Pre-applied waterproofing sheet and preparation method therefor

Abstract

The present invention relates to a pre-applied waterproofing sheet and a preparation method therefor. The pre-applied waterproofing sheet comprises a base material layer, an adhesive layer, and a protective coating which are sequentially stacked, the protective coating is formed by coating the adhesive layer with protective coating slurry and curing, and the protective coating slurry comprises a photo-crosslinkable silicone resin emulsion and a room-temperature self-crosslinking acrylic resin emulsion. Through research, the present application finds that by using a compound of the photo-crosslinkable silicone resin emulsion and the room-temperature self-crosslinking acrylic resin emulsion as a film-forming substance of the protective coating of the pre-applied waterproofing sheet, the prepared pre-applied waterproofing sheet after rolling does not crack at a low temperature, does not have after-tack at a high temperature and has good adhesion to concrete.

Description

Pre-laid waterproof roll and preparation method thereof Technical Field

[0001] The present invention belongs to the technical field of waterproof rolls, and in particular relates to a pre-laid waterproof roll and a preparation method thereof. Background Art

[0002] Pre-laid waterproof membrane generally refers to structural concrete directly poured on the waterproof membrane. The self-adhesive layer of the membrane has good adhesion with the concrete, achieving the pre-laid anti-adhesive effect of the waterproof membrane. It is mainly composed of the main sheet, the self-adhesive layer, and the surface anti-(reducing) adhesion protective layer. It has the advantages of low requirements for the base surface, high construction freedom, reliable bonding, safety and environmental protection. It is widely used in underground waterproofing projects such as basements, subway tunnels, air-raid shelters, and grain warehouses, and has become one of the main categories of waterproof membranes.

[0003] Surface anti-adhesion (or anti-sticking) protective layers typically utilize inorganic sands such as quartz sand and sintered sand, or materials such as PET isolation film. However, the sand surface protective layer is prone to shedding and is heavy, making transport of the roll difficult and costly. Removal of the PET isolation film exposes the self-adhesive adhesive, which is then sprinkled on the adhesive layer before concrete is poured. This process is prone to sticking, contaminating the adhesive layer, resulting in reduced adhesion. Furthermore, construction is inconvenient and time-consuming. To address these issues, a method has been proposed for preparing pre-laid waterproof rolls using a coating material instead of isolation sand or isolation film. This method primarily involves applying an anti-adhesion coating to the adhesive layer to form an isolation layer. The resulting coating exhibits strong adhesion to concrete. For example, Chinese Patent CN108841268B discloses an anti-adhesion coating for pre-laid waterproof rolls and its preparation method. The coating employed is formulated with an acrylic emulsion or a silicone emulsion and other additives. Chinese patent CN115419117A discloses a pre-laid waterproofing membrane, comprising a main waterproof sheet layer, a pressure-sensitive adhesive layer and a polymer coating layer, wherein the polymer coating layer is composed of an acrylic emulsion, a filler and an air entraining agent.

[0004] Although the coating layer used in the above patent can play an anti-sticking role and has good adhesion to concrete, in actual use, the high-temperature anti-stick property of the acrylic coating itself makes it very easy to cause difficulty in unwinding the roll during transportation and construction. The alternating hot and cold temperatures can cause the coating to crack and leak glue, bringing inconvenience to construction. At the same time, the anti-stick nature of the coating leads to risks in bonding with concrete, limiting the application range of the roll. Therefore, how to balance the coating's anti-adhesion to the substrate and its adhesion to concrete is the core problem in solving the problem of using the coating to replace isolation sand in the preparation of lightweight waterproof rolls. Summary of the Invention

[0005] The technical problem actually solved by the present invention is to address the deficiencies of the existing technology and provide a pre-laid waterproof roll that does not crack at low temperatures, does not stick again at high temperatures, and has good adhesion to concrete after being rolled up.

[0006] In order to achieve the above object, the technical solution adopted by the present invention is:

[0007] A pre-laid waterproofing membrane comprises a substrate layer, an adhesive layer and a protective coating layer stacked in sequence, wherein the protective coating layer is formed by coating a protective coating slurry on the adhesive layer and curing the protective coating slurry, wherein the protective coating slurry comprises a photocrosslinkable silicone resin emulsion and a room temperature self-crosslinking acrylate resin emulsion;

[0008] The photocrosslinkable silicone resin emulsion is prepared by first subjecting the silicone polymer monomer to a hydrolysis and condensation reaction in the presence of a solvent, then subjecting the monomer to an end-capping reaction with an end-capping agent to obtain a prepolymer, then adding a photoinitiator to the mixture, removing the solvent, and emulsifying the mixture with water.

[0009] The organosilicon polymerization monomer includes a multifunctional acrylate monomer containing a siloxane structure, a siloxane monomer containing a long carbon chain, and an aminosiloxane monomer, and the molar ratio of the multifunctional acrylate monomer containing a siloxane structure, the siloxane monomer containing a long carbon chain, and the aminosiloxane monomer is 1~5:10~25:10~25.

[0010] In some embodiments, the multifunctional acrylate monomer containing a siloxane structure is prepared by reacting a siloxane containing an isocyanate functional group with an acrylate containing a hydroxyl group and at least two double bonds.

[0011] In some specific embodiments, the method for preparing the multifunctional acrylate monomer containing a siloxane structure comprises mixing an isocyanate-functional siloxane, an inhibitor, a catalyst, and a solvent, heating the mixture to 50-55° C., dropwise adding the acrylate containing a hydroxyl group and at least two double bonds, and continuing the reaction for 10-12 hours after the dropwise addition is complete to obtain a product, wherein the product is the multifunctional acrylate monomer containing a siloxane structure.

[0012] Furthermore, the method for preparing the multifunctional acrylate monomer containing a siloxane structure further comprises the step of washing the product with n-hexane after the reaction is completed, and the washing frequency is 3 to 5 times.

[0013] Furthermore, in the preparation method of the multifunctional acrylate monomer containing a siloxane structure, the polymerization inhibitor is one or a combination of 4-methoxyphenol, 2,6-di-tert-butyl-p-cresol, and 2-tert-butylhydroquinone; the catalyst is dibutyltin dilaurate; and the solvent is one or a combination of methyl ethyl ketone and cyclohexanone.

[0014] In some specific embodiments, the molar ratio of the siloxane containing an isocyanate functional group to the acrylate containing a hydroxyl group and at least two double bonds is 1:0.8:1.2.

[0015] In some specific embodiments, the siloxane containing an isocyanate functional group is one or a combination of 3-isocyanatepropyltrimethoxysilane, isocyanatepropyltriethoxysilane, and 1-dimethoxy(methyl)silylmethyl isocyanate.

[0016] In some specific embodiments, the acrylate containing a hydroxyl group and at least two double bonds is pentaerythritol triacrylate.

[0017] In some embodiments, the long carbon chain is a carbon chain having a carbon number of 3 to 15. The use of a siloxane monomer containing a long carbon chain helps to improve the flexibility of the protective coating.

[0018] In some specific embodiments, the siloxane monomer containing a long carbon chain is one or a combination of propyltrimethoxysilane, n-propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, pentyltriethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, and decyltrimethoxysilane.

[0019] The long carbon chain is a straight chain structure.

[0020] In some specific embodiments, the aminosiloxane monomer is one or a combination of aminopropyltrimethoxysilane, aminopropyltriethoxysilane, and N-(2-aminoethyl)-3-aminopropyltrimethoxysilane.

[0021] In some specific embodiments, the capping agent is hexamethyldisiloxane, hexaethyldisiloxane, or a combination of hexamethyldisiloxane and hexaethyldisiloxane.

[0022] In some specific embodiments, the photoinitiator is one or a combination of benzophenone ammonium chloride, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide, and poly[2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone];

[0023] The amount of the photoinitiator is 2-4% of the total mass of the organosilicon polymerization monomer;

[0024] The solvent is one or a combination of ethanol, isopropanol, and n-propanol.

[0025] In some embodiments, the preparation method of the photocrosslinkable silicone resin emulsion includes: mixing a silicone polymerization monomer, an inhibitor and a solvent under light-proof conditions, adding hydrochloric acid dropwise, then heating to 55~70°C for reaction, then adding a capping agent, performing a capping reaction at 60~80°C, cooling, adding a photoinitiator and mixing, then removing the solvent by reduced pressure distillation, and adding water for emulsification to obtain the photocrosslinkable silicone resin emulsion.

[0026] In some specific embodiments, the preparation method of the photocrosslinkable silicone resin emulsion includes: mixing a silicone polymerization monomer, an inhibitor and a solvent under light-proof conditions, adding hydrochloric acid dropwise, then heating to 55~70°C for reaction for 3~7 hours, then adding a capping agent, performing a capping reaction at 60~80°C for 1~3 hours, cooling, adding a photoinitiator and mixing, then removing the solvent by reduced pressure distillation, and adding water for emulsification to obtain the photocrosslinkable silicone resin emulsion.

[0027] In some specific embodiments, the solid content of the photo-crosslinkable silicone resin emulsion is 20-40%.

[0028] In some embodiments, the room temperature self-crosslinking acrylic resin emulsion has a core-shell structure, the core layer structure is obtained by polymerizing the core layer monomer, and the shell layer is obtained by polymerizing the shell layer monomer. The shell layer monomer includes a room temperature self-crosslinking monomer, a soft monomer, a hard monomer and a hydrophilic monomer, wherein the room temperature self-crosslinking monomer is one or a combination of N-hydroxyethyl acrylamide, N-hydroxymethyl acrylamide, N-isobutoxymethyl acrylamide, and N-n-butoxymethyl acrylamide.

[0029] In some specific embodiments, the molar ratio of the room temperature self-crosslinking monomer, the soft monomer, the hard monomer and the hydrophilic monomer is 1:10-15:10-15:1-5.

[0030] In some specific embodiments, in the shell monomers, the soft monomer is one or a combination of ethyl acrylate, butyl acrylate, octyl acrylate, lauryl acrylate, lauryl methacrylate, and hydroxyethyl acrylate; the hard monomer is one or a combination of methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, isobornyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and styrene; and the hydrophilic monomer is one or a combination of acrylic acid, methacrylic acid, and acrylamide.

[0031] In some specific embodiments, the core layer monomers include a hard monomer, a soft monomer, and a hydrophilic monomer, and the molar ratio of the hard monomer, the soft monomer, and the hydrophilic monomer is 15-20:15-20:1;

[0032] The molar ratio of the core layer monomer to the shell layer monomer is 1:0.4-1.5.

[0033] In some specific embodiments, in the core layer monomers, the hard monomer is one or a combination of methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, isobornyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and styrene; the soft monomer is one or a combination of ethyl acrylate, butyl acrylate, octyl acrylate, lauryl acrylate, lauryl methacrylate, and hydroxyethyl acrylate; and the hydrophilic monomer is one or a combination of acrylic acid, methacrylic acid, and acrylamide.

[0034] The room temperature self-crosslinking acrylic ester resin emulsion is a core-shell structured room temperature self-crosslinking acrylic ester resin emulsion obtained by pre-emulsification semi-continuous seed emulsion polymerization.

[0035] In some specific embodiments, the method for preparing the room temperature self-crosslinking acrylic resin emulsion comprises the following steps:

[0036] (1) Mixing core layer monomer, emulsifier and water to obtain core layer monomer pre-emulsion;

[0037] (2) mixing the shell monomer, emulsifier and water to obtain a shell monomer pre-emulsion;

[0038] (3) adding a portion of the core layer monomer pre-emulsion and the first portion of the initiator to a reactor containing a buffer solution to initiate polymerization to obtain a seed emulsion;

[0039] (4) adding the second portion of the initiator aqueous solution and the remaining shell monomer pre-emulsion dropwise into the reactor to carry out core layer polymerization reaction;

[0040] (5) Add the remaining initiator aqueous solution and the shell monomer pre-emulsion dropwise into the reactor to carry out shell polymerization reaction to obtain the room temperature self-crosslinking acrylic resin emulsion.

[0041] Furthermore, in step (1), the amount of the emulsifier is 0.8-1.5% of the total mass of the core layer monomer and the shell layer monomer;

[0042] In step (2), the amount of the emulsifier is 0.8-1.5% of the total mass of the core layer monomer and the shell layer monomer;

[0043] In step (3), the buffer solution comprises water, a buffering agent, and an emulsifier, wherein the amount of water is 35-55% of the total mass of the room temperature self-crosslinking acrylic resin emulsion, and the amount of the emulsifier is 0.8-1.5% of the total mass of the core layer monomer and the shell layer monomer;

[0044] In step (3), the portion of the core layer monomer pre-emulsion accounts for 10-30% of the total amount of the core layer monomer pre-emulsion, and the initiation polymerization is carried out at 60-70° C.;

[0045] In step (4), the core layer polymerization reaction is carried out at 60-70°C;

[0046] In step (5), the shell polymerization reaction is carried out at 70-90°C;

[0047] The total mass of the initiators in step (3), step (4) and step (5) is 0.2-0.4% of the total mass of the core layer monomers and the shell layer monomers, and the first part of the initiator in step (3) accounts for 10-30% of the total amount of the initiator, and the second part of the initiator in step (4) accounts for 10-30% of the total amount of the initiator.

[0048] The solid content of the room temperature self-crosslinking acrylic resin emulsion is 35-45%.

[0049] In some specific embodiments, the mass ratio of the photo-crosslinkable silicone resin emulsion to the room temperature self-crosslinking acrylate resin emulsion is 1:4-10.

[0050] In some specific embodiments, the substrate layer is a polymer substrate layer, such as polyvinyl chloride; and the adhesive layer is a hot melt pressure-sensitive adhesive.

[0051] In some specific embodiments, the protective coating slurry further includes powder and additives, wherein the powder includes one or a combination of titanium dioxide and calcium carbonate, and the additives include one or a combination of dispersants, defoamers, antioxidants, ultraviolet absorbers, and bactericides.

[0052] Furthermore, the powder is a combination of titanium dioxide and calcium carbonate, and the titanium dioxide accounts for 25-35% of the weight of the powder. Specifically, titanium dioxide is Japanese Ishihara R930, and heavy calcium carbonate is Chinese Jiangsu Qunxin 051A.

[0053] In some specific embodiments, the protective coating slurry comprises, by weight:

[0054] 5-10 parts of photocrosslinkable silicone resin emulsion

[0055] 40~50 parts of room temperature self-crosslinking acrylic resin emulsion

[0056] 13~16 parts powder

[0057] 5~10 parts of additives

[0058] 25~30 parts water.

[0059] In some embodiments, the method for preparing the protective coating slurry comprises the following steps:

[0060] (A) Add water, dispersant, defoamer and powder to a high-speed dispersion kettle and disperse at a speed of 800-1000 rpm for 20-30 minutes;

[0061] (B) reducing the speed to 400-500 rpm, slowly adding the photocrosslinkable silicone resin emulsion and the room temperature self-crosslinking acrylate resin emulsion, and continuing to disperse for 20-30 minutes;

[0062] (C) Add antioxidant, ultraviolet absorber and fungicide to the dispersion kettle in sequence, reduce the speed to 200~300rpm, disperse for 20~30min and then filter.

[0063] The second technical solution adopted by the present invention is: the preparation method of the pre-laid waterproof coiled material, the preparation method of the pre-laid waterproof coiled material comprises the following steps:

[0064] S1. preparing an adhesive layer on the substrate layer;

[0065] S2. Applying the protective coating slurry on the adhesive layer, drying it at a temperature of 60-70° C., and then curing it with ultraviolet light to form the protective coating.

[0066] Furthermore, in step S2, the wavelength of the ultraviolet light irradiation is 310-420 nm, the maximum light intensity is 100±10 mW / cm2, and the irradiation time is 60±10 s;

[0067] The thickness of the protective coating is 20-100 μm.

[0068] Due to the application of the above technical solution, the present invention has the following advantages compared with the prior art:

[0069] The inventors of the present application have discovered through research that by using a compound of a photocrosslinkable silicone resin emulsion and a room temperature self-crosslinking acrylic resin emulsion as the film-forming substance for the protective coating of pre-laid waterproof membranes, the prepared pre-laid waterproof membranes will not crack at low temperatures, will not become sticky at high temperatures, and will have good adhesion to concrete after being rolled up. DETAILED DESCRIPTION

[0070] As described in the background art, ordinary acrylic resin emulsions usually have high-temperature re-sticking characteristics when applied to polymer pre-laid waterproof membranes. The reason for this is that the molecular structure of the acrylic resin relaxes at high temperatures.

[0071] Through research, the inventors of this application have discovered that a composite of a photocrosslinkable silicone resin emulsion and a room-temperature self-crosslinking acrylate resin emulsion can be used as the film-forming substance for the protective coating of pre-laid waterproofing membranes. During the curing process, the two form a moderately crosslinked network protective coating. The crosslinked acrylate resin molecules and the crosslinked silicone resin molecules entangle internally to form an interpenetrating structure. The crosslinked acrylate resin molecular structure is further stabilized, which helps improve the inherent high-temperature re-adhesion properties of the acrylate resin coating, reduces its temperature sensitivity, and can also alleviate the phenomenon of cracking and adhesive leakage caused by temperature. In addition, the surface migration properties of the silicone resin can be used to improve the coating's anti-adhesion properties, avoiding the difficulty in unwinding the pre-laid waterproofing membrane due to adhesion between the protective coating and the backing substrate layer. The core-shell structure of the acrylate resin has excellent film-forming properties, ensuring effective adhesion between the protective coating and the concrete.

[0072] The technical solutions of the present invention are described in detail below in conjunction with 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. Example 1

[0073] The pre-laid waterproofing membrane provided in this embodiment includes a substrate layer, an adhesive layer and a protective coating layer stacked in sequence. The protective coating layer is formed by coating a protective coating slurry on the adhesive layer and curing it.

[0074] In this example, the base material layer is polyvinyl chloride with a thickness of 1 mm; the adhesive layer is SIS hot melt pressure sensitive adhesive.

[0075] In this example, the protective coating slurry used in the protective coating is composed of the following components: 8 parts photocrosslinkable silicone resin emulsion, 45 parts room temperature self-crosslinking acrylate resin emulsion, 4 parts titanium dioxide, 10 parts heavy calcium carbonate, 1 part dispersant, 1 part defoamer, 10101 parts antioxidant, 3291 parts UV absorber, 0.5 parts fungicide, and 25 parts water. It is prepared by the following method: water, dispersant, defoamer, titanium dioxide, and heavy calcium carbonate are sequentially added to a high-speed dispersing kettle, and the mixture is dispersed at 900 rpm for 25 minutes; the speed is reduced to 450 rpm, and the photocrosslinkable silicone resin emulsion and room temperature self-crosslinking acrylate resin emulsion are slowly added, and dispersion is continued for another 25 minutes; then, the antioxidant, UV absorber, and fungicide are added, the speed is reduced to 250 rpm, and dispersion is continued for 25 minutes, followed by filtration to obtain the protective coating slurry.

[0076] The photocrosslinkable silicone resin emulsion is prepared by the following method:

[0077] (1) Preparation of multifunctional acrylate monomers containing siloxane structures

[0078] 3-Isocyanatepropyltrimethoxysilane (1 mol, 205 g), 2,6-di-tert-butyl-p-cresol (1 g), and dibutyltin dilaurate (0.5 g) were dissolved in methyl ethyl ketone (100 g) and then added to a reactor equipped with a mechanical stirrer, a thermometer, and a reflux condenser. After mixing evenly, the mixture was heated to 55°C. Then, an equal molar amount of pentaerythritol triacrylate (1 mol, 298 g) to 3-isocyanatepropyltrimethoxysilane was added dropwise. After the addition was complete, the reaction was continued for 11 hours. The obtained product was washed with n-hexane 4 times to obtain a multifunctional acrylate monomer containing a siloxane structure (427 g, yield of about 85%).

[0079] (2) Preparation of photocrosslinkable silicone resin emulsion

[0080] A multifunctional acrylate monomer containing a siloxane structure (1 mol, 503 g), butyltrimethoxysilane (6 mol, 1069.8 g), aminopropyltrimethoxysilane (6 mol, 1075.8 g) and 2,6-di-tert-butyl-p-cresol (15 g) were dissolved in isopropanol (1500 g) and mixed evenly. The mixture was then added to a reactor equipped with a mechanical stirrer, a thermometer, and a condenser reflux tube. The temperature was raised to 55°C, 3 mL of concentrated hydrochloric acid (36%) was slowly added dropwise, and the temperature was then raised to 65°C for reaction for 5 h. Hexamethyldisiloxane was then added for end-capping, the temperature was raised to 75°C, and the reaction was maintained at this temperature for 2 h. After the reaction, the temperature was lowered to room temperature, and a photoinitiator (2-hydroxy-2-methyl-1-phenyl-1-propanone) (3% by weight of the total monomer mass) was added and mixed evenly in the dark. The solvent and low-boiling residues were then removed by reduced pressure distillation at 50°C / 130 mmHg. Deionized water was then added and emulsified with high-speed stirring to obtain a photocrosslinkable silicone resin emulsion with a solid content of 40%.

[0081] The room temperature self-crosslinking acrylic resin emulsion is prepared by the following method:

[0082] Step S1: preparing the core layer monomer pre-emulsion

[0083] Methyl methacrylate (18 mol, 1801.8 g), butyl acrylate (18 mol, 2307.6 g), acrylic acid (1 mol, 72.1 g), sodium lauryl sulfate (71 g) and water (1500 g) were mixed to obtain a core layer monomer pre-emulsion.

[0084] Step S2: preparing shell monomer pre-emulsion

[0085] N-Hydroxyethyl acrylamide (1 mol, 115.1 g), butyl acrylate (12 mol, 1538.4 g), methyl methacrylate (12 mol, 1201.2 g), acrylic acid (1 mol, 72.1 g), sodium lauryl sulfate (71 g) and water (1400 g) were mixed to obtain a shell monomer pre-emulsion.

[0086] Step S3, adding 20% ​​of the core layer monomer pre-emulsion and 4.2 g of ammonium persulfate to a reactor containing a buffer solution (71 g of sodium lauryl sulfate, 2 g of sodium carbonate, and water), and initiating polymerization at 65° C. until the temperature no longer rises, to obtain a seed emulsion;

[0087] Step S4: dropwise add an aqueous solution of ammonium persulfate prepared by mixing 4.2 g of ammonium persulfate and 20 g of water and the remaining core layer monomer pre-emulsion into the reactor, maintain the temperature at 65° C. for core layer polymerization, and control the dropwise addition time to 2 h. After the dropwise addition is completed, continue the reaction for 1 h.

[0088] Step S5: dropwise add an aqueous solution of ammonium persulfate prepared by mixing 13.6 g of ammonium persulfate and 72 g of water and the shell monomer pre-emulsion into the reactor, carry out shell polymerization at 75° C., and control the dropwise addition time to 2 h. After the dropwise addition is completed, continue the reaction for 1 h.

[0089] Step S6: adding ammonia water to the reaction kettle to adjust the pH to 7-8, stirring for 20 minutes, and then filtering to obtain a room temperature self-crosslinking acrylic resin emulsion with a solid content of 40%.

[0090] The pre-laid waterproof membrane is prepared by the following method:

[0091] A 0.3 mm thick SIS hot melt pressure sensitive adhesive was applied to a 1 mm thick polyvinyl chloride sheet to form an adhesive layer, and then a protective coating slurry was applied on the adhesive layer. The layer was dried at 65°C and then irradiated with 320 nm wavelength ultraviolet light for 60 seconds to obtain a protective coating with a thickness of 80 μm. The maximum light intensity was 100 mW / cm2. Example 2

[0092] The pre-laid waterproof membrane provided in this embodiment is different from that in Example 1 in that the protective coating slurry used in the protective coating is composed of the following components: 10 parts of photocrosslinkable silicone resin emulsion, 50 parts of room temperature self-crosslinking acrylate resin emulsion, 4 parts of titanium dioxide, 10 parts of heavy calcium, 1 part of dispersant, 1 part of defoaming agent, 10101 parts of antioxidant, 3291 parts of ultraviolet absorber, 0.5 part of fungicide and 25 parts of water.

[0093] In this example, when preparing the photocrosslinkable silicone resin emulsion, 5 mol of n-octyltrimethoxysilane is used instead of butyltrimethoxysilane; 8 mol of aminopropyltriethoxysilane is used instead of aminopropyltrimethoxysilane. Example 3

[0094] The pre-laid waterproof membrane provided in this embodiment is different from that in Example 1 in that the protective coating slurry used in the protective coating is composed of the following components: 5 parts of photocrosslinkable silicone resin emulsion, 45 parts of room temperature self-crosslinking acrylic resin emulsion, 5 parts of titanium dioxide, 10 parts of heavy calcium, 1 part of dispersant, 1 part of defoaming agent, 10101 parts of antioxidant, 3291 parts of ultraviolet absorber, 0.5 part of fungicide and 25 parts of water.

[0095] In this example, when preparing the room temperature self-crosslinking acrylic resin emulsion, 15 mol of isobutyl methacrylate is used instead of methyl methacrylate, and 15 mol of lauryl acrylate is used instead of butyl acrylate in the preparation of the core layer monomer pre-emulsion. Example 4

[0096] The pre-laid waterproof membrane provided in this embodiment is different from that in Example 1 in that: when preparing the room temperature self-crosslinking acrylic resin emulsion, 1 mol of N-hydroxymethyl acrylamide is used instead of N-hydroxyethyl acrylamide, 10 mol of lauryl acrylate is used instead of butyl acrylate, and 10 mol of isobutyl methacrylate is used instead of methyl methacrylate in the preparation of the shell monomer pre-emulsion.

[0097] Comparative Example 1

[0098] The pre-laid waterproof membrane provided in this comparative example is different from that in Example 1 in that the protective coating slurry used in the protective coating is composed of the following components: 20 parts of photocrosslinkable silicone resin emulsion, 45 parts of room temperature self-crosslinking acrylate resin emulsion, 4 parts of titanium dioxide, 10 parts of heavy calcium, 1 part of dispersant, 1 part of defoaming agent, 10101 parts of antioxidant, 3291 parts of ultraviolet absorber, 0.5 part of fungicide and 25 parts of water.

[0099] Comparative Example 2

[0100] The pre-laid waterproof membrane provided in this comparative example is different from that in Example 1 in that no photo-crosslinkable silicone resin emulsion is used in the protective coating slurry.

[0101] Comparative Example 3

[0102] The pre-laid waterproofing membrane provided in this comparative example is different from that in Example 1 in that butyltrimethoxysilane is not added when preparing the photocrosslinkable silicone resin emulsion.

[0103] Comparative Example 4

[0104] The pre-laid waterproofing membrane provided in this comparative example is different from that in Example 1 in that: when preparing the room temperature self-crosslinking acrylic resin emulsion, the amount of each component is the same as that in Example 1, and the amount of each component in step S1 and step S2 of Example 1 is referred to for preparation, the core layer monomer, the shell layer monomer, the emulsifier and water are mixed to prepare a monomer pre-emulsion, which is then divided into a first pre-emulsion accounting for 10% and a second pre-emulsion accounting for 90%, and then prepared with reference to the preparation method of the room temperature self-crosslinking acrylic resin emulsion in Example 1, first adding a buffer solution and the first pre-emulsion to a reactor, initiating polymerization under the action of an initiator to obtain a seed emulsion, and then adding an initiator (the initiator is the total amount of the initiator in steps S4 and S5) and the second pre-emulsion dropwise to the seed emulsion, and the dripping is completed over 4 hours, and a polymerization reaction is carried out to obtain an acrylic resin emulsion.

[0105] Performance Testing

[0106] The pre-laid waterproof membranes of Examples 1 to 4 and Comparative Examples 1 to 4 were tested for low-temperature flexural properties, low-temperature flexibility, and peeling strength with post-cast concrete in accordance with GB / T 23457-2017 Pre-laid Waterproof Membrane. The results are shown in Table 1.

[0107] Among them, the test method for anti-adhesion refers to "FZ / T01063-2008 Determination of Anti-adhesion of Coated Fabrics".

[0108]

[0109] The above embodiments are intended only to illustrate the technical concepts and features of the present invention. Their purpose is to enable those skilled in the art to understand the contents of the present invention and implement them accordingly. They are not intended to limit the scope of protection of the present invention. Any equivalent changes or modifications made in accordance with the spirit of the present invention are intended to be covered by the scope of protection of the present invention.

[0110] The endpoints of the ranges and any values ​​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 endpoints of each range, the endpoints of each range and individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered to be specifically disclosed herein.

Claims

1. A pre-laid waterproofing coiled material, comprising a substrate layer, an adhesive layer and a protective coating layer stacked in sequence, wherein the protective coating layer is formed by coating a protective coating slurry on the adhesive layer and curing the protective coating slurry, characterized in that: The protective coating slurry includes a photo-crosslinkable silicone resin emulsion and a room temperature self-crosslinking acrylate resin emulsion; The photo-crosslinkable silicone resin emulsion is prepared by first subjecting the silicone polymer monomer to a hydrolysis and condensation reaction in the presence of a solvent, then subjecting the monomer to a capping reaction with a capping agent to obtain a prepolymer, then adding a photoinitiator to mix, removing the solvent, and emulsifying with water; The organosilicon polymerization monomers include multifunctional acrylate monomers containing siloxane structures, siloxane monomers containing long carbon chains, and aminosiloxane monomers, and the feeding molar ratio of the multifunctional acrylate monomers containing siloxane structures, the siloxane monomers containing long carbon chains, and the aminosiloxane monomers is 1~5:10~25:10~25.

2. The pre-laid waterproofing membrane according to claim 1, characterized in that: The multifunctional acrylate monomer containing a siloxane structure is prepared by reacting a siloxane containing an isocyanate functional group with an acrylate containing a hydroxyl group and at least two double bonds.

3. The pre-laid waterproofing membrane according to claim 2, characterized in that: The siloxane containing isocyanate functional groups is one or a combination of 3-isocyanate propyl trimethoxy silane, isocyanate propyl triethoxy silane, 1-dimethoxy (methyl) silyl methyl isocyanate; and / or, the acrylate containing hydroxyl groups and at least two double bonds is pentaerythritol triacrylate.

4. The pre-laid waterproofing membrane according to claim 1, characterized in that: The long carbon chain is a carbon chain having 3 to 15 carbon atoms.

5. The pre-laid waterproofing membrane according to claim 4 is characterized in that: The siloxane monomer containing a long carbon chain is one or a combination of propyltrimethoxysilane, n-propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, pentyltriethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane and decyltrimethoxysilane.

6. The pre-laid waterproofing membrane according to claim 1, characterized in that: The aminosiloxane monomer is one or a combination of aminopropyltrimethoxysilane, aminopropyltriethoxysilane, and N-(2-aminoethyl)-3-aminopropyltrimethoxysilane.

7. The pre-laid waterproofing membrane according to claim 1 is characterized in that: The end-capping agent is one or a combination of hexamethyldisiloxane and hexaethyldisiloxane; and / or, The photoinitiator is one or a combination of benzophenone ammonium chloride, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide, and poly[2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone]; and / or, The amount of the photoinitiator is 2-4% of the total mass of the organosilicon polymerization monomer; and / or, The solvent is one or a combination of ethanol, isopropanol and n-propanol.

8. The pre-laid waterproofing membrane according to any one of claims 1 to 7, characterized in that: The preparation method of the photo-crosslinkable silicone resin emulsion comprises: mixing silicone polymerization monomers, inhibitors and solvents under light-proof conditions, adding hydrochloric acid dropwise, then heating to 55-70° C. for reaction, then adding a capping agent, performing a capping reaction at 60-80° C., cooling, adding a photoinitiator and mixing, then removing the solvent by reduced pressure distillation, and adding water for emulsification to obtain the photo-crosslinkable silicone resin emulsion.

9. The pre-laid waterproofing membrane according to claim 1, characterized in that: The room temperature self-crosslinking acrylic resin emulsion is a core-shell structure, wherein the core layer structure is obtained by polymerizing the core layer monomer, and the shell layer is obtained by polymerizing the shell layer monomer. The shell layer monomer includes a room temperature self-crosslinking monomer, a soft monomer, a hard monomer and a hydrophilic monomer, wherein the room temperature self-crosslinking monomer is one or a combination of N-hydroxyethyl acrylamide, N-hydroxymethyl acrylamide, N-isobutoxymethyl acrylamide and N-n-butoxymethyl acrylamide.

10. The pre-laid waterproofing membrane according to claim 9, characterized in that: The molar ratio of the room temperature self-crosslinking monomer, the soft monomer, the hard monomer and the hydrophilic monomer is 1:10-15:10-15:1-5.

11. The pre-laid waterproofing membrane according to claim 9, characterized in that: In the shell monomers, the soft monomer is one or a combination of ethyl acrylate, butyl acrylate, octyl acrylate, lauryl acrylate, lauryl methacrylate, and hydroxyethyl acrylate; the hard monomer is one or a combination of methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, isobornyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and styrene; and the hydrophilic monomer is one or a combination of acrylic acid, methacrylic acid, and acrylamide.

12. The pre-laid waterproofing membrane according to claim 9, characterized in that: The core layer monomers include hard monomers, soft monomers and hydrophilic monomers, and the molar ratio of the hard monomers, soft monomers and hydrophilic monomers is 15-20:15-20:1; and / or, The molar ratio of the core layer monomer to the shell layer monomer is 1:0.4-1.

5.

13. The pre-laid waterproofing membrane according to claim 12, characterized in that: In the core layer monomers, the hard monomer is one or a combination of methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, isobornyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and styrene; the soft monomer is one or a combination of ethyl acrylate, butyl acrylate, octyl acrylate, lauryl acrylate, lauryl methacrylate, and hydroxyethyl acrylate; and the hydrophilic monomer is one or a combination of acrylic acid, methacrylic acid, and acrylamide.

14. The pre-laid waterproofing membrane according to any one of claims 9 to 13, characterized in that: The method for preparing the room temperature self-crosslinking acrylic resin emulsion comprises the following steps: (1) mixing a core layer monomer, an emulsifier and water to obtain a core layer monomer pre-emulsion; (2) mixing a shell monomer, an emulsifier and water to obtain a shell monomer pre-emulsion; (3) adding a portion of the core layer monomer pre-emulsion and the first portion of the initiator into a reaction kettle containing a buffer solution to initiate polymerization to obtain a seed emulsion; (4) adding the second part of the initiator aqueous solution and the remaining shell monomer pre-emulsion to the reaction kettle to carry out core layer polymerization reaction; (5) Add the remaining initiator aqueous solution and the shell monomer pre-emulsion dropwise into the reaction kettle to carry out shell polymerization reaction to obtain the room temperature self-crosslinking acrylic resin emulsion.

15. The pre-laid waterproofing membrane according to claim 14, characterized in that: In step (1), the amount of the emulsifier is 0.8-1.5% of the total mass of the core layer monomer and the shell layer monomer; and / or, In step (2), the amount of the emulsifier is 0.8-1.5% of the total mass of the core layer monomer and the shell layer monomer; In step (3), the buffer comprises water, a buffer and an emulsifier, the amount of water is 35-55% of the total mass of the room temperature self-crosslinking acrylic resin emulsion, and the amount of the emulsifier is 0.8-1.5% of the total mass of the core layer monomer and the shell layer monomer; and / or, In step (3), the portion of the core layer monomer pre-emulsion accounts for 10-30% of the total amount of the core layer monomer pre-emulsion, and the initiation polymerization is carried out at 60-70° C.; and / or, In step (4), the core layer polymerization reaction is carried out at 60-70° C.; and / or, In step (5), the shell polymerization reaction is carried out at 70-90° C.; and / or, The total mass of the initiator in step (3), step (4) and step (5) is 0.2-0.4% of the total mass of the core layer monomer and the shell layer monomer, and the first part of the initiator in step (3) accounts for 10-30% of the total amount of the initiator, and the second part of the initiator in step (4) accounts for 10-30% of the total amount of the initiator.

16. The pre-laid waterproofing membrane according to any one of claims 1 to 7 and 9 to 13, characterized in that: The mass ratio of the photo-crosslinkable silicone resin emulsion to the room temperature self-crosslinking acrylate resin emulsion is 1:4-10; and / or, The substrate layer is polyvinyl chloride; and / or, The adhesive layer is a hot melt pressure sensitive adhesive.

17. The pre-laid waterproofing membrane according to claim 16, characterized in that: The protective coating slurry also includes powder and additives. The powder includes one or a combination of titanium dioxide and calcium carbonate. The additives include one or a combination of dispersants, defoamers, antioxidants, ultraviolet absorbers, and bactericides.

18. The pre-laid waterproofing membrane according to claim 17, characterized in that: The protective coating slurry comprises, by weight: 5~10 parts of photo-crosslinkable silicone resin emulsion 40~50 parts of room temperature self-crosslinking acrylic resin emulsion 13~16 servings of powder 5~10 parts of additives 25~30 parts of water.

19. The method for preparing the pre-laid waterproofing roll according to any one of claims 1 to 18, characterized in that: The preparation method of the pre-laid waterproofing coiled material comprises the following steps: S1, preparing an adhesive layer on the substrate layer; S2, coating the protective coating slurry on the adhesive layer, drying it at a temperature of 60-70° C., and then curing it through ultraviolet light to form the protective coating.

20. The method for preparing the pre-laid waterproofing membrane according to claim 19, characterized in that: In step S2, the wavelength of the ultraviolet light irradiation is 310-420 nm, and the irradiation time is 60±10 s; And / or, the thickness of the protective coating is 20-100 μm.

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