High oil resistance non-asphalt-based pre-laid waterproofing roll material and preparation method thereof

Abstract

The application provides a high oil resistance non-asphalt-based pre-laid waterproof coiled material and a preparation method thereof. The coiled material comprises a reverse adhesion layer, a hot melt pressure sensitive adhesive layer, a polymer sheet layer, a reinforcing layer and a bottom layer which are sequentially stacked from top to bottom. The reverse adhesion layer is a natural inorganic mineral particle sand layer. The hot melt pressure sensitive adhesive layer is an oil-free non-asphalt self-adhesive layer. The polymer sheet layer is an HDPE-based oil-resistant sheet layer. The reinforcing layer is a short fiber needle-punched geotextile layer. The bottom layer is made of the same material as the polymer sheet layer. The hot melt pressure sensitive adhesive layer of the coiled material has little influence on the aging of the polymer sheet layer caused by oil. In particular, the polymer sheet layer has excellent oil penetration resistance and swelling resistance. After the coiled material is bonded with the asphalt self-adhesive layer of an asphalt-based coiled material, the coiled material still has good performance after 28 days of heat aging, thereby achieving excellent oil resistance and ensuring good construction application performance.

Description

Technical Field

[0001] This invention relates to the field of waterproof membrane technology, specifically to a high oil-resistant non-asphalt-based pre-laid waterproof membrane and its preparation method. Background Technology

[0002] Non-bitumen-based pre-laid waterproof membranes were first invented and introduced to the Chinese market by GRACE Waterproofing Company in the United States. Subsequently, the Chinese government issued relevant standards in 2008, vigorously promoting pre-laid waterproof membrane systems and construction technologies. Currently, many cities in my country are carrying out underground integrated pipe gallery and tunnel construction projects, providing a broad application field for non-bitumen-based polymer waterproof membranes. In April 2023, GB55030-2022 "General Specification for Waterproofing of Building and Municipal Engineering" (hereinafter referred to as "General Specification") clearly stipulates the main waterproofing methods for open-cut underground engineering. In the first-level waterproofing grade, no less than two external waterproofing layers are required. In the original GB50108-2008 "Technical Specification for Waterproofing of Underground Engineering", single-layer polymer pre-laid waterproof membranes no longer meet the requirements for first-level waterproofing. To meet the first-level waterproofing requirements, non-bitumen-based pre-laid waterproof membranes need to be used in combination with another waterproofing material. Bitumen-based membranes are increasingly considered for use in combination with non-bitumen-based pre-laid waterproof membranes due to their wide variety, long application history, and lower cost. However, asphalt-based waterproof membranes typically contain various oils (such as asphalt, softening oil, base oil, and aromatic oil). The small molecules in these oils migrate into the polymer matrix of non-asphalt-based pre-laid waterproof membranes that come into contact with them. Additionally, oils in the hot-melt pressure-sensitive adhesive layer (such as mineral oil, white oil, and naphthenic rubber oil) within the membrane's structure also migrate into the polymer matrix. This leads to aging of the polymer matrix, loss of adhesion of the self-adhesive layer, and ultimately, failure of the waterproof layer. Therefore, to meet the construction requirements of good compatibility and full adhesion between waterproof layers, non-asphalt-based pre-laid waterproof membranes are incompatible with asphalt-based membranes and cannot be directly mixed and used. This severely limits the promotion and use of non-asphalt-based pre-laid waterproof membranes. Summary of the Invention

[0003] To address the problem that existing non-asphalt-based pre-laid waterproof membranes on the market suffer from reduced waterproofing performance when used in conjunction with asphalt-based membranes due to incompatibility, this invention provides a high oil-resistant non-asphalt-based pre-laid waterproof membrane and its preparation method.

[0004] To achieve high oil resistance, the present invention employs the following technical solution:

[0005] A high oil-resistant, non-asphalt-based pre-laid waterproof membrane comprises, from top to bottom, a reverse adhesive layer, a hot-melt pressure-sensitive adhesive layer, a polymer sheet layer, a reinforcing layer, and a bottom layer, wherein the reverse adhesive layer is a natural inorganic mineral granular sand layer, the hot-melt pressure-sensitive adhesive layer is an oil-free, non-asphalt self-adhesive layer, the polymer sheet layer is an HDPE-based oil-resistant sheet layer, the reinforcing layer is a short-fiber needle-punched geotextile layer, and the bottom layer is made of the same material as the polymer sheet layer.

[0006] The natural inorganic mineral particles are selected from one or more of white marble sand, marble sand, and calcium sand, with a particle size of 28-55 mesh, and 0.4-0.8 kg are used per square meter of the roll material.

[0007] The oil-free, non-asphalt self-adhesive layer comprises, by weight, the following raw materials: 20-35 parts ultra-high diblock SIS, 15-35 parts high-activity polyisobutylene, 20-45 parts DCPD hydrogenated C5 petroleum resin, 1-15 parts maleic anhydride-grafted aliphatic hydrocarbon petroleum resin, 0.3-0.5 parts antioxidant, 0.3-0.5 parts ultraviolet absorber, and 0.25-0.5 parts light stabilizer.

[0008] Furthermore, the polystyrene content in the ultra-high diblock SIS is not less than 18%, and the diblock content is not less than 75%. Specifically, the ultra-high diblock SIS is selected from one or a combination of several of Yueyang Petrochemical SIS4016, Shandong Jusheng SIS4270, and American Kraton SIS4187A;

[0009] Furthermore, the highly active polyisobutylene is a liquid thickener with end-group activity of not less than 80% and a number-average molecular weight of 3000-5000.

[0010] The DCPD hydrogenated C5 petroleum resin is a light-colored hydrogenated petroleum resin that has good adhesion to polyolefin materials and a softening point of 100℃~120℃.

[0011] The maleic anhydride-grafted aliphatic hydrocarbon petroleum resin is a light-colored tackifier with significant acidity, an acid value of not less than 20 mg KOH / g, a number-average molecular weight of 1300-1500, and a softening point of 100℃-130℃.

[0012] Furthermore, the antioxidant is a compound of hindered phenolic antioxidants and phosphite antioxidants, wherein the weight ratio of the hindered phenolic antioxidant to the phosphite antioxidant is 1 to 3:1.

[0013] The hindered phenolic antioxidant is preferably pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] ester.

[0014] The preferred antioxidant of the phosphite class is tris[2,4-di-tert-butylphenyl]phosphite.

[0015] Furthermore, the ultraviolet absorber is one or a combination of several of the following: 2-(5-chloro(2H)-benzotriazol-2-yl)-4-(methyl)-6-(tert-butyl)phenol, 2-(2H-benzotriazol-2-yl)-4-tert-butyl-6-sec-butylphenol, 2,4-di-tert-butyl-6-(5-chloro-2H-benzotriazol-2-yl)phenol, and 2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol.

[0016] Furthermore, the light stabilizer is a hindered amine light stabilizer.

[0017] Preferably, it is a combination of one or more of the following: bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol) ester, and poly-{[6-[(1,1,3,3-tetramethylbutyl)-imino]-1,3,5-triazine-2,4-diyl][2-(2,2,6,6-tetramethylpiperidinyl)-amino]-hexylene-[4-(2,2,6,6-tetramethylpiperidinyl)]-imino]}.

[0018] The HDPE-based oil-resistant sheet layer comprises, by weight, the following components: 100 parts HDPE resin, 20-40 parts polyamide-6 resin (PA6), 10-25 parts LLDPE resin, and 1-10 parts additives.

[0019] Furthermore, the HDPE resin is a high-density polyethylene resin, selected with a tensile strength grade and a melt index of 0.5–1.5 g / 10 min (2.16 kg / 190 °C). More preferably, it is one of the following: HDPE5000s from Lanzhou Petrochemical Company, HDPE 6094 from Shaanxi Yanchang Petrochemical Company, HDPE8010 from Formosa Plastics Group, and HDPE108 from ExxonMobil.

[0020] The polyamide-6 resin is a translucent or opaque milky white plastic particle with thermoplasticity, chemical resistance, and a melting point of 225°C. Specifically, it is Toray Industries CM1011G-30 from Japan.

[0021] The LLDPE resin is linear low-density polyethylene resin with a melt index of 1.0–3.0 g / 10 min (2.16 kg / 190 °C). More preferably, it is LLDPE7042 from Lanzhou Petrochemical Company.

[0022] The additive is PA6 compatibilizer, which can promote the adhesion and compatibility between polar and non-polar materials, preferably maleic anhydride grafted polyethylene resin MAH-g-HDPE.

[0023] The short-fiber needle-punched geotextile layer is a nonwoven fabric made from synthetic short fibers, formed by dry web formation and needle-punching reinforcement, with a unit area mass of 70-350 g / m². 2 Further preferred is 100–250 g / m³. 2 .

[0024] This invention provides a high oil-resistant non-asphalt-based pre-laid waterproof membrane and its preparation method. The preparation method of the waterproof membrane includes the following steps:

[0025] S1: Preparation of hot-melt pressure-sensitive adhesive layer: High-activity polyisobutylene, half-DCPD hydrogenated C5 petroleum resin, antioxidant, ultraviolet absorber and light stabilizer are added to the production equipment, nitrogen is introduced, and the mixture is stirred at 30-40 r / min to make the materials uniformly mixed. The mixture is heated to 170℃-180℃. Then, ultra-high diblock SIS is added, and the mixture is kept warm and stirred for 60-90 min until the rubber is completely melted. Then, half-DCPD hydrogenated C5 petroleum resin and maleic anhydride grafted aliphatic hydrocarbon petroleum resin are added, and the mixture is kept warm and stirred for 30-40 min until it is uniformly melted. The vacuum degree is controlled at -0.06MPa to -0.1MPa, and the mixture is kept warm and stirred for 30-60 min before being discharged to form pre-made blocks for packaging. Finally, the oil-free non-asphalt self-adhesive for non-asphalt-based pre-laid waterproof membrane is obtained.

[0026] S2: Preparation of the bottom layer and its composite with the reinforcing layer: HDPE resin, polyamide-6 resin, LLDPE resin, and additives are added to a twin-screw extruder through a loss-in-weight metering feeding system. The extruder operating temperature is controlled at 210℃~240℃. After melt plasticization, the sheet material flowing from the die is composited with short-fiber needle-punched geotextile on a five-roll calender. After calendering, traction shaping, and edge trimming, the short-fiber needle-punched geotextile layer is composited on the upper surface of the bottom layer to obtain a short-fiber needle-punched geotextile layer / bottom layer composite layer. The bottom layer thickness is 0.1~1.0mm and the width is 1.0~2.0m.

[0027] S3: Preparation of Polymer Sheet Layer: HDPE resin, polyamide-6 resin, LLDPE resin, and additives are added to a twin-screw extruder via a loss-in-weight metering system. The extruder operating temperature is controlled at 210℃~240℃. After melt plasticization, the HDPE-based oil-resistant sheet layer flowing from the die is laminated with the short-fiber needle-punched geotextile layer / bottom layer on a five-roll calender. After calendering, traction shaping, and edge trimming, the short-fiber needle-punched geotextile layer / bottom layer is laminated onto the lower surface of the HDPE-based oil-resistant sheet layer, with an 80~120mm width reserved on the long side, resulting in a three-layer composite layer consisting of an HDPE-based oil-resistant sheet layer, a short-fiber needle-punched geotextile layer, and a bottom layer. The prepared HDPE-based oil-resistant sheet layer has a thickness of 0.7~2.0mm and a width of 1.0~2.0m.

[0028] S4: Roll Material Preparation: The oil-free, non-asphalt self-adhesive is pre-melted in a melt-bonding box to the required coating temperature of 150℃~160℃. The oil-free, non-asphalt self-adhesive is then applied to the surface of the three-layer composite polymer sheet using a coating machine, forming a hot-melt pressure-sensitive adhesive layer. Natural inorganic mineral granules are then covered with sand using a sand-spreading machine and pressed into the hot-melt pressure-sensitive adhesive layer. An 80-120mm wide strip of sand is left uncovered on the long side away from the pre-reserved edge on the lower surface of the polymer sheet, and a PE release film is pasted onto this portion of the hot-melt pressure-sensitive adhesive layer as the upper overlap edge. Simultaneously, the oil-free, non-asphalt self-adhesive is hot-melted onto the pre-reserved edge on the lower surface of the polymer sheet, and a PE release film is pasted onto this strip as the lower overlap edge. Finally, the roll is wound up to obtain the non-asphalt-based pre-laid waterproof roll material.

[0029] Preferably, the thickness of the hot-melt pressure-sensitive adhesive layer is controlled at 0.25mm to 0.5mm, the pressure applied is set at 0.3MPa to 0.6MPa, and the amount of natural inorganic mineral particles used for covering is 0.45kg / m². 2 ~0.65kg / m 2 .

[0030] Furthermore, in the waterproofing construction of the high oil resistance non-asphalt-based pre-laid waterproof membrane provided by the present invention, the long side overlap of the membrane is made by reserving a self-adhesive edge, that is, the upper overlap edge of the membrane is bonded to the lower overlap edge; the short side of the membrane is treated by conventional overlap tape.

[0031] The high oil-resistant non-asphalt-based pre-laid waterproof membrane of the present invention has undergone extensive optimization in the use of raw materials for each component, especially in the following four parts:

[0032] ① The raw materials used in the hot melt pressure-sensitive adhesive layer do not contain "oil", that is, mineral softening oil is not used. Instead, ultra-high diblock SIS is used in combination with highly active polyisobutylene, which avoids the migration of small molecule components in the pressure-sensitive adhesive layer into the polymer sheet layer.

[0033] ② The specific incorporation of maleic anhydride-grafted aliphatic hydrocarbon petroleum resin significantly enhances the polarity of the pressure-sensitive adhesive, enabling the adhesive layer to achieve good compatibility and bonding strength with the covered natural inorganic mineral particles. The polar groups of the pressure-sensitive adhesive attract each other to the polar sites of the inorganic mineral particles, and when the distance between them is less than [a certain value], [the adhesion strength increases]. When the following conditions are met, van der Waals forces or hydrogen bonds are formed between molecules, resulting in good adhesion. Therefore, polar materials are easy to bond together.

[0034] ③ In addition to conventional HDPE and LLDPE raw materials, the polymer sheet layer and the bottom layer introduce polyamide-6 resin, which increases the polarity of the substrate and enhances the oil resistance of the substrate to weakly polar or non-polar oils (such as softening oil, base oil, aromatic oil, etc.). From the design of the roll material itself, it greatly improves the anti-swelling and anti-permeation performance against oils.

[0035] ④ The reinforced layer and the bottom layer are set for the pre-laid waterproof membrane of the present invention. These two layers can be used to block the oil in the self-adhesive layer of the bitumen-based membrane that is in contact with the membrane from chemically corroding the membrane substrate of the present invention, and can also achieve the requirement of full adhesion between the non-bitumen-based pre-laid membrane and the bitumen-based membrane.

[0036] The beneficial effects of this invention are as follows:

[0037] ① The high oil resistance non-asphalt-based pre-laid waterproof membrane of the present invention enables direct full adhesion with asphalt-based membranes and can be combined with any other waterproof membrane, solving the problem that different types of membranes cannot be reasonably combined and greatly expanding the application range of non-asphalt-based pre-laid waterproof membranes.

[0038] ② The high oil resistance non-asphalt-based pre-laid waterproof membrane of the present invention has excellent oil resistance. After the membrane is bonded to the asphalt self-adhesive layer of the asphalt-based membrane and subjected to 28 days of heat aging treatment, the performance of the polymer sheet layer can still be maintained at more than 90%.

[0039] ③ The high oil resistance non-asphalt-based pre-laid waterproof membrane of the present invention uses natural inorganic mineral sand directly as the isolation and anti-adhesion layer of the pre-laid membrane, without the need for modification treatment or artificial synthesis of natural inorganic mineral sand (existing technology), which simplifies the process and saves costs. Detailed Implementation

[0040] To enable those skilled in the art to better understand the technical solutions of this invention, the technical solutions in the embodiments of this invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of this invention, and not all embodiments. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort should fall within the scope of protection of this invention.

[0041] Example 1

[0042] A high oil-resistant, non-asphalt-based pre-laid waterproof membrane comprises, from top to bottom, a reverse adhesive layer, a hot-melt pressure-sensitive adhesive layer, a polymer sheet layer, a reinforcing layer, and a bottom layer, wherein the reverse adhesive layer is a natural inorganic mineral granular sand layer, the hot-melt pressure-sensitive adhesive layer is an oil-free, non-asphalt self-adhesive layer, the polymer sheet layer is an HDPE-based oil-resistant sheet layer, the reinforcing layer is a short-fiber needle-punched geotextile layer, and the bottom layer is made of the same material as the polymer sheet layer.

[0043] Furthermore, the natural inorganic mineral granular sand is selected from white marble sand with a particle size of 28-55 mesh, and 0.5 kg is used per square meter of the roll material.

[0044] The oil-free, non-asphalt self-adhesive layer comprises, by weight, the following raw materials: 28 parts ultra-high diblock SIS, 30 parts high-activity polyisobutylene, 40 parts DCPD hydrogenated C5 petroleum resin, 5 parts maleic anhydride grafted aliphatic hydrocarbon petroleum resin, 0.5 parts antioxidant, 0.5 parts ultraviolet absorber, and 0.5 parts light stabilizer.

[0045] The ultra-high diblock SIS is selected from Yueyang Petrochemical SIS4016, with a styrene content of 18.5% and a diblock content of 75%.

[0046] The maleic anhydride-grafted aliphatic hydrocarbon petroleum resin used is D200 from Zeon Corporation of Japan.

[0047] The antioxidant is a compound of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and tris[2,4-di-tert-butylphenyl] phosphite from BASF in a weight ratio of 1:1.

[0048] The ultraviolet absorber is selected from 2-(5-chloro(2H)-benzotriazol-2-yl)-4-(methyl)-6-(tert-butyl)phenol;

[0049] The stabilizer is selected as bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacic acid ester.

[0050] The HDPE-based oil-resistant sheet layer comprises, by weight, the following components: 100 parts HDPE resin, 20 parts polyamide-6 resin (PA6), 20 parts LLDPE resin, and 3 parts additives.

[0051] The HDPE resin used is HDPE5000s from Lanzhou Petrochemical Company.

[0052] The additive is selected from DuPont's MAH-g-HDPE series, specifically grade E265.

[0053] The short-fiber needle-punched geotextile layer has a unit area mass of 250g / m². 2 .

[0054] The method for preparing a high oil-resistant, non-asphalt-based pre-laid waterproof membrane provided by this invention includes the following steps:

[0055] S1: Preparation of hot-melt pressure-sensitive adhesive layer: 30 parts of polyisobutylene, 20 parts of DCPD hydrogenated C5 petroleum resin, 0.5 parts of antioxidant, 0.5 parts of ultraviolet absorber and 0.5 parts of light stabilizer are added to the production equipment, nitrogen is introduced, and the mixture is stirred at 30-40 r / min to make the materials evenly mixed. The mixture is heated to 170℃-180℃. Then, 28 parts of ultra-high diblock SIS are added, and the mixture is kept warm and stirred for 60-90 minutes until the rubber is completely melted. Then, 20 parts of DCPD hydrogenated C5 petroleum resin and 5 parts of maleic anhydride grafted aliphatic hydrocarbon petroleum resin are added, and the mixture is kept warm and stirred for 30-40 minutes until it is evenly melted. The vacuum degree is controlled at -0.06MPa to -0.1MPa, and the mixture is kept warm and stirred for 30-60 minutes before being discharged to form pre-made blocks for packaging. Finally, the oil-free non-asphalt self-adhesive for non-asphalt-based pre-laid waterproof membrane is obtained.

[0056] S2: Preparation of the bottom layer and its composite preparation with the short-fiber needle-punched geotextile layer: 100 parts of HDPE 5000s resin, 20 parts of polyamide-6 resin, 20 parts of LLDPE resin, and 3 parts of additives are added to a twin-screw extruder through a loss-in-weight metering feeding system. The extruder operating temperature is controlled at 210℃~240℃. After melt plasticization, the sheet material flowing from the die is composited with the short-fiber needle-punched geotextile on a five-roll calender. After calendering, traction shaping, and edge trimming, the short-fiber needle-punched geotextile layer is composited on the upper surface of the bottom layer to obtain a short-fiber needle-punched geotextile layer / bottom layer composite layer. The bottom layer thickness is 0.3mm and the width is 2.0m.

[0057] S3: Preparation of Polymer Sheet Layer: 100 parts HDPE 5000s resin, 20 parts polyamide-6 resin, 20 parts LLDPE resin, and 3 parts additives were added to a twin-screw extruder via a loss-in-weight metering system. The extruder operating temperature was controlled at 210℃~240℃. After melt plasticization, the HDPE-based oil-resistant sheet layer flowing from the die was laminated with the short-fiber needle-punched geotextile layer / bottom layer on a five-roll calender. After calendering, traction shaping, and edge trimming, the short-fiber needle-punched geotextile layer / bottom layer was laminated onto the lower surface of the HDPE-based oil-resistant sheet layer, with an 80mm width reserved on the long side, resulting in a three-layer composite layer consisting of an HDPE-based oil-resistant sheet layer, a short-fiber needle-punched geotextile layer, and a bottom layer. The prepared HDPE-based oil-resistant sheet layer has a thickness of 1.2mm and a width of 2.0m.

[0058] S4: Roll Material Preparation: The oil-free, non-asphalt self-adhesive is pre-melted in a melt-bonding box to the required coating temperature of 150℃~160℃. The oil-free, non-asphalt self-adhesive is then applied to the surface of the three-layer composite polymer sheet using a coating machine, forming a hot-melt pressure-sensitive adhesive layer. Natural inorganic mineral granules are then covered with sand using a sand-spreading machine, and pressure is applied to embed them into the hot-melt pressure-sensitive adhesive layer. An 80mm wide section of the long side away from the pre-reserved edge on the lower surface of the polymer sheet is left uncovered with sand, and a PE release film is pasted onto this portion of the hot-melt pressure-sensitive adhesive layer as the upper overlap edge. Simultaneously, the oil-free, non-asphalt self-adhesive is hot-melted onto the pre-reserved edge on the lower surface of the polymer sheet, and a PE release film is pasted onto it as the lower overlap edge. The thickness of the hot-melt pressure-sensitive adhesive layer is controlled to be 0.30mm, and the pressure is set to 0.6MPa. Finally, the roll is wound up to obtain the non-asphalt-based pre-laid waterproof roll material.

[0059] Example 2

[0060] A high oil-resistant, non-asphalt-based pre-laid waterproof membrane comprises, from top to bottom, a reverse adhesive layer, a hot-melt pressure-sensitive adhesive layer, a polymer sheet layer, a reinforcing layer, and a bottom layer, wherein the reverse adhesive layer is a natural inorganic mineral granular sand layer, the hot-melt pressure-sensitive adhesive layer is an oil-free, non-asphalt self-adhesive layer, the polymer sheet layer is an HDPE-based oil-resistant sheet layer, the reinforcing layer is a short-fiber needle-punched geotextile layer, and the bottom layer is made of the same material as the polymer sheet layer.

[0061] Furthermore, the natural inorganic mineral granular sand is selected from calcium sand with a particle size of 28-55 mesh, and 0.5 kg is used per square meter of the roll material;

[0062] The oil-free, non-asphalt self-adhesive layer comprises, by weight, the following raw materials: 25 parts ultra-high diblock SIS, 32 parts high-activity polyisobutylene, 40 parts DCPD hydrogenated C5 petroleum resin, 3 parts maleic anhydride grafted aliphatic hydrocarbon petroleum resin, 0.5 parts antioxidant, 0.3 parts ultraviolet absorber, and 0.3 parts light stabilizer.

[0063] The ultra-high diblock SIS is made from Shandong Jusheng SIS4270, with a styrene content of 20% and a diblock content of 77%.

[0064] The HDPE-based oil-resistant sheet layer comprises, by weight, the following components: 100 parts HDPE resin, 30 parts polyamide-6 resin (PA6), 20 parts LLDPE resin, and 8 parts additives.

[0065] The HDPE resin used is HDPE5000s from Lanzhou Petrochemical Company.

[0066] The short-fiber needle-punched geotextile layer has a unit area mass of 100 g / m². 2 ;

[0067] The rest is the same as in Example 1.

[0068] Example 3

[0069] A high oil-resistant, non-asphalt-based pre-laid waterproof membrane comprises, from top to bottom, a reverse adhesive layer, a hot-melt pressure-sensitive adhesive layer, a polymer sheet layer, a reinforcing layer, and a bottom layer, wherein the reverse adhesive layer is a natural inorganic mineral granular sand layer, the hot-melt pressure-sensitive adhesive layer is an oil-free, non-asphalt self-adhesive layer, the polymer sheet layer is an HDPE-based oil-resistant sheet layer, the reinforcing layer is a short-fiber needle-punched geotextile layer, and the bottom layer is made of the same material as the polymer sheet layer.

[0070] Furthermore, the oil-free, non-asphalt self-adhesive layer comprises, by weight, the following raw materials: 33 parts ultra-high diblock SIS, 25 parts high-activity polyisobutylene, 32 parts DCPD hydrogenated C5 petroleum resin, 10 parts maleic anhydride grafted aliphatic hydrocarbon petroleum resin, 0.4 parts antioxidant, 0.5 parts ultraviolet absorber, and 0.4 parts light stabilizer.

[0071] The HDPE-based oil-resistant sheet layer comprises, by weight, the following components: 100 parts HDPE resin, 30 parts polyamide-6 resin (PA6), 10 parts LLDPE resin, and 6 parts additives.

[0072] The rest is the same as in Example 1.

[0073] Comparative Example 1

[0074] The difference between Comparative Example 1 and Example 1 lies in the hot-melt pressure-sensitive adhesive layer. In Comparative Example 1, the ultra-high diblock SIS in the raw materials of the hot-melt pressure-sensitive adhesive layer was replaced with Yueyang Petrochemical SIS1105 in equal amounts, while the rest was the same as in Example 1. The SIS1105 contained 15% styrene and 0% diblock content.

[0075] Comparative Example 2

[0076] The difference between Comparative Example 2 and Example 1 lies in the hot melt pressure-sensitive adhesive layer. In Comparative Example 2, the high-activity polyisobutylene in the hot melt pressure-sensitive adhesive layer is replaced with naphthenic oil KN-4010 in equal amounts, while the rest is the same as in Example 1.

[0077] Comparative Example 3

[0078] The difference between Comparative Example 3 and Example 1 lies in the hot melt pressure-sensitive adhesive layer. The raw materials of the pressure-sensitive adhesive used in Comparative Example 3 are 45 parts of DCPD hydrogenated C5 petroleum resin and 0 parts of maleic anhydride grafted aliphatic hydrocarbon petroleum resin, and the rest are the same as in Example 1.

[0079] Comparative Example 4

[0080] The difference between Comparative Example 4 and Example 1 is that the polymer sheet layer is different. The raw materials of the polymer sheet layer used in Comparative Example 4 contain 0 parts of polyamide-6 resin (PA6), and the rest are the same as in Example 1.

[0081] Comparative Example 5

[0082] The difference between Comparative Example 5 and Example 1 lies in the hot melt pressure-sensitive adhesive layer and the polymer sheet layer. In Comparative Example 5, the high-activity polyisobutylene in the raw materials of the hot melt pressure-sensitive adhesive layer is replaced with naphthenic oil KN-4010 in equal amounts, and the polyamide-6 resin (PA6) in the raw materials of the polymer sheet layer is 0 parts, and the rest is the same as in Example 1.

[0083] Comparative Example 6

[0084] The difference between Comparative Example 6 and Example 1 is that Comparative Example 6 has no reinforcing layer and no bottom layer, but otherwise it is the same as Example 1.

[0085] Comparative Example 7

[0086] Comparative Example 7 is a non-bitumen-based pre-laid waterproof membrane with existing domestic technology. The membrane has a thickness of 1.5mm, with a polymer sheet layer thickness of 1.2mm and an adhesive layer thickness of 0.3mm.

[0087] The oil resistance of the above-mentioned non-asphalt-based pre-laid waterproof membrane was tested, and the test results are shown in Table 1 below.

[0088] ① The roll material specimens obtained in Examples 1-3 and Comparative Examples 1-7 were placed under standard experimental conditions for 24 hours. Then, three groups were taken from each group. The first group was subjected to heat aging treatment at 80℃ for 28 days. The second group was subjected to heat aging treatment at 80℃ for 28 days after simulating the bonding of two roll materials with the asphalt self-adhesive layer of the asphalt-based roll material. The third group served as a blank control experiment.

[0089] ②After the treatment, the bitumen-based membrane was removed from the non-bitumen-based pre-laid waterproof membrane, and the tensile strength of the three groups of samples was tested.

[0090] ③ Compare the tensile strength of the first and second groups with that of the third group, and calculate the tensile strength retention rate.

[0091] The overlap performance of the above-mentioned non-asphalt-based pre-laid waterproof membrane was tested. That is, after the overlap edge of the upper surface of the membrane was bonded to the overlap edge of the lower surface of the membrane, it was subjected to heat aging treatment at 80℃ for 14 days, and the peel strength between the membranes was tested. The test results are shown in Table 2 below.

[0092] Table 1. Oil resistance test results of waterproof membranes in Examples 1-3 and Comparative Examples 1-7

[0093] Tensile strength retention rate % Group 1 Group 2 Example 1 98 95 Example 2 96 95 Example 3 99 97 Comparative Example 1 95 96 Comparative Example 2 91 88 Comparative Example 3 97 93 Comparative Example 4 95 84 Comparative Example 5 85 70 Comparative Example 6 98 89 Comparative Example 7 83 62

[0094] Table 2. Test results of the overlap performance of waterproof membranes in Examples 1-3 and Comparative Examples 1-7.

[0095] Peel strength between rolls (N / mm) Test results Example 1 2.05 Example 2 1.75 Example 3 1.50 Comparative Example 1 1.00 Comparative Example 2 1.35 Comparative Example 3 1.85 Comparative Example 4 1.80 Comparative Example 5 1.15 Comparative Example 6 2.00 Comparative Example 7 1.20

[0096] As can be seen from Tables 1 and 2, the non-asphalt-based pre-laid waterproof membrane of the present invention has high oil resistance. Comparing Comparative Examples 1-7 with Example 1, it can be seen that the ultra-high diblock SIS, highly active polyisobutylene, and maleic anhydride-grafted aliphatic hydrocarbon petroleum resin in the pressure-sensitive adhesive all contribute to the high oil resistance of the membrane; the polyamide-6 resin (PA6) in the polymer sheet, as well as the reinforcing layer and the bottom layer, all play a good role in the high oil resistance and oil resistance of the membrane, and only when they are used together can a better effect be achieved.

[0097] The high oil-resistant non-asphalt-based pre-laid waterproof membrane of the present invention has minimal impact on the aging of the polymer sheet layer caused by oil in its own structure, and the polymer sheet layer has excellent anti-penetration and anti-swelling properties against oil. After the membrane is bonded to the asphalt self-adhesive layer of the asphalt-based membrane, it can still achieve excellent oil resistance after 28 days of accelerated heat aging, ensuring good construction and application performance of the membrane.

[0098] Although the present invention has been described in detail by way of preferred embodiments, the present invention is not limited thereto. Various equivalent modifications or substitutions can be made to the embodiments of the present invention by those skilled in the art without departing from the spirit and essence of the invention, and such modifications or substitutions should all be within the scope of the present invention. Any variations or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention should also be covered within the protection scope of the present invention. Therefore, the protection scope of the present invention should be determined by the scope of the claims.

Claims

1. A high oil resistance non-bituminous based pre-paved waterproofing membrane, characterized in that: The self-adhesive waterproof roll material comprises, from top to bottom, an anti-sticking bonding layer, a hot melt pressure-sensitive adhesive layer, a polymer sheet layer, a reinforcing layer and a bottom layer, wherein the hot melt pressure-sensitive adhesive layer is an oil-free non-asphalt self-adhesive layer, and the polymer sheet layer is an HDPE-based oil-resistant sheet layer. The oil-free non-asphalt self-adhesive layer comprises, by weight, 20-35 parts of super-high two-block SIS, 15-35 parts of high-activity polyisobutylene, 20-45 parts of DCPD hydrogenated carbon five petroleum resin, 1-15 parts of maleic anhydride grafted aliphatic petroleum resin, 0.3-0.5 parts of antioxidant, 0.3-0.5 parts of ultraviolet absorber and 0.25-0.5 parts of light stabilizer. The HDPE-based oil-resistant sheet layer comprises, by weight, 100 parts of HDPE resin, 20-40 parts of polyamide-6 resin, 10-25 parts of LLDPE resin and 1-10 parts of additive.

2. The high oil resistance non-asphalt based pre-paved waterproofing membrane according to claim 1, characterized in that: The anti-sticking bonding layer is a natural inorganic mineral particle sand layer, which is selected from one or a combination of several of Hanbaiyu sand, marble sand and calcium sand, and has a particle size of 28-55 mesh.

3. The high oil resistance non-asphalt based pre-paved waterproofing membrane according to claim 1, characterized in that: The reinforcing layer is a short fiber needle-punched geotextile layer with a unit area mass of 70-350 g / m 2 ; the bottom layer is of the same material as the high polymer sheet layer.

4. The high oil-resistant non-asphalt-based pre-laid waterproof roll material according to claim 1, wherein the super-high two-block SIS has a polystyrene content of not less than 18% and a two-block content of not less than 75%. The high-activity polyisobutylene is a liquid tackifier, has an end group activity of not less than 80% and a number average molecular weight of 3000-5000. The maleic anhydride grafted aliphatic petroleum resin is a light-colored tackifier with significant acidity, has an acid value of not less than 20 mgKOH / g, a number average molecular weight of 1300-1500 and a softening point of 100-130°C.

5. The high oil-resistant non-asphalt-based pre-laid waterproof roll material according to claim 1, wherein the polyamide-6 resin is a translucent or opaque milky white plastic particle, has a melting point of 225°C. The additive is a PA6 compatible agent. The preparation method comprises the following steps: S1: preparation of the hot melt pressure-sensitive adhesive layer; 6. A process for the preparation of a high oil resistance non bituminous based pre-paved waterproofing sheet, characterized in that, S2: preparation of the bottom layer and compounding with the reinforcing layer: the sheet extruded from the die and the short fiber needled geotextile are compounded on a five-roller calender, the bottom layer has a thickness of 0.1-1.0 mm and a width of 1.0-2.0 m; S3: preparation of the polymer sheet layer: the short fiber needled geotextile layer / bottom layer is compounded on the lower surface of the HDPE-based oil-resistant sheet layer, and 80-120 mm wide long edges are reserved on one side, the HDPE-based oil-resistant sheet layer has a thickness of 0.7-2.0 mm and a width of 1.0-2.0 m; S4: preparation of the roll material: 80-120 mm wide long edges are reserved on one side away from the lower surface of the polymer sheet, and the reserved edges are not covered with sand, serving as the upper lap joint edges; meanwhile, the oil-free non-asphalt self-adhesive hot melt is coated on the lower surface of the polymer sheet, serving as the lower lap joint edges. ​ ​