A three-ply base polymer self-adhesive pre-laid waterproof roll material and a preparation method thereof

Abstract

This invention relates to the field of waterproof membrane technology, and proposes a three-layer polymer self-adhesive pre-laid waterproof membrane and its preparation method. The three-layer polymer self-adhesive pre-laid waterproof membrane, from top to bottom, comprises a protective layer, adhesive layer I, polymer film layer I, adhesive layer II, polymer film layer II, adhesive layer III, polymer film layer III, a self-adhesive layer, and a release layer. At least one of adhesive layer I, adhesive layer II, adhesive layer III, and the self-adhesive layer includes the following components: styrene-butadiene-styrene block copolymer, asphalt, carboxylated styrene-butadiene rubber, tetraneedle-shaped zinc oxide whiskers I and II, and additives. Tetraneedle-shaped zinc oxide whisker I is a compound modifying tetraneedle-shaped zinc oxide whisker with phenyl and epoxy groups in its molecular structure, and tetraneedle-shaped zinc oxide whisker II is an aminosiloxane modified tetraneedle-shaped zinc oxide whisker. This technical solution solves the problem of poor puncture resistance in pre-laid waterproof membranes in related technologies.

Description

Technical Field

[0001] This invention relates to the field of waterproof membrane technology, specifically to a three-layer polymer self-adhesive pre-laid waterproof membrane and its preparation method. Background Technology

[0002] Waterproof membranes are one of the main materials used in waterproofing projects, including elastomeric modified bitumen waterproof membranes, plastomeric modified bitumen waterproof membranes, pre-laid waterproof membranes, wet-laid waterproof membranes, self-adhesive polymer modified bitumen waterproof membranes, polymer waterproof sheets, and polyvinyl chloride waterproof membranes.

[0003] Pre-laid waterproof membrane refers to a waterproof membrane composed of a main material (plastic, asphalt, rubber), self-adhesive, a surface anti-adhesion or anti-adhesion protective layer (excluding the overlapping area of ​​the membrane), and a release material. It is bonded to the subsequently poured concrete and can effectively prevent water from seeping into the bonding surface. It is suitable for waterproofing underground and tunnel projects.

[0004] During the construction of pre-laid waterproof membranes, workers walk directly on the membrane after it is installed and tie reinforcing bars to it. Therefore, the membrane needs to have good puncture resistance. To improve the puncture resistance of pre-laid waterproof membranes, researchers tend to add needle-like or fibrous inorganic fillers, such as tetraneedle zinc oxide whiskers, to the adhesive layer. However, the poor compatibility between inorganic fillers and the polymer matrix of the adhesive layer prevents the improvement effect from being fully realized. Summary of the Invention

[0005] This invention proposes a three-layer polymer self-adhesive pre-laid waterproof membrane and its preparation method, which solves the problem of poor puncture resistance of pre-laid waterproof membranes in related technologies.

[0006] The technical solution of the present invention is as follows: This invention proposes a three-layer polymer self-adhesive pre-laid waterproof membrane, which, from top to bottom, comprises a protective layer, adhesive layer I, polymer film layer I, adhesive layer II, polymer film layer II, adhesive layer III, polymer film layer III, self-adhesive layer, and release layer. At least one of adhesive layer I, adhesive layer II, adhesive layer III, and self-adhesive layer comprises the following components: styrene-butadiene-styrene block copolymer, asphalt, carboxylated styrene-butadiene rubber, tetraneedle zinc oxide whisker I, tetraneedle zinc oxide whisker II, and additives. The tetraneedle zinc oxide whisker I is a tetraneedle zinc oxide whisker modified with a compound containing phenyl and epoxy groups in its molecular structure, and the tetraneedle zinc oxide whisker II is a tetraneedle zinc oxide whisker modified with aminosiloxane.

[0007] Preferably, the mass ratio of the tetraneedle zinc oxide whiskers I to the tetraneedle zinc oxide whiskers II is 3~7:1.

[0008] Preferably, the raw material for the tetraneedle zinc oxide whisker I includes tetraneedle zinc oxide whiskers in a mass ratio of 100:1 to 10 and compounds whose molecular structure includes phenyl and epoxy groups.

[0009] Preferably, the preparation method of the tetraneedle zinc oxide whisker I includes the following steps: dispersing the tetraneedle zinc oxide whisker in a solvent, adding a compound whose molecular structure includes phenyl and epoxy groups for mixing, concentrating, and drying to obtain the tetraneedle zinc oxide whisker I.

[0010] Preferably, the mass ratio of the styrene-butadiene-styrene block copolymer, asphalt, carboxylated styrene-butadiene rubber, and additives is 10:40:2~4:7~12; The mass ratio of the tetraneedle zinc oxide whiskers I and II to the mass ratio of the styrene-butadiene-styrene block copolymer is 5~7:2.

[0011] Preferably, the additive includes at least one of the following characteristics: plasticizer, antioxidant, ultraviolet absorber, tackifying resin, and colorant.

[0012] Preferably, the additive is composed of a plasticizer, an antioxidant, and a tackifying resin in a mass ratio of 5~7:1:3~5.

[0013] Preferably, the plasticizer includes one or more of phthalates, dicarboxylic acid esters, and phosphate esters, and / or The antioxidant includes one or more of antioxidant 1010, antioxidant 168, and antioxidant 3114, and / or The tackifying resin includes one or more of terpene resin, petroleum resin, and coumarone resin.

[0014] This invention also proposes a method for preparing a three-layer polymer self-adhesive pre-laid waterproof membrane, which includes the following steps: A. After melting the asphalt, add the remaining components and mix evenly to obtain the adhesive; B. Add adhesive between the protective layer and polymer film layer I to obtain adhesive layer I; C. Add an adhesive between polymer film layer I and polymer film layer II to obtain adhesive layer II; D. Add an adhesive between polymer film layer II and polymer film layer III to obtain adhesive layer III; E. Add adhesive between polymer film layer III and the isolation layer to obtain a self-adhesive layer, and calender to obtain a three-layer polymer self-adhesive pre-laid waterproof membrane.

[0015] This invention also proposes a method for preparing a three-layer polymer self-adhesive pre-laid waterproof membrane, which includes the following steps: A. After melting the asphalt, add styrene-butadiene-styrene block copolymer, carboxylated styrene-butadiene rubber, and tetraneedle zinc oxide whiskers I and mix evenly. Then add the remaining components and mix evenly to obtain the adhesive. B. Add adhesive between the protective layer and polymer film layer I to obtain adhesive layer I; C. Add an adhesive between polymer film layer I and polymer film layer II to obtain adhesive layer II; D. Add an adhesive between polymer film layer II and polymer film layer III to obtain adhesive layer III; E. Add adhesive between polymer film layer III and the isolation layer to obtain a self-adhesive layer, and calender to obtain a three-layer polymer self-adhesive pre-laid waterproof membrane.

[0016] The working principle and beneficial effects of this invention are as follows: In this invention, tetra-needle zinc oxide whiskers I and tetra-needle zinc oxide whiskers II are used in combination to improve the dispersibility of inorganic filler tetra-needle zinc oxide whiskers in the adhesive layer and self-adhesive layer and their compatibility with the polymer base material of the adhesive layer and self-adhesive layer, thereby improving the puncture resistance of the pre-laid waterproof membrane.

[0017] Among them, tetra-needle zinc oxide whisker I is a tetra-needle zinc oxide whisker modified with a compound containing phenyl and epoxy groups in its molecular structure. The modification is achieved by forming hydrogen bonds between the epoxy groups in the molecular structure and the hydroxyl groups on the surface of the tetra-needle zinc oxide whisker. After being modified with a compound containing phenyl and epoxy groups in its molecular structure, the surface of the tetra-needle zinc oxide whisker is organic and contains phenyl and epoxy groups. The phenyl groups can form π-π interactions with the phenyl groups in the polymer matrix, while the epoxy groups can react with the amino groups on the surface of the aminosiloxane-modified tetra-needle zinc oxide whisker. The hydroxyl groups generated after the reaction can form hydrogen bonds with the carboxyl groups in the carboxylated styrene-butadiene rubber. Ultimately, this improves the dispersibility of the inorganic filler tetra-needle zinc oxide whisker in the material and its compatibility with the polymer matrix, thereby improving the puncture resistance of the pre-laid waterproof membrane. Detailed Implementation

[0018] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0019] It should be understood that, unless the context clearly indicates otherwise, the terms "comprising," "including," or "having" as used herein refer to the presence of a particular element, but do not exclude the presence or addition of one or more other elements. Furthermore, as used herein, "comprising" and / or "including" specify the presence of shapes, numbers, steps, operations, members, elements, and / or combinations thereof, and do not exclude the presence or addition of one or more other shapes, numbers, operations, elements, and / or combinations thereof.

[0020] In this invention, the numerical range indicated by "~" refers to the range of values ​​specified as the lower and upper limits, respectively, before or after the term. When multiple values ​​for the upper or lower limit of any numerical range are mentioned, the range disclosed herein can be understood as a range with any one of the mentioned upper limits as its upper limit and any one of the mentioned lower limits as its lower limit.

[0021] The following will describe in detail the three-layer polymer self-adhesive pre-laid waterproof membrane and its preparation method according to embodiments of the present invention.

[0022] According to one aspect of the present invention, a three-layer polymer self-adhesive pre-laid waterproof membrane is provided, comprising, from top to bottom, a protective layer, an adhesive layer I, a polymer film layer I, an adhesive layer II, a polymer film layer II, an adhesive layer III, a polymer film layer III, a self-adhesive layer, and a release layer. At least one of the adhesive layers I, II, III, and the self-adhesive layer comprises the following components: styrene-butadiene-styrene block copolymer, asphalt, carboxylated styrene-butadiene rubber, tetraneedle zinc oxide whiskers I and II, and additives. The tetraneedle zinc oxide whiskers I are modified tetraneedle zinc oxide whiskers with compounds including phenyl and epoxy groups in their molecular structure, and the tetraneedle zinc oxide whiskers II are aminosiloxane modified tetraneedle zinc oxide whiskers.

[0023] In this invention, modified asphalt is used as an adhesive, which ensures that adhesive layer I, adhesive layer II, adhesive layer III and self-adhesive layer have good comprehensive performance.

[0024] Styrene-butadiene-styrene block copolymer (SBS) is a copolymer produced by anionic polymerization of butadiene and styrene monomers with the addition of solvents, initiators, and activators. It exhibits good elasticity at room temperature without vulcanization, and its application in modifying asphalt can improve the high and low temperature properties of asphalt.

[0025] Carboxylated styrene-butadiene rubber (SBR) is a copolymer or copolymer emulsion polymerized from butadiene, styrene, and a small amount of unsaturated carboxylic acids (acrylic acid or methacrylic acid). It possesses high strength, high thermal stability, excellent abrasion resistance, cold resistance, tear resistance, and high resistance to repeated flexural bending. It does not require sulfur or accelerator vulcanization; instead, it undergoes self-crosslinking under the influence of oxygen. When used to modify asphalt, it can improve elasticity, heat resistance, and mechanical strength.

[0026] Tetranephrite zinc oxide whiskers are crystals with a three-dimensional spatial structure, exhibiting a three-dimensional tetranephrite shape. When used to modify asphalt, they can improve strength and heat resistance.

[0027] In one embodiment of the present invention, the mass ratio of tetraneedle zinc oxide whisker I to tetraneedle zinc oxide whisker II is 3~7:1.

[0028] In one embodiment of the present invention, the raw material for tetraneedle zinc oxide whisker I includes tetraneedle zinc oxide whiskers in a mass ratio of 100:1 to 10 and a compound whose molecular structure includes phenyl and epoxy groups.

[0029] Compounds containing phenyl and epoxy groups in their molecular structure can be any compound having both phenyl and epoxy groups in its molecular structure, preferably one or both of glycidyl 2-methoxyphenyl ether and 9,9-bis(4-epoxypropyloxophenyl)fluorene.

[0030] In one embodiment of the present invention, the preparation method of tetraneedle zinc oxide whisker I includes the following steps: dispersing tetraneedle zinc oxide whiskers in a solvent, adding a compound whose molecular structure includes phenyl and epoxy groups for mixing, concentrating, and drying to obtain tetraneedle zinc oxide whisker I.

[0031] The solvent is used to dissolve compounds whose molecular structure includes phenyl and epoxy groups. Therefore, the solvent in this invention can be any solvent that can dissolve compounds whose molecular structure includes phenyl and epoxy groups, preferably a low-boiling-point solvent such as methanol or chloroform.

[0032] The raw materials for tetraneedle zinc oxide whiskers II can be any conventional raw materials and amounts used in the art, preferably including tetraneedle zinc oxide whiskers and aminosiloxane in a mass ratio of 10:1 to 5.

[0033] The aminosiloxane can be any siloxane with an amino group in its molecular structure, and is preferably one or both of silane coupling agents KH-550 and KH-540.

[0034] The tetra-needle-shaped zinc oxide whiskers II can be prepared using any conventional method in the art. Preferably, the preparation method includes the following steps: After hydrolyzing aminosiloxane in acidic ethanol solution, tetraneedle-shaped zinc oxide whiskers were added for modification. The product was then diluted, washed, filtered, and dried sequentially to obtain tetraneedle-shaped zinc oxide whiskers II.

[0035] In one embodiment of the present invention, the mass ratio of styrene-butadiene-styrene block copolymer, asphalt, carboxylated styrene-butadiene rubber and additives is 10:40:2~4:7~12; The mass ratio of tetraneedle zinc oxide whiskers I and II to the mass ratio of styrene-butadiene-styrene block copolymer is 5~7:2.

[0036] In one embodiment of the present invention, the additives include at least one of the following characteristics: plasticizer, antioxidant, ultraviolet absorber, tackifying resin, and colorant.

[0037] In one embodiment of the present invention, the additive is composed of a plasticizer, an antioxidant, and a tackifying resin in a mass ratio of 5~7:1:3~5.

[0038] Plasticizers can increase the plasticity of polymer systems, reduce melting temperature and melt viscosity, improve processing performance, and also improve flexibility. For example, they can be one or more of phthalate esters, dicarboxylic acid esters, phosphate esters, polyol esters, epoxidized oils, and epoxidized oleate esters, preferably including one or more of phthalate esters, dicarboxylic acid esters, and phosphate esters, and more preferably phthalate esters.

[0039] Antioxidants can prevent the thermo-oxidative degradation of polymers at certain temperatures during processing or use. For example, they can be one or more of antioxidants 1010, 168, 1076, 264, 300, and 3114, preferably including one or more of antioxidants 1010, 168, and 3114, and more preferably antioxidants 1010 and 168 in a mass ratio of 1:2.

[0040] Tackifying resins can improve adhesive strength. For example, they can be one or more of terpene resins, petroleum resins, rosin resins, coumarone resins, and xylene resins, preferably including one or more of terpene resins, petroleum resins, and coumarone resins, and more preferably terpene resins.

[0041] According to another aspect of the present invention, the present invention also provides a method for preparing a three-layer polymer self-adhesive pre-laid waterproof membrane, which includes the following steps: A. After melting the asphalt, add the remaining components and mix evenly to obtain the adhesive; B. Add adhesive between the protective layer and polymer film layer I to obtain adhesive layer I; C. Add an adhesive between polymer film layer I and polymer film layer II to obtain adhesive layer II; D. Add an adhesive between polymer film layer II and polymer film layer III to obtain adhesive layer III; E. Add adhesive between polymer film layer III and the isolation layer to obtain a self-adhesive layer, and calender to obtain a three-layer polymer self-adhesive pre-laid waterproof membrane.

[0042] This invention also proposes a method for preparing a three-layer polymer self-adhesive pre-laid waterproof membrane, which includes the following steps: A. After melting the asphalt, add styrene-butadiene-styrene block copolymer, carboxylated styrene-butadiene rubber, and tetraneedle zinc oxide whiskers I and mix evenly. Then add the remaining components and mix evenly to obtain the adhesive. B. Add adhesive between the protective layer and polymer film layer I to obtain adhesive layer I; C. Add an adhesive between polymer film layer I and polymer film layer II to obtain adhesive layer II; D. Add an adhesive between polymer film layer II and polymer film layer III to obtain adhesive layer III; E. Add adhesive between polymer film layer III and the isolation layer to obtain a self-adhesive layer, and calender to obtain a three-layer polymer self-adhesive pre-laid waterproof membrane.

[0043] When preparing the adhesive, adding tetra-needle zinc oxide whisker I first, followed by tetra-needle zinc oxide whisker II, can further improve the puncture resistance of the pre-laid waterproof membrane. This is because tetra-needle zinc oxide whisker I has phenyl and epoxy groups on its surface, resulting in weaker interactions between particles. Adding it first allows for good dispersion through the interaction between the phenyl groups and the base material. On the other hand, tetra-needle zinc oxide whisker II has amino groups on its surface, which can form hydrogen bonds, resulting in relatively stronger interactions between particles. Adding it subsequently allows for good dispersion with the help of tetra-needle zinc oxide whisker I.

[0044] The following will describe in detail, with reference to examples, the three-layer polymer self-adhesive pre-laid waterproof membrane and its preparation method according to the present invention. The embodiments of the present invention described below can be modified in various forms; therefore, the scope of the present invention should not be construed as limited to the embodiments described in detail below. The embodiments are provided to help those skilled in the art to more readily understand the present invention.

[0045] Unless otherwise specified, in the following examples and comparative examples, the styrene-butadiene-styrene block copolymer is Baling Petrochemical SBS YH-1301; the asphalt is No. 90 asphalt; the carboxylated styrene-butadiene rubber is BASF 417 carboxylated styrene-butadiene latex; the tetraneedle-shaped zinc oxide whiskers have a diameter of 0.5~5μm and a length of 10~50μm; and the terpene resin is terpene resin T110. The three-layer polymer self-adhesive pre-laid waterproof membrane is prepared by the following method: (1) An adhesive is added between a polyethylene film with a thickness of 0.05 mm and a polyethylene terephthalate film with a thickness of 0.15 mm to obtain adhesive layer I; (2) An adhesive is added between a polyethylene terephthalate film with a thickness of 0.15 mm and a polyethylene terephthalate film with a thickness of 0.1 mm to obtain adhesive layer II; (3) An adhesive is added between a polyethylene terephthalate film with a thickness of 0.1 mm and a polyethylene terephthalate film with a thickness of 0.15 mm to obtain adhesive layer III; (4) An adhesive is added between a polyethylene terephthalate film with a thickness of 0.15 mm and a polyethylene film with a thickness of 0.05 mm to obtain a self-adhesive layer. The self-adhesive pre-laid waterproof membrane is obtained by calendering.

[0046] The preparation method of the adhesive is as follows: Example 1 According to the mass fraction, 40 parts of asphalt were heated to 180°C and melted, then 10 parts of styrene-butadiene-styrene block copolymer, 4 parts of carboxylated styrene-butadiene rubber, and 30 parts of modified tetraneedle-shaped zinc oxide whiskers were added and mixed evenly. The mixture was then cooled to 135°C and 7 parts of di-n-butyl phthalate, 1 part of antioxidant, and 3 parts of terpene resin were added and mixed until uniform to obtain the adhesive. The modified tetraneedle zinc oxide whiskers are composed of tetraneedle zinc oxide whisker I and tetraneedle zinc oxide whisker II in a mass ratio of 3:1; the antioxidant is composed of antioxidant 1010 and antioxidant 168 in a mass ratio of 1:2. The preparation method of tetraneedle-shaped zinc oxide whiskers I includes the following steps: 100 parts of tetraneedle-shaped zinc oxide whiskers were ultrasonically dispersed in 500 parts of methanol. The ultrasonic power was 500W, the ultrasonic frequency was 60kHz, the ultrasonic temperature was 30℃, and the ultrasonic time was 25min. 7 parts of glycidyl 2-methoxyphenyl ether were added and stirred at 250rpm for 15min. The mixture was then concentrated and dried to obtain tetraneedle-shaped zinc oxide whiskers I. The method for preparing tetra-needle-shaped zinc oxide whiskers II includes the following steps: Anhydrous ethanol and water were mixed in a mass ratio of 9:1 to prepare 1500 parts of ethanol solution. Acetic acid was added to adjust the pH of the ethanol solution to 4. 50 parts of KH-550 were added, and after hydrolysis for 3 hours, 100 parts of tetraneedle-shaped zinc oxide whiskers were added. The mixture was stirred at 60°C for 24 hours under a condenser. The product was diluted with anhydrous ethanol at room temperature, washed, filtered, and dried to obtain tetraneedle-shaped zinc oxide whiskers II.

[0047] Example 2 According to the mass fraction, 40 parts of asphalt were heated to 185°C to melt, and then 10 parts of styrene-butadiene-styrene block copolymer, 2 parts of carboxylated styrene-butadiene rubber, and 25 parts of modified tetraneedle-shaped zinc oxide whiskers were added and mixed evenly. The mixture was then cooled to 135°C and 5 parts of di-n-butyl phthalate, 1 part of antioxidant, and 5 parts of terpene resin were added and mixed until evenly mixed to obtain the adhesive. The modified tetraneedle zinc oxide whiskers consist of tetraneedle zinc oxide whisker I and tetraneedle zinc oxide whisker II in a mass ratio of 7:1; the antioxidant consists of antioxidant 1010 and antioxidant 168 in a mass ratio of 1:2. The preparation method of tetraneedle-shaped zinc oxide whiskers I includes the following steps: 100 parts of tetraneedle-shaped zinc oxide whiskers were ultrasonically dispersed in 500 parts of methanol. The ultrasonic power was 500W, the ultrasonic frequency was 60kHz, the ultrasonic temperature was 30℃, and the ultrasonic time was 25min. 4 parts of glycidyl 2-methoxyphenyl ether were added and stirred at 250rpm for 15min. The mixture was then concentrated and dried to obtain tetraneedle-shaped zinc oxide whiskers I. The method for preparing tetra-needle-shaped zinc oxide whiskers II includes the following steps: Anhydrous ethanol and water were mixed in a mass ratio of 9:1 to prepare 1500 parts of ethanol solution. Acetic acid was added to adjust the pH of the ethanol solution to 4. 20 parts of KH-550 were added and hydrolyzed for 1.5 h. Then 100 parts of tetraneedle-shaped zinc oxide whiskers were added and stirred at 60°C for 20 h under a condenser. The product was diluted with anhydrous ethanol at room temperature, washed, filtered, and dried to obtain tetraneedle-shaped zinc oxide whiskers II.

[0048] Example 3 The only difference from Example 1 is: According to the mass fraction, 40 parts of asphalt were heated to 180°C and melted, then 10 parts of styrene-butadiene-styrene block copolymer, 4 parts of carboxylated styrene-butadiene rubber, and 22.5 parts of tetraneedle zinc oxide whiskers I were added and mixed evenly. Then, 7.5 parts of tetraneedle zinc oxide whiskers II were added and mixed evenly. The mixture was cooled to 135°C and 7 parts of di-n-butyl phthalate, 1 part of antioxidant, and 3 parts of terpene resin were added and mixed until uniform to obtain the adhesive.

[0049] Example 4 The only difference from Example 1 is: By weight, 40 parts of asphalt were heated to 180°C and melted. Then, 10 parts of styrene-butadiene-styrene block copolymer, 4 parts of carboxylated styrene-butadiene rubber, and 7.5 parts of tetraneedle zinc oxide whiskers II were added and mixed evenly. Then, 22.5 parts of tetraneedle zinc oxide whiskers I were added and mixed evenly. The mixture was cooled to 135°C and 7 parts of di-n-butyl phthalate, 1 part of antioxidant, and 3 parts of terpene resin were added and mixed evenly to obtain the adhesive.

[0050] Comparative Example 1 The only difference from Example 1 is that the modified tetra-needle zinc oxide whiskers are tetra-needle zinc oxide whiskers I.

[0051] Comparative Example 2 The only difference from Example 1 is that the modified tetra-needle zinc oxide whiskers are tetra-needle zinc oxide whiskers II.

[0052] Comparative Example 3 The only difference from Example 1 is that the modified tetra-needle zinc oxide whiskers are replaced with an equal amount of tetra-needle zinc oxide whiskers.

[0053] Puncture resistance: Puncture strength test was conducted in accordance with GB / T 23457-2017. The final test result is the average of the results of 5 test specimens, and is recorded in Table 1.

[0054] Table 1. Test results of puncture resistance of three-layer polymer self-adhesive pre-laid waterproof membrane

[0055] The puncture resistance of Examples 1-4 is higher than that of Comparative Examples 1-3, indicating that the combined use of tetra-needle zinc oxide whiskers I and II improves the puncture resistance of the three-layer polymer self-adhesive pre-laid waterproof membrane. Furthermore, the puncture resistance of the three-layer polymer self-adhesive pre-laid waterproof membrane provided by this invention is significantly higher than that of existing three-layer polymer self-adhesive pre-laid waterproof membranes.

[0056] In addition, various performance tests were conducted on the three-layer polymer self-adhesive pre-laid waterproof membranes prepared in the above embodiments with reference to GB / T 23457-2017. The test results showed that all the performance of the products met the index of PY type pre-laid waterproof membranes.

[0057] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A three-layer polymer self-adhesive pre-laid waterproof membrane, comprising, from top to bottom, a protective layer, an adhesive layer I, a polymer film layer I, an adhesive layer II, a polymer film layer III, an adhesive layer III, a self-adhesive layer, and a release layer, characterized in that, At least one of the adhesive layer I, adhesive layer II, adhesive layer III, and self-adhesive layer comprises the following components: styrene-butadiene-styrene block copolymer, asphalt, carboxylated styrene-butadiene rubber, tetraneedle zinc oxide whisker I, tetraneedle zinc oxide whisker II, and additives. The tetraneedle zinc oxide whisker I is a tetraneedle zinc oxide whisker modified with a compound containing phenyl and epoxy groups in its molecular structure, and the tetraneedle zinc oxide whisker II is a tetraneedle zinc oxide whisker modified with aminosiloxane.

2. The three-layer polymer self-adhesive pre-laid waterproof membrane according to claim 1, characterized in that, The mass ratio of the tetraneedle zinc oxide whiskers I and II is 3~7:

1.

3. The three-layer polymer self-adhesive pre-laid waterproof membrane according to claim 1, characterized in that, The raw materials for the tetra-needle zinc oxide whisker I include tetra-needle zinc oxide whiskers in a mass ratio of 100:1 to 10 and compounds whose molecular structure includes phenyl and epoxy groups.

4. The three-layer polymer self-adhesive pre-laid waterproof membrane according to claim 1, characterized in that, The preparation method of the tetra-needle zinc oxide whisker I includes the following steps: dispersing the tetra-needle zinc oxide whisker in a solvent, adding a compound whose molecular structure includes phenyl and epoxy groups for mixing, concentrating, and drying to obtain the tetra-needle zinc oxide whisker I.

5. The three-layer polymer self-adhesive pre-laid waterproof membrane according to claim 1, characterized in that, The mass ratio of the styrene-butadiene-styrene block copolymer, asphalt, carboxylated styrene-butadiene rubber and additives is 10:40:2~4:7~12; The mass ratio of the tetraneedle zinc oxide whiskers I and II to the mass ratio of the styrene-butadiene-styrene block copolymer is 5~7:

2.

6. The three-layer polymer self-adhesive pre-laid waterproof membrane according to claim 1, characterized in that, The additives include at least one of the following characteristics: plasticizer, antioxidant, ultraviolet absorber, tackifying resin, and colorant.

7. A three-layer polymer self-adhesive pre-laid waterproof membrane according to claim 6, characterized in that, The additives consist of plasticizers, antioxidants, and tackifying resins in a mass ratio of 5~7:1:3~5.

8. A three-layer polymer self-adhesive pre-laid waterproof membrane according to claim 7, characterized in that, The plasticizer includes one or more of phthalates, dicarboxylic acid esters, and phosphate esters, and / or The antioxidant includes one or more of antioxidant 1010, antioxidant 168, and antioxidant 3114, and / or The tackifying resin includes one or more of terpene resin, petroleum resin, and coumarone resin.

9. A method for preparing a three-layer polymer self-adhesive pre-laid waterproof membrane, used to prepare the three-layer polymer self-adhesive pre-laid waterproof membrane according to any one of claims 1 to 8, characterized in that, Includes the following steps: A. After melting the asphalt, add the remaining components and mix evenly to obtain the adhesive; B. Add adhesive between the protective layer and polymer film layer I to obtain adhesive layer I; C. Add an adhesive between polymer film layer I and polymer film layer II to obtain adhesive layer II; D. Add an adhesive between polymer film layer II and polymer film layer III to obtain adhesive layer III; E. Add adhesive between polymer film layer III and the isolation layer to obtain a self-adhesive layer, and calender to obtain a three-layer polymer self-adhesive pre-laid waterproof membrane.

10. A method for preparing a three-layer polymer self-adhesive pre-laid waterproof membrane, used to prepare the three-layer polymer self-adhesive pre-laid waterproof membrane according to any one of claims 1 to 8, characterized in that, Includes the following steps: A. After melting the asphalt, add styrene-butadiene-styrene block copolymer, carboxylated styrene-butadiene rubber, and tetraneedle zinc oxide whiskers I and mix evenly. Then add the remaining components and mix evenly to obtain the adhesive. B. Add adhesive between the protective layer and polymer film layer I to obtain adhesive layer I; C. Add an adhesive between polymer film layer I and polymer film layer II to obtain adhesive layer II; D. Add an adhesive between polymer film layer II and polymer film layer III to obtain adhesive layer III; E. Add adhesive between polymer film layer III and the isolation layer to obtain a self-adhesive layer, and calender to obtain a three-layer polymer self-adhesive pre-laid waterproof membrane.

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