealing performance due to the use of self-adhesive bitumen for bonding and overlapping, thus ensuring high reliability of the waterproofing system.

[0046] The technical solutions of the present invention will be described in detail below with reference to specific embodiments, so that those skilled in the art can better understand and implement the technical solutions of the present invention, but the present invention is not limited to the scope of the examples described.

[0047] Some of the raw materials and their sources in the following examples are as follows:

[0048] Petroleum asphalt: 70# asphalt, 200# asphalt, Shandong Jingbo Petrochemical Co., Ltd.;

[0049] Tackifying resins: C5 petroleum resin, C9 petroleum resin, Shandong Jingshun Chemical Co., Ltd.;

[0050] Low pour point naphthenic oil: KN4006, pour point -28℃, Hengshui Diyi Petrochemical Co., Ltd.;

[0051] Low pour point paraffin oil: SpectraSyn 8, pour point -48℃, Dongguan Hongli Chemical Technology Co., Ltd.;

[0052] Aromatic oil: SYA1220, pour point 8℃, Luoyang Jiasheng Oil Products Co., Ltd.;

[0053] Ordinary paraffin oil: 68#, pour point -25℃, Jining Guoyun Lubricating Oil Co., Ltd.;

[0054] Styrene-butadiene-styrene block copolymer (SBS): 791, Baling Petrochemical Co., Ltd.;

[0055] Styrene-butadiene rubber: Emulsion styrene-butadiene rubber, SBR-50, Shandong Gaoshi Science & Technology Co., Ltd.;

[0056] Modified silica powder: KH550 modified silica, Shijiazhuang Zhuzhong Technology Co., Ltd.;

[0057] Polyolefin elastomer membrane: homogeneous TPO membrane, thickness 0.2 mm and 0.4 mm;

[0058] Adhesive barrier layer: PP-g-MAH / PA / PE-g-MAH three-layer co-extruded film;

[0059] HDPE cross-laminated film and PET metallized film: 0.10mm and 0.06mm respectively, Shanghai Youpusi Materials Technology Co., Ltd.

[0060] Example 1

[0061] The polyolefin elastomer membrane self-adhesive bitumen waterproof membrane provided in this embodiment includes, from top to bottom, a polyolefin elastomer membrane layer, a barrier adhesive layer, a self-adhesive polymer modified bitumen layer, and a release membrane layer.

[0062] Among them, the polyolefin elastomer film layer is a homogeneous TPO film with a thickness of 0.2 mm;

[0063] The barrier adhesive layer is a 0.05mm thick PP-g-MAH / PA / PE-g-MAH three-layer co-extruded film.

[0064] The release liner is a 0.035mm thick PET release liner.

[0065] The raw material formula for the self-adhesive polymer-modified asphalt layer is 45kg 70# petroleum asphalt, 6kg C5 petroleum resin, 10kg low pour point naphthenic oil, 5kg low pour point paraffin oil, 3kg SBS, 7kg styrene-butadiene rubber, 21kg talc powder and 3kg KH550 modified silica.

[0066] The self-adhesive bitumen waterproof membrane made of polyolefin elastomer film is prepared by the following method:

[0067] (1) Preparation of self-adhesive polymer-modified asphalt

[0068] Petroleum asphalt, low-pour-point naphthenic oil, and low-pour-point paraffin oil were stirred and dehydrated for 30 minutes at 145-150℃. Then, SBS and styrene-butadiene rubber were added, and the mixture was heated to 175-180℃ and sheared for 3 hours. Then, tackifying resin was added, and the mixture was sheared for 30 minutes at 175-180℃. Then, filler was added, and the mixture was sheared for 1 hour at 175-180℃. The mixture was then cooled to obtain self-adhesive polymer-modified asphalt.

[0069] (2) Preparation of polyolefin elastomer / barrier adhesive layer composite film

[0070] A polyolefin elastomer film and a first adhesive layer of a barrier adhesive layer are hot-pressed together at a temperature of 130–140°C to prepare a polyolefin elastomer / barrier adhesive layer composite film.

[0071] (3) Preparation of polyolefin elastomer film self-adhesive bitumen waterproof membrane

[0072] The self-adhesive polymer-modified asphalt is cooled to 140-150°C and transported to an oiling tank. The self-adhesive asphalt is coated on the surface of the release membrane, and the thickness is fixed by a thickness roller. Then, it is floated and cooled in a water bed. When the surface of the self-adhesive polymer-modified asphalt is cooled to 40-60°C, the polyolefin elastomer / barrier adhesive layer composite film is extruded and bonded to the roll material, and then cooled and shaped to obtain the polyolefin elastomer film self-adhesive asphalt waterproof roll material.

[0073] Example 2

[0074] The polyolefin elastomer film self-adhesive bitumen waterproof membrane provided in this embodiment is basically the same as that in Embodiment 1, except that:

[0075] The raw material formula for the self-adhesive polymer modified asphalt layer is 30kg 70# petroleum asphalt, 15kg 200# petroleum asphalt, 6kg C5 petroleum resin, 8kg low pour point naphthenic oil, 5kg low pour point paraffin oil, 5kg SBS, 5kg styrene-butadiene rubber, 22kg talc powder and 4kg KH550 modified silica.

[0076] Example 3

[0077] The polyolefin elastomer membrane self-adhesive bitumen waterproof membrane provided in this embodiment is basically the same as that in Embodiment 1, except that the polyolefin elastomer membrane layer is made of a 0.40mm thick homogeneous TPO membrane.

[0078] Example 4

[0079] The polyolefin elastomer membrane self-adhesive bitumen waterproof membrane provided in this embodiment is basically the same as in Embodiment 1, except that the raw material formula of the self-adhesive polymer modified bitumen layer is 42kg 70# petroleum bitumen, 8kg C9 petroleum resin, 10kg low pour point naphthenic oil, 5kg low pour point paraffin oil, 3kg SBS, 7kg styrene-butadiene rubber, 22kg kaolin and 3kg KH550 modified silica.

[0080] Comparative Example 1

[0081] The self-adhesive modified bitumen waterproof membrane provided in this comparative example is a conventional PET film self-adhesive modified bitumen waterproof membrane. The raw material formula of the self-adhesive polymer modified bitumen layer is the same as that in Example 1. The difference from Example 1 is that a PET aluminized film is used instead of the polyolefin elastomer film layer and the barrier adhesive layer.

[0082] Comparative Example 2

[0083] The polyolefin elastomer membrane self-adhesive bitumen waterproof membrane provided in this comparative example is basically the same as that in Example 1. The difference from Example 1 is that no barrier adhesive layer is provided, and the polyolefin elastomer membrane layer is directly bonded to the self-adhesive polymer modified bitumen layer.

[0084] Comparative Example 3

[0085] The polyolefin elastomer membrane self-adhesive bitumen waterproof membrane provided in this comparative example is basically the same as that in Example 1. The difference from Example 1 is that a five-layer co-extruded barrier film of PP / TIE / PA / TIE / PE commonly used in the market is used instead of the three-layer co-extruded film of PP-g-MAH / PA / PE-g-MAH.

[0086] Comparative Example 4

[0087] The polyolefin elastomer membrane self-adhesive bitumen waterproof membrane provided in this comparative example is basically the same as that in Example 1, except that no modified powder is added to the raw material formula of the self-adhesive polymer modified bitumen layer.

[0088] Comparative Example 5

[0089] The polyolefin elastomer membrane self-adhesive bitumen waterproof membrane provided in this comparative example is basically the same as that in Example 1, except that the low pour point naphthenic oil in the raw material formulation of the self-adhesive polymer modified bitumen layer is replaced by aromatic oil, and the low pour point paraffin oil is replaced by ordinary paraffin oil.

[0090] Comparative Example 6

[0091] The self-adhesive bitumen waterproof membrane provided in this comparative example is basically the same as that in Example 1, except that the polyolefin elastic film layer is replaced by a conventional 0.10mm HDPE cross-laminated film.

[0092] The waterproof membranes prepared in Examples 1-4 and Comparative Examples 1-6 were tested according to GB23441-2009 "Self-adhesive polymer modified bitumen waterproof membranes", and the results are shown in Table 1.

[0093] Table 1. Test results of Examples 1-4 and Comparative Examples 1-6

[0094]

[0095]

[0096] The results show that in Examples 1-4 and Comparative Examples 2-5, using polyolefin elastomer films as the reinforcing layer of the self-adhesive polymer-modified bitumen waterproof membrane, the elongation at break is above 750%, while in Comparative Examples 1 and 6, using PET aluminized film and HDPE cross-laminated film as reinforcing films respectively, the elongation at break is only 125% and 385%, respectively. The polyolefin elastomer film self-adhesive bitumen waterproof membrane prepared by this invention has stronger conformability and adaptability to the substrate, and can meet the waterproofing needs of expansion joints, deformation joints, or areas with severe foundation settlement.

[0097] Examples 1-4 use a polyolefin elastomer film as the reinforcing layer of the self-adhesive polymer-modified bitumen waterproof membrane, a PP-g-MAH / PA / PE-g-MAH three-layer co-extruded film as the barrier adhesive layer, and a composite modified bitumen of KH550 modified silica, low-pour-point naphthenic oil, and low-pour-point paraffin oil. This effectively ensures the adhesive performance of the waterproof membrane, showing cohesive failure at room temperature and no film separation even at -20℃. Furthermore, thermal aging results demonstrate that Examples 1-4 exhibit excellent aging resistance; not only is there no change in appearance before and after thermal aging, but tensile test results show excellent tensile strength retention, exceeding 95%.

[0098] Comparative Example 1 used a PET aluminized film as the reinforcing film. At -20℃, film separation occurred, indicating that the PET aluminized film, due to its material properties, has poor adhesion to the self-adhesive polymer-modified asphalt. Comparative Example 2, compared to Example 1, did not have a barrier adhesive layer. After heat aging, it yellowed in appearance, and the tensile strength retention rate was only 75%, indicating that oil migration occurred in the self-adhesive polymer-modified asphalt during heat aging, leading to changes in the appearance and a decline in the mechanical properties of the waterproof membrane before and after heat aging. Simultaneously, the peel performance test at -20℃ showed a peel strength of only 0.38 N / mm, indicating film separation. These results demonstrate that the presence of a barrier adhesive layer not only improves the adhesion between the polyolefin elastomer film and the self-adhesive polymer-modified asphalt but also prevents oil migration that leads to changes in the appearance and a decline in the mechanical properties of the waterproof membrane.

[0099] Compared to Example 1, Comparative Example 3 used a commercially available five-layer co-extruded barrier film of PP / TIE / PA / TIE / PE instead of the three-layer co-extruded film of PP-g-MAH / PA / PE-g-MAH. Although there was no significant change in appearance before and after heat aging, and the tensile strength retention rate was also high, indicating that the five-layer co-extruded barrier film of PP / TIE / PA / TIE / PE also has good barrier performance. However, the peel performance test showed that because the commercially available five-layer co-extruded barrier film of PP / TIE / PA / TIE / PE does not have a dedicated adhesive layer for connecting with the polyolefin elastomer film and the self-adhesive polymer modified bitumen, the peel strength was low, and film separation occurred during the test.

[0100] Compared with Example 1, Comparative Examples 4 and 5, since no modified powder and low pour point softening oil were added respectively, although the waterproof membrane also showed cohesive failure during the peel test at room temperature, film separation occurred during the test at -20℃. This indicates that the modified powder and low pour point softening oil work synergistically to achieve the low-temperature bonding performance of the waterproof membrane.

[0101] Compared with Example 1, Comparative Example 6 used a 0.10 mm HDPE cross-laminated film instead of the polyolefin elastic film layer. During the low temperature test, film separation occurred between the HDPE cross-laminated film and the barrier adhesive layer. This was because the upper surface material of the barrier adhesive layer was PP-MAH resin, which had poor compatibility with HDPE and poor adhesion.

[0102] The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the content of the present invention and implement it accordingly. They should not be construed as limiting the scope of protection of the present invention. All equivalent changes or modifications made in accordance with the spirit and essence of the present invention should be covered within the scope of protection of the present invention.

[0103] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

Claims

1. A polyolefin elastomer membrane self-adhesive bitumen waterproof membrane, comprising, from top to bottom, a polyolefin elastomer membrane layer, a self-adhesive polymer-modified bitumen layer, and a release membrane layer, characterized in that, The polyolefin elastomer membrane self-adhesive bitumen waterproof membrane further includes a barrier adhesive layer disposed between the polyolefin elastomer membrane layer and the self-adhesive polymer modified bitumen layer. The raw materials of the self-adhesive polymer modified bitumen layer include petroleum asphalt, tackifying resin, modifier, softening oil and filler. The mass ratio of petroleum asphalt, tackifying resin, modifier, softening oil and filler is 40-50:2-10:5-20:5-25:15-35. The filler contains at least modified powder, which is silica powder or quartz powder whose surface has been modified by an aminosilane coupling agent. The barrier adhesive layer comprises at least a first adhesive layer bonded to the polyolefin elastomer film layer, a second adhesive layer bonded to the self-adhesive polymer modified bitumen layer, and a barrier layer located between the first adhesive layer and the second adhesive layer. The first adhesive layer is a maleic anhydride-grafted polypropylene layer, the second adhesive layer is a maleic anhydride-grafted polyethylene layer, and the barrier layer is a polyester layer or a polyamide layer. The softening oil is at least one of low pour point naphthenic oil and low pour point paraffinic oil; the pour point of the low pour point naphthenic oil is below -25°C, and the pour point of the low pour point paraffinic oil is below -40°C. The polyolefin elastomer film layer is a TPO film or a POE film.

2. The polyolefin elastomer membrane self-adhesive bitumen waterproof membrane according to claim 1, characterized in that: The aminosilane coupling agent is one or a combination of several of γ-aminopropyltriethoxysilane and γ-aminopropyltrimethoxysilane.

3. The polyolefin elastomer film self-adhesive bitumen waterproof membrane according to claim 1, characterized in that: The mass ratio of the modified powder to the filler is 1:3 to 18.

4. The polyolefin elastomer membrane self-adhesive bitumen waterproof membrane according to claim 1, characterized in that: The filler also includes at least one of talc, heavy calcium carbonate, light calcium carbonate, montmorillonite, and kaolin.

5. The polyolefin elastomer membrane self-adhesive bitumen waterproof membrane according to claim 4, characterized in that: The softening oil is a mixture of low pour point naphthenic oil and low pour point paraffin oil in a mass ratio of 0.5 to 5:

1.

6. The polyolefin elastomer membrane self-adhesive bitumen waterproof membrane according to claim 1, characterized in that: The modifier is one or more of styrene-based thermoplastic elastomers and styrene-butadiene rubber; and / or, the petroleum asphalt is at least one of 70#, 90#, and 200# petroleum asphalt; and / or, the tackifying resin is at least one of C5 petroleum resin, C9 petroleum resin, C5 / C9 copolymer petroleum resin, rosin resin, and hydrogenated rosin resin.

7. The polyolefin elastomer film self-adhesive bitumen waterproof membrane according to claim 6, characterized in that: The modifier is a combination of styrene-based thermoplastic elastomer and styrene-butadiene rubber in a mass ratio of 0.3 to 1.6:1; and / or, the styrene-based thermoplastic elastomer is at least one of SBS, SEBS, SIS, and SEPS; and / or, the styrene-butadiene rubber is at least one of emulsion styrene-butadiene rubber and solution styrene-butadiene rubber.

8. The polyolefin elastomer film self-adhesive bitumen waterproof membrane according to any one of claims 1 to 7, characterized in that: The mass ratio of the petroleum asphalt, tackifying resin, modifier, softening oil, and filler is 40-50:5-10:8-15:10-20:20-35.

9. The polyolefin elastomer membrane self-adhesive bitumen waterproof membrane according to claim 1, characterized in that: The barrier adhesive layer is a multilayer co-extruded film; and / or, the thickness of the barrier adhesive layer is 0.02 to 0.12 mm.

10. The polyolefin elastomer film self-adhesive bitumen waterproof membrane according to any one of claims 1 to 7, characterized in that: The polyolefin elastomer film layer is a homogeneous polyolefin elastomer film, a fiber-reinforced polyolefin elastomer film, or a polyolefin elastomer film with a fiber backing.

11. The polyolefin elastomer film self-adhesive bitumen waterproof membrane according to any one of claims 1 to 7, characterized in that: The thickness of the polyolefin elastomer film is 0.1–0.4 mm.

12. The polyolefin elastomer film self-adhesive bitumen waterproof membrane according to any one of claims 1 to 7, characterized in that: The thickness of the polyolefin elastomer membrane self-adhesive bitumen waterproof membrane is 1.5 to 2.2 mm; and / or, the thickness of the self-adhesive polymer modified bitumen layer is 1.0 to 1.9 mm.

13. A method for preparing the polyolefin elastomer film self-adhesive bitumen waterproof membrane according to any one of claims 1 to 12, characterized in that, Includes the following steps: (1) Preparation of self-adhesive polymer-modified asphalt Petroleum asphalt and softening oil are stirred and dehydrated at 140–150°C, then modifiers, tackifying resins and fillers are added, and the mixture is sheared and mixed at 170–180°C to obtain the self-adhesive polymer-modified asphalt. (2) Preparation of polyolefin elastomer film / barrier adhesive layer composite film A polyolefin elastomer film and a barrier adhesive layer are hot-pressed together at a temperature of 120–150°C to prepare a polyolefin elastomer film / barrier adhesive layer composite film. (3) Preparation of polyolefin elastomer film self-adhesive bitumen waterproof membrane The self-adhesive polymer-modified bitumen is coated onto the surface of the release membrane at 140-150°C and cooled. After the surface of the self-adhesive polymer-modified bitumen cools to 40-60°C, a polyolefin elastomer film / barrier adhesive layer composite film is applied, extruded and bonded, and cooled to form the polyolefin elastomer film self-adhesive bitumen waterproof membrane.

14. Use of the polyolefin elastomer membrane self-adhesive bitumen waterproof membrane according to any one of claims 1 to 12 in the field of waterproofing buildings or structures.

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