Polyurethane waterproof coating, preparation method and waterproof product

Abstract

The invention provides a polyurethane waterproof coating, a preparation method and a waterproof product. The polyurethane waterproof coating comprises the following raw materials in parts by weight: 206 parts of a polyurethane prepolymer; the polyurethane prepolymer is formed by reaction of hydroxyl-terminated polybutadiene acrylonitrile, organic silicon dihydric alcohol, polyether polyol and polyisocyanate; and 3 to 7 parts of oxazolidine end-capped modified resin based on 206 parts of the polyurethane prepolymer; 6-12 parts of a latent curing agent; 40 to 85 parts of an epoxy plasticizer; and 130 to 300 parts of an additive. According to the polyurethane waterproof coating, organic silicon dihydric alcohol, hydroxyl-terminated polybutadiene acrylonitrile and polyisocyanate react to form an NCO-terminated prepolymer, oxazolidine-terminated modified resin contains terminal group oxazolidine, and the terminal group oxazolidine is hydrolyzed to release secondary hydroxyl and amino to participate in the reaction; the peeling strength of the waterproof material formed by compounding the polyurethane coating and the coiled material is improved.

Description

Technical Field

[0001] The present application belongs to the field of waterproof coatings, and specifically relates to a polyurethane waterproof coating, a preparation method and a waterproof product. Background Art

[0002] In recent years, composite waterproofing technology represented by coatings and membranes has become a hot topic in the field of building / road and bridge waterproofing. The traditional construction restrictions on asphalt membranes have become more stringent. Therefore, it is particularly important to use environmentally friendly construction methods instead of fire baking processes that produce toxic and harmful smoke.

[0003] The commonly used construction process of asphalt membrane is to use adhesive to achieve membrane paving. The construction method is to first apply the waterproof coating on the base surface, and then cover the asphalt waterproof membrane on the coating layer. The coating layer also acts as a binder, perfectly bonding the base surface and the membrane together through the cold construction method. There is no emission of harmful substances during the construction process, realizing truly environmentally friendly construction. The composite use of waterproof coating and asphalt waterproof membrane forms an actual double-channel waterproofing, which improves the waterproofing stability. However, the waterproof material formed by the composite of traditional polyurethane waterproof coating and materials (such as asphalt membrane) has low peeling strength and poor bonding effect, which affects the application scope of polyurethane waterproof coating. Summary of the invention

[0004] The present application provides a polyurethane waterproof coating, a preparation method and a waterproof product, aiming to improve the peel strength of a waterproof material formed by a composite of the polyurethane waterproof coating and a material.

[0005] The first aspect of the present application provides a polyurethane waterproof coating, comprising the following raw materials in parts by weight:

[0006] Polyurethane prepolymer, 206 parts; polyurethane prepolymer is formed by reacting terminal hydroxyl polybutadiene acrylonitrile, silicone diol, polyether polyol and polyisocyanate; and the following components, all based on 206 parts of polyurethane prepolymer: oxazolidine end-capping modified resin, 3 to 7 parts; latent curing agent, 6 to 12 parts; epoxy plasticizer, 40 to 85 parts; additives, 130 to 300 parts.

[0007] In a feasible implementation of the first aspect of the present application, one oxazolidine-terminated modified resin molecule in the oxazolidine-terminated modified resin further includes at least two epoxy groups.

[0008] In a feasible implementation of the first aspect of the present application, the number average molecular weight of the oxazolidine-terminated modified resin is 1000-3000.

[0009] In a feasible implementation manner of the first aspect of the present application, the epoxy equivalent of the oxazolidine-terminated modified resin is 330 g / mol to 380 g / mol.

[0010] In a feasible embodiment of the first aspect of the present application, the oxazolidine-terminated modified resin includes the following

[0011] The structure shown in formula 1:

[0012]

[0013] In Formula 1, n is an integer of 1 to 2, X is an integer of 1 to 3, R is an alkyl group or a phenyl group, R1 is selected from H, an alkyl group or a phenyl group, and m is an integer of 1 to 5.

[0014] In a feasible implementation of the first aspect of the present application, the number average molecular weight of the hydroxy-terminated polybutadiene acrylonitrile is 2000-3500.

[0015] In a feasible implementation manner of the first aspect of the present application, the hydroxyl value of the hydroxy-terminated polybutadiene acrylonitrile is 0.50-0.70 mmol / g.

[0016] In a feasible embodiment of the first aspect of the present application, the polyurethane prepolymer is made of the following raw materials in parts by weight: 100 parts of terminal hydroxyl polybutadiene acrylonitrile; and the following, all based on 100 parts of terminal hydroxyl polybutadiene acrylonitrile: 14 to 35 parts of silicone diol; 30 to 50 parts of polyether polyol; and 16 to 32 parts of polyisocyanate.

[0017] In a feasible implementation manner of the first aspect of the present application, the number average molecular weight of the organosilicon diol is 1000-4000.

[0018] In a feasible embodiment of the first aspect of the present application, the organosilicon diol comprises the following formula 2 or

[0019] The structure shown in formula 3:

[0020]

[0021] Wherein, R1 and R2 are each independently an alkyl group, and n and m are each independently 8 to 50.

[0022] In a feasible implementation manner of the first aspect of the present application, the epoxy plasticizer includes one or more of epoxy soybean oil, epoxy linseed oil, epoxy cottonseed oil, epoxy rice bran oil and epoxy sunflower oil.

[0023] In a feasible implementation of the first aspect of the present application, the latent curing agent includes one or more of aldimines, ketimines and oxazolidines.

[0024] In a feasible implementation of the first aspect of the present application, the polyurethane waterproof coating satisfies at least one of the following characteristics:

[0025] a. polyether polyols include one or a combination of polyether diols and polyether triols;

[0026] b. The polyisocyanate includes one or a combination of aromatic diisocyanates and aliphatic diisocyanates; one or more of toluene diisocyanate, diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, xylylene diisocyanate and tetramethyl-m-xylylene diisocyanate can be selected;

[0027] c. Additives include one or more of petroleum asphalt, pigments, fillers and catalysts;

[0028] Optionally, the petroleum asphalt includes one or more of 50# asphalt, 70# asphalt, 90# asphalt, 110# asphalt and 200# asphalt;

[0029] Optionally, the pigments and fillers include one or more of fumed silica, titanium dioxide, kaolin, heavy calcium, talc, barium sulfate, silicon micropowder, nano calcium carbonate, calcium oxide, magnesium oxide, carbon black and wollastonite;

[0030] Optionally, the catalyst includes one or more of dibutyltin dilaurate, stannous octoate, lead isooctanoate, bismuth isooctanoate, and zinc neodecanoate.

[0031] The second aspect of the present application provides a method for preparing the polyurethane waterproof coating of the first aspect of the present application, comprising the following steps:

[0032] Allowing predetermined weight portions of hydroxy-terminated polybutadiene acrylonitrile, silicone diol, polyether polyol, polyisocyanate, epoxy plasticizer and additive to react under a first condition to obtain a first reactant;

[0033] The first reactant and the oxazolidine-terminated modified resin are reacted under a second condition to obtain a second reactant; the second reactant and the latent curing agent are reacted under a catalytic condition to obtain a polyurethane waterproof coating.

[0034] In a feasible implementation of the second aspect of the present application, in the step of reacting the first reactant and the oxazolidine-terminated modified resin under a second condition to obtain the second reactant, the preparation of the oxazolidine-terminated modified resin includes: reacting bisphenol A-type epoxy resin with methacrylate glycerol or 3,4-epoxyhexyl methacrylate through free radical polymerization to obtain reactant A; reacting reactant A with polyisocyanate to obtain reactant B; reacting reactant B with hydroxyoxazolidine to obtain the oxazolidine-terminated modified resin.

[0035] The third aspect of the present application provides a waterproof product, comprising: a waterproof coating and an asphalt waterproof roll covering the waterproof coating, wherein the waterproof coating is formed by the polyurethane coating provided by the first aspect of the present application.

[0036] In the polyurethane waterproof coating of the present application, the low surface energy and good system compatibility of the organosilicon diol, the terminal hydroxyl polybutadiene acrylonitrile and the polyisocyanate react to form an NCO-terminated prepolymer, which has good compatibility with the components of most materials (such as asphalt coil), does not separate and does not swell; further, the oxazolidine-terminated modified resin contains terminal oxazolidine, and the terminal oxazolidine is hydrolyzed to release secondary hydroxyl and amino groups, and its secondary hydroxyl will undergo a cross-linking reaction with the NCO-terminated prepolymer, and its amino group and the amino group released by the hydrolysis of the latent curing agent can be together with the epoxy group in the epoxy plasticizer to undergo a ring-opening cross-linking reaction, so that the various components in the polyurethane coating, especially the plasticizer, can be well cross-linked. Since there is no free plasticizer in this system and no solvent is added, the migration and penetration of the plasticizer and the solvent into the asphalt coil to cause it to swell is avoided, and the peel strength of the waterproof material formed by the composite of the polyurethane coating and the asphalt coil is improved. DETAILED DESCRIPTION

[0037] In order to make the invention purpose, technical scheme and beneficial technical effect of the present application clearer, the present application is further described in detail below in conjunction with the embodiments. It should be understood that the embodiments described in this specification are only for explaining the present application, not for limiting the present application.

[0038] For simplicity, only some numerical ranges are explicitly disclosed herein. However, any lower limit can be combined with any upper limit to form an unambiguous range; and any lower limit can be combined with other lower limits to form an unambiguous range, and any upper limit can be combined with any other upper limit to form an unambiguous range. In addition, although not explicitly stated, each point or single value between the range endpoints is included in the range. Thus, each point or single value can be combined with any other point or single value as its own lower limit or upper limit or with other lower limits or upper limits to form an unambiguous range.

[0039] In the description herein, when a composition is described as containing, comprising or including specific components, or when a process is described as containing, comprising or including specific process steps, it is expected that the composition of the present application also consists essentially of or consists of the components, and the process of the present application also consists essentially of or consists of the process steps.

[0040] The use of the terms "including," "comprising," "containing," and "having" should generally be interpreted as open ended and non-limiting unless expressly stated otherwise.

[0041] In the description of this article, it should be noted that, unless otherwise specified, “above” and “below” are inclusive of the number itself, and the “multiple” in “one or more” means more than two.

[0042] The above-mentioned summary of the invention of the present application is not intended to describe each disclosed embodiment or each implementation in the present application. The following description more specifically illustrates exemplary embodiments. In many places throughout the application, guidance is provided by a series of examples, which can be used in various combinations. In each example, enumeration is only used as a representative group and should not be interpreted as exhaustive.

[0043] In order to improve the problem of low peel strength of asphalt waterproofing membrane, the inventor conducted a large number of experimental studies and concluded that the reason may be due to the swelling of the asphalt waterproofing membrane, which reduced the intermolecular force inside the membrane, resulting in a decrease in the cohesion of the material and low peel strength. Further, the inventor conducted an in-depth analysis and believed that the reason for the swelling of the asphalt waterproofing membrane may be that the organic solvents and plasticizers contained in ordinary polyurethane waterproof coatings will gradually migrate and penetrate into the asphalt of the membrane during use, causing the swelling of asphalt and other components, resulting in low peel strength of the asphalt waterproofing membrane.

[0044] In view of this, the inventor has conducted a lot of experimental research and demonstration, and provided a polyurethane waterproof coating, a preparation method and a waterproof product in this application. In the first aspect of this application, the polyurethane waterproof coating is provided, comprising the following raw materials in parts by weight:

[0045] Polyurethane prepolymer, 206 parts; polyurethane prepolymer is formed by reacting terminal hydroxyl polybutadiene acrylonitrile, silicone diol, polyether polyol and polyisocyanate; and the following components, all based on 206 parts of polyurethane prepolymer: 3 to 7 parts of oxazolidine end-capping modified resin; 6 to 12 parts of latent curing agent; 40 to 85 parts of epoxy plasticizer; and 130 to 300 parts of additives.

[0046] In the polyurethane waterproof coating provided by the present application, the low surface energy and good system compatibility of the organosilicon diol, the terminal hydroxyl polybutadiene acrylonitrile and the polyisocyanate can react to form an NCO-terminated prepolymer, which has good compatibility with the components of most materials (such as coiled asphalt), does not separate and does not swell; further, the oxazolidine-terminated modified resin contains terminal oxazolidine, and the terminal oxazolidine is hydrolyzed to release secondary hydroxyl and amino groups, and its secondary hydroxyl groups will cross-link with the NCO-terminated prepolymer, and its amino groups and the amino groups released by the hydrolysis of the latent curing agent can be together with the epoxy groups in the epoxy plasticizer for ring-opening cross-linking reaction, so that the components in the polyurethane coating, especially the plasticizer, can be well cross-linked. Since there is no free plasticizer in this system and no solvent is added, the migration and penetration of the plasticizer and the solvent into the asphalt coil to cause it to swell is avoided, and the peel strength of the waterproof material formed by the composite of the polyurethane coating and the asphalt coil is improved.

[0047] At the same time, the comprehensive introduction of oxazolidine-terminated modified resin, silicone diol, and hydroxy-terminated polybutadiene acrylonitrile in the coating of the present application can also improve the curing speed, adhesion, water resistance, tensile strength, tear strength and flexibility of the polyurethane coating film. In addition, the coating of the present application does not generate bubbles during the curing process and is less affected by the construction temperature and humidity.

[0048] In order to better reduce the migration of components in the coating and penetrate into the coiled material, the effect of the oxazolidine end-blocking modified resin including multiple epoxy groups is better. On the one hand, the oxazolidine end-blocking modified resin not only has the end group oxazolidine hydrolyzed secondary hydroxyl and amino groups to cross-link with other components, and the epoxy groups in its multiple epoxy groups and epoxy plasticizers can also react with the amino groups of latent curing agents and open-loop cross-linking, and can also react with the amino groups hydrolyzed by the end group oxazolidine itself, it can be seen that the cross-linking degree between each component is higher, and the cross-linking density is larger, which can better reduce the migration of components in polyurethane waterproof coating. Moreover, the introduction of multiple epoxy groups in the oxazolidine end-blocking modified resin can make the system cure faster, further improve construction efficiency. In some embodiments, an oxazolidine end-blocking modified resin molecule in the oxazolidine end-blocking modified resin also includes at least 2 epoxy groups, for example, it can be any value in 2,3,4,5,6 or 2 to 6 intervals.

[0049] The inventors found that it is not only the functional group in the oxazolidine end-blocking modified resin, but also the range of its number average molecular weight can also have an impact on the performance of the coating. On the basis of the terminal oxazolidine and multiple epoxy groups contained in the oxazolidine end-blocking modified resin, its number average molecular weight is too small to have a certain impact on the crosslinking degree or bonding performance, which is easy to cause undesirable bonding performance. And its number average molecular weight is too large, then the activity will be relatively low, and the crosslinking reaction between each component will also be affected, thereby affecting the physical properties of the coating. In some embodiments, the number average molecular weight of the oxazolidine end-blocking modified resin is 1000~3000, for example, it can be 1000, 1500, 2000, 2500, 3000 or any value in the interval of 1000~3000.

[0050] In some embodiments, the epoxy equivalent of the oxazolidine-terminated modified resin is 330 g / mol to 380 g / mol. Furthermore, the oxazolidine-terminated modified resin of the present application also has a suitable epoxy equivalent range, high activity, fast crosslinking speed, and high crosslinking density.

[0051] Bisphenol A epoxy resin contains multiple epoxy groups and has good activity. Using bisphenol A epoxy resin as the skeleton structure, introducing glycidyl acrylate chain segments, isocyanate chain segments and terminal oxazolidines, the strength of the coating can be further improved, such as bonding strength, tensile strength and tear strength. In some embodiments, the oxazolidine-terminated modified resin includes the structure of Formula 1:

[0052]

[0053] In Formula 1, n is an integer of 1 to 2, X is an integer of 1 to 3, R is an alkyl group or a phenyl group, each occurrence of R1 can be independently selected from H, an alkyl group or a phenyl group, and m is an integer of 1 to 5. For example, n can be 1 or 2, X can be 1 or 2 or 3, and m can be 1 or 2 or 3 or 4 or 5.

[0054] The plasticizer selected in the present application is a plasticizer with an epoxy group. It is precisely because it contains an epoxy group that it can undergo a ring-opening crosslinking reaction with the amino group hydrolyzed by the oxazolidine-terminated modified resin and the amino group released by the hydrolysis of the latent curing agent, thereby fixing the plasticizer in the coating film and becoming a part of the coating film itself, preventing it from migrating and penetrating into the coiled material. In some embodiments, the epoxy plasticizer can include one or more of epoxy soybean oil, epoxy linseed oil, epoxy cottonseed oil, epoxy rice bran oil and epoxy sunflower oil.

[0055] The curing agent selected in the present application is a latent curing agent that can hydrolyze to release amino groups. As can be seen from the above, the hydrolyzed amino groups in the curing agent in the present application can undergo cross-linking reactions with various components in the coating, so that there is no free plasticizer and solvent in the coating system to reduce the swelling effect on the coil. In some embodiments, the latent curing agent can include one or more of aldimines, ketimines and oxazolidines.

[0056] In some embodiments, the polyurethane prepolymer is prepared by including the following raw materials in parts by weight: 100 parts of terminal hydroxyl polybutadiene acrylonitrile; and based on 100 parts of terminal hydroxyl polybutadiene acrylonitrile: 14 to 35 parts of organosilicon diol; 30 to 50 parts of polyether polyol; and 16 to 32 parts of polyisocyanate.

[0057] The polyurethane waterproof coating of the present application comprises a low surface energy, a good system compatibility of organosilicon diol, a terminal hydroxyl polybutadiene acrylonitrile and a polyisocyanate to react to form an NCO-terminated prepolymer. The NCO-terminated prepolymer contains nitrile groups and acrylic acid groups introduced by terminal hydroxyl polybutadiene acrylonitrile, which can further enhance the bonding ability of the polyurethane film-forming resin. In some embodiments, the number average molecular weight of the terminal hydroxyl polybutadiene acrylonitrile can be 2000 to 3500. Optionally, its hydroxyl value is 0.50 mmol / g to 0.70 mmol / g.

[0058] In addition, the NCO-terminated prepolymer in the present application also includes a polysiloxane molecular chain with a siloxane bond (-Si-O-Si-) introduced by an organosilicon diol as a skeleton, which has low surface energy and good compatibility with various components. The resins with terminal hydroxyl groups such as terminal hydroxyl polybutadiene acrylonitrile, organosilicon diol and polyether polyol react with isocyanate to form an NCO-terminated prepolymer, and then the NCO-terminated prepolymer reacts with the secondary hydroxyl group, amino group of the hydrolyzed oxazolidine-terminated modified resin and the amino group released by the latent curing agent, thereby increasing the crosslinking degree of various components in the system.

[0059] In the present application, the introduction of oxazolidine-terminated modified resin, silicone diol, and hydroxy-terminated polybutadiene acrylonitrile comprehensively improves the adhesion, water resistance, heat resistance, weather resistance, and flexibility of the coating. In some embodiments, the number average molecular weight of the silicone diol can be 1000 to 4000, and the optional silicone diol can include the structure shown in Formula 2 or Formula 3:

[0060]

[0061] Wherein, R1 and R2 may be independently an alkyl group, and n and m may be independently 8 to 50.

[0062] The present application can also select the following different types of polyether polyols, polyisocyanates and additives for compounding according to the needs to obtain polyurethane coatings of different components. In some embodiments, the polyurethane waterproof coating can meet at least one of the following conditions: a. The polyether polyol includes one or a combination of polyether diols and polyether triols; b. The polyisocyanate includes one or a combination of aromatic diisocyanates and aliphatic diisocyanates; c. The additive includes one or more of petroleum asphalt, pigments and fillers, and catalysts.

[0063] The polyisocyanate may include one or more of toluene diisocyanate, diphenylmethane-4,4,-diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, xylylene diisocyanate and tetramethyl-m-xylylene diisocyanate.

[0064] The petroleum asphalt may include one or more of 50# asphalt, 70# asphalt, 90# asphalt, 110# asphalt, and 200# asphalt. The pigment filler may include one or more of fumed silica, titanium dioxide, kaolin, heavy calcium, talcum powder, barium sulfate, silicon micropowder, nano calcium carbonate, calcium oxide, magnesium oxide, carbon black, and wollastonite. The catalyst may include one or more of dibutyltin dilaurate, stannous octoate, lead isooctanoate, bismuth isooctanoate, and zinc neodecanoate.

[0065] The polyurethane waterproof coating provided in the present application can be prepared by the following method. The second aspect of the present application provides the preparation method, comprising:

[0066] Allowing predetermined weight portions of hydroxy-terminated polybutadiene acrylonitrile, silicone diol, polyether polyol, polyisocyanate, plasticizer and additive to react under a first condition to obtain a first reactant;

[0067] The first reactant and the oxazolidine-terminated modified resin are reacted under the second condition to obtain the second reactant; the second reactant and the latent curing agent are reacted under the catalytic condition to obtain the polyurethane waterproof coating.

[0068] Specifically, the preparation of the first reactant may include mixing predetermined weight portions of terminal hydroxyl polybutadiene acrylonitrile, silicone diol, polyether triol, plasticizer, petroleum asphalt, and pigments and fillers in a high-speed disperser, then transferring the mixture to a synthesis kettle, stirring and heating the mixture to 100°C to 110°C, and dehydrating the mixture under vacuum conditions of -0.08MPa to -0.1MPa for 2h to 3h; cooling the mixture to 70°C to 80°C, adding diisocyanate under stirring, and then heating the mixture to 75°C to 85°C, and reacting the mixture for 3h to 4h to obtain the first reactant.

[0069] Specifically, the preparation of the second reactant may include cooling the first reactant to 70° C. to 80° C., adding the oxazolidine-terminated modified resin under stirring, and reacting for 1 h to 2 h to obtain the second reactant.

[0070] Specifically, the preparation of the polyurethane waterproof coating also includes cooling the second reactant to 50°C to 60°C, adding a latent curing agent and a catalyst under stirring, and reacting for 0.5h to 1h; cooling to below 50°C, filling with nitrogen for protection, and discharging to obtain a single-component polyurethane waterproof coating.

[0071] The oxazolidine-terminated modified resin can be obtained by free radical polymerization of bisphenol A epoxy resin and glyceryl methacrylate, and then further reacting with diisocyanate and hydroxy oxazolidine.

[0072] In some embodiments, in the step of reacting the first reactant and the oxazolidine-terminated modified resin under a second condition to obtain the second reactant, the preparation of the oxazolidine-terminated modified resin includes: reacting bisphenol A epoxy resin with methacrylate glycerol or 3,4-epoxyhexyl methacrylate through free radical polymerization to obtain reactant A; reacting reactant A with polyisocyanate to obtain reactant B; reacting reactant B with hydroxyoxazolidine to obtain the oxazolidine-terminated modified resin.

[0073] Specifically, the oxazolidine-terminated modified resin may be prepared by the following method:

[0074] S01: Put the calculated amount of dried bisphenol A epoxy resin E44 into the reactor, add a mixed solvent of n-butanol and ethylene glycol butyl ether (mass ratio is 1:2), start stirring until the epoxy resin is completely dissolved, and control the material temperature to 85°C; then add the calculated amount of glycidyl methacrylate (or 3,4-epoxyhexyl methacrylate) and benzoyl peroxide dropwise into the reactor, control a certain dropwise reaction speed, continue to heat and stir the reaction, control the temperature to 90°C ~ 95°C, react at a constant temperature for 6h ~ 7h, then evacuate, and distill under reduced pressure for 0.5h ~ 1h to obtain reactant A.

[0075] The amount of the mixed solvent of n-butanol and ethylene glycol butyl ether is 10% to 15% of the total mass of the reaction, and the amount of benzaldehyde peroxide is 0.3% to 0.5% of the total mass of the reaction. Reactant A may include a structure as shown in Formula 4 below.

[0076]

[0077] In Formula 4, n is an integer of 1-2, and X is an integer of 1-3.

[0078] S02: The product reactant A obtained in step S01 is put into the reactor according to the calculated amount, and a mixed solvent of DMF and acetone (mass ratio 1:1) is added, and stirring is started. Then, the calculated amount of diisocyanate and catalyst DABCO (1,4-diazobicyclo [2,2,2] octane) are added to the reactor, the mixed solvent of DMF and acetone (mass ratio 1:1) accounts for 12% to 25% of the total mass of the total preparation raw materials, and the catalyst DABCO (1,4-diazobicyclo [2,2,2] octane accounts for 1 / 10,000 to 3 / 10,000 of the total mass of the total preparation raw materials. The temperature is raised and stirred in an oil bath for reaction, the temperature is controlled at 75°C to 85°C, and the reaction is kept at a constant temperature for 3h to 5h to obtain reactant B; reactant B may include the structure shown in Formula 5:

[0079]

[0080] In Formula 5, n is an integer of 1 to 2, X is an integer of 1 to 3, and R is an alkyl group or a phenyl group.

[0081] S03: Control the temperature at 75°C to 85°C, continue to drip the calculated amount of hydroxyoxazolidine into the reactor, react at a constant temperature for 2h to 3h under nitrogen protection, then evacuate, distill for 0.5h to 1h, cool to 50°C to 60°C, and discharge to obtain an oxazolidine-terminated modified resin. The structural formula of the oxazolidine-terminated modified resin can be shown in Formula 1 above.

[0082] The molar ratio of bisphenol A epoxy resin E44: glycidyl methacrylate: diisocyanate: hydroxyoxazolidine is 1: (1-3): (1-1.05): (1-1.05).

[0083] The hydroxyoxazolidine may be an oxazolidine compound including one active hydroxyl group, and may include a structure as shown in Formula 6 below:

[0084]

[0085] In Formula 6, R1 is H, an alkyl group or a phenyl group, and m is an integer of 1 to 5.

[0086] The hydroxyoxazolidine may also include one or more of 2-isopropyl-3-hydroxyethyl-1,3-oxazolidine, 3-hydroxyethyl-1,3-oxazolidine, and 2-phenyl-3-hydroxyethyl-1,3-oxazolidine.

[0087] The third aspect of the present application provides a waterproof product, comprising: a waterproof coating and an asphalt waterproof roll covering the waterproof coating, wherein the waterproof coating is formed by the polyurethane coating provided by the first aspect of the present application.

[0088] Example

[0089] The following examples more specifically describe the disclosure of the present application, which are intended for illustrative purposes only, as it will be apparent to those skilled in the art that various modifications and variations are possible within the scope of the disclosure of the present application. Unless otherwise stated, all parts, percentages, and ratios reported in the following examples are by weight, and all reagents used in the examples are commercially available or synthesized according to conventional methods and can be used directly without further processing, and the instruments used in the examples are commercially available.

[0090] The sources of the raw materials used in the following examples and comparative examples are as follows: hydroxy-terminated polybutadiene acrylonitrile: number average molecular weight of 2000-3500, hydroxyl value of 0.50-0.70 mmol / g, purchased from Shandong Zibo Qilong Chemical Co., Ltd. Silicone diol, model SC-HP6002, purchased from Anhui Zhongen Chemical Co., Ltd. Polyether triol EP330N (functionality of 3, number average molecular weight of 5000), purchased from Shandong Bluestar Dongda Co., Ltd. Aldimine curing agent XY-401, purchased from Suzhou Xiangyuan New Materials Co., Ltd. Polyether diol DL-2000D (functionality of 2, number average molecular weight of 2000), purchased from Shandong Bluestar Dongda Co., Ltd. Other raw materials not specifically stated are all common commercial products.

[0091] Preparation Example 1

[0092] The oxazolidine-terminated modified resin is prepared by the following method:

[0093] S01: Put the calculated amount of dried bisphenol A epoxy resin E44 into the reactor, add the calculated amount of a mixed solvent of n-butanol and ethylene glycol butyl ether (mass ratio is 1:2), start stirring until the epoxy resin is completely dissolved, and control the material temperature to 85°C; then drop the calculated amount of glycidyl methacrylate and benzoyl peroxide into the reactor, control the dropwise reaction speed to a certain level, continue to heat and stir the reaction, control the temperature to 92°C, react at a constant temperature for 6 hours, then evacuate, and distill under reduced pressure for 1 hour to obtain reactant A1.

[0094] S02: Add the product reactant A1 obtained in step S01 into the reactor according to the calculated amount, add the calculated amount of DMF and acetone (mass ratio 1:1) mixed solvent, start stirring, and then add the calculated amount of toluene diisocyanate and catalyst DABCO (1,4-diazobicyclo[2,2,2]octane) into the reactor. Heat and stir in an oil bath to react, the temperature is controlled at 80°C, and the reaction is kept at this temperature for 5 hours to obtain reactant B1;

[0095] S03: Control the temperature at 80°C, continue to drip the calculated amount of 3-hydroxyethyl-1,3-oxazolidine into the reactor, react at a constant temperature for 3 hours under nitrogen protection, then evacuate, distill for 1 hour, cool to 50°C, discharge, and obtain an oxazolidine-terminated modified resin (number average molecular weight is 2100, epoxy equivalent is 350 g / eq).

[0096] The molar ratio of bisphenol A epoxy resin E44: glycidyl methacrylate: diisocyanate: hydroxyoxazolidine is 1:2.02:1.02:1.02, and the general structural formula is shown in Formula 1 above.

[0097] Preparation Example 2

[0098] The oxazolidine-terminated modified resin is prepared by the following method:

[0099] S01: Put the calculated amount of dried bisphenol A epoxy resin E44 into the reactor, add a mixed solvent of n-butanol and ethylene glycol butyl ether (mass ratio is 1:2), start stirring until the epoxy resin is completely dissolved, and control the material temperature to 85°C; then add the calculated amount of glycidyl methacrylate and benzoyl peroxide dropwise into the reactor, control the dropwise reaction speed to a certain level, continue to heat and stir the reaction, control the temperature to 92°C, react at a constant temperature for 6 hours, then evacuate, and distill under reduced pressure for 1 hour to obtain reactant A2.

[0100] S02: Add the product reactant A2 obtained in step S01 into the reactor according to the calculated amount, add the calculated amount of DMF and acetone (mass ratio 1:1) mixed solvent, start stirring, and then add the calculated amount of toluene diisocyanate and catalyst DABCO (1,4-diazobicyclo[2,2,2]octane) into the reactor. Heat and stir in an oil bath to react, control the temperature to 80°C, and keep the temperature for 5 hours to obtain reactant B2;

[0101] S03: Control the temperature at 80°C, continue to drip the calculated amount of 3-hydroxyethyl-1,3-oxazolidine into the reactor, react at a constant temperature for 3 hours under nitrogen protection, then evacuate, distill for 1 hour, cool to 50°C, discharge, and obtain oxazolidine-terminated modified resin (number average molecular weight of 3400, epoxy equivalent of 242 g / eq).

[0102] The molar ratio of bisphenol A epoxy resin E44: glycidyl methacrylate: diisocyanate: hydroxyoxazolidine is 1:4.02:1.02:1.02.

[0103] Preparation Example 3

[0104] Compared with Preparation Example 1, the main difference is that the skeleton resin of the oxazolidine-terminated modified resin is other resins that do not contain a bisphenol rigid structure, poly[(2-oxiranyl)-1,2-cyclohexanediol] 2-ethyl-2-(hydroxymethyl)-1,3-propylene glycol ether.

[0105] The oxazolidine-terminated modified resin is prepared by the following method:

[0106] S01: Add a calculated amount of dried poly[(2-oxiranyl)-1,2-cyclohexanediol] 2-ethyl-2-(hydroxymethyl)-1,3-propylene glycol ether into a reactor, add a calculated amount of a mixed solvent of n-butanol and ethylene glycol butyl ether (mass ratio is 1:2), start stirring until the resin is completely dissolved, and control the material temperature to 85°C; then add a calculated amount of glycidyl methacrylate and benzoyl peroxide dropwise into the reactor, control the dropwise reaction speed to a certain level, continue to heat and stir the reaction, control the temperature to 92°C, react at a constant temperature for 6 hours, then evacuate, and distill under reduced pressure for 1 hour to obtain reactant A3.

[0107] S02: Weigh the product reactant A3 obtained in step S01 and put it into the reactor according to the calculated amount, add the calculated amount of DMF and acetone (mass ratio 1:1) mixed solvent, start stirring, and then add the calculated amount of toluene diisocyanate and catalyst DABCO (1,4-diazobicyclo[2,2,2]octane) into the reactor. Heat and stir in an oil bath to react, control the temperature to 80°C, and keep the temperature for 5 hours to obtain reactant B3;

[0108] S03: Control the temperature at 80°C, continue to drip the calculated amount of 3-hydroxyethyl-1,3-oxazolidine into the reactor, react at a constant temperature for 3 hours under nitrogen protection, then evacuate, distill for 1 hour, cool to 50°C, discharge, and obtain an oxazolidine-terminated modified resin (number average molecular weight of 1960, epoxy equivalent of 326 g / eq).

[0109] The molar ratio of poly[(2-oxiranyl)-1,2-cyclohexanediol]2-ethyl-2-(hydroxymethyl)-1,3-propylene glycol ether: glycidyl methacrylate: diisocyanate: hydroxyoxazolidine is 1:2.02:1.02:1.02.

[0110] Example 1

[0111] The one-component polyurethane waterproof coating for bonding asphalt coiled material in this embodiment includes the following components in parts by weight:

[0112] End-hydroxyl polybutadiene acrylonitrile, 100 parts by weight; silicone diol, 32 parts by weight; polyether triol, 48 parts by weight; epoxy linseed oil, 74 parts by weight; 50# asphalt, 14 parts by weight; toluene diisocyanate, 28 parts by weight; talcum powder, 100 parts by weight; heavy calcium, 160 parts by weight; oxazolidine end-capped modified resin (the above-mentioned Preparation Example 1, the number average molecular weight is 2100-2400, and the epoxy equivalent is 350g / eq), 6 parts by weight; aldimine curing agent XY-401, 11 parts by weight; stannous octoate, 0.4 parts by weight.

[0113] The preparation method of the one-component polyurethane waterproof coating of this embodiment comprises the following steps:

[0114] (1) Predetermined weight portions of hydroxy-terminated polybutadiene acrylonitrile, silicone diol, polyether triol, epoxy linseed oil, 50# asphalt, and pigments and fillers are mixed uniformly in a high-speed disperser, and then transferred to a synthesis reactor, stirred and heated to 105° C., and dehydrated for 2.5 hours under a vacuum condition of -0.09 MPa; then cooled to 75° C., diisocyanate is added under stirring, and then heated to 80° C. and reacted for 3.5 hours to obtain a first reactant;

[0115] (2) cooling the first reactant to 75° C., adding the oxazolidine-terminated modified resin under stirring, and reacting for 1.5 hours to obtain the second reactant;

[0116] (3) The second reactant is cooled to 55° C., aldimine and a catalyst are added under stirring, and after reacting for 0.8 h, the temperature is lowered to below 50° C., nitrogen is filled for protection, and the material is discharged to obtain a polyurethane waterproof coating.

[0117] Example 2

[0118] The one-component polyurethane waterproof coating for bonding asphalt coiled material in this embodiment comprises the following components in parts by weight: 100 parts by weight of terminal hydroxyl polybutadiene acrylonitrile; 30 parts by weight of organosilicon diol; 50 parts by weight of polyether triol; 74 parts by weight of epoxy linseed oil; 14 parts by weight of 50# asphalt; 27 parts by weight of toluene diisocyanate; 100 parts by weight of talc; 160 parts by weight of heavy calcium; 6 parts by weight of oxazolidine end-capped modified resin (same as in Example 1); 11 parts by weight of aldimine curing agent XY-401; 0.4 parts by weight of stannous octoate;

[0119] The preparation process of the one-component polyurethane waterproof coating in this embodiment is basically the same as that in Example 1, and will not be repeated here.

[0120] Example 3

[0121] The one-component polyurethane waterproof coating for bonding asphalt coiled materials in this embodiment includes the following components in parts by weight: terminal hydroxyl polybutadiene acrylonitrile, 100 parts by weight; silicone diol, 30 parts by weight; polyether triol, 48 parts by weight; epoxy linseed oil, 74 parts by weight; 50# asphalt, 15 parts by weight; toluene diisocyanate, 28 parts by weight; talcum powder, 100 parts by weight; heavy calcium, 160 parts by weight; oxazolidine end-capped modified resin (the same as in Example 1), 7 parts by weight; aldimine curing agent XY-401, 11 parts by weight; stannous octoate, 0.4 parts by weight.

[0122] The preparation process of the polyurethane waterproof coating in this embodiment is basically the same as that in Example 1, and will not be repeated here.

[0123] Example 4

[0124] The one-component polyurethane waterproof coating for bonding asphalt coiled materials in this embodiment includes the following components in parts by weight: terminal hydroxyl polybutadiene acrylonitrile, 90 parts by weight; silicone diol, 35 parts by weight; polyether triol, 48 parts by weight; epoxy linseed oil, 76 parts by weight; 50# asphalt, 14 parts by weight; toluene diisocyanate, 28 parts by weight; talcum powder, 100 parts by weight; heavy calcium, 160 parts by weight; oxazolidine end-capped modified resin (the same as in Example 1), 6 parts by weight; aldimine curing agent XY-401, 11 parts by weight; stannous octoate, 0.4 parts by weight.

[0125] The preparation process of the polyurethane waterproof coating in this embodiment is basically the same as that in Example 1, and will not be repeated here.

[0126] Example 5

[0127] Compared with Example 1, the difference is that the oxazolidine-terminated modified resin used is the above-mentioned Preparation Example 2, the number average molecular weight is 3300-3600, and the epoxy equivalent is 242 g / eq.

[0128] The preparation process of the polyurethane waterproof coating in this embodiment is basically the same as that in Example 1, and will not be repeated here.

[0129] Example 6

[0130] Compared with Example 1, the difference is that the oxazolidine end-blocking modified resin used is the above-mentioned Preparation Example 3, the number average molecular weight of the obtained oxazolidine end-blocking modified resin is 1960, and the epoxy equivalent is 326g / eq; and the skeleton resin of the oxazolidine end-blocking modified resin is poly[(2-oxiranyl)-1,2-cyclohexanediol] 2-ethyl-2-(hydroxymethyl)-1,3-propylene glycol ether which does not contain a bisphenol rigid structure,

[0131] The preparation process of the polyurethane waterproof coating in this embodiment is basically the same as that in Example 1, and will not be repeated here.

[0132] Comparative Example 1

[0133] A one-component polyurethane waterproof coating, whose composition and preparation process are similar to those of Example 1, except that the terminal hydroxyl polybutadiene acrylonitrile in Example 1 is removed and replaced by an equal weight portion of polyether diol DL-2000D, which has a functionality of 2 and a number average molecular weight of 2000 and is purchased from Shandong Bluestar Dongda Co., Ltd.

[0134] The preparation process of the polyurethane waterproof coating of each comparative example is roughly the same as that of Example 1, and will not be repeated here.

[0135] Comparative Example 2

[0136] A one-component polyurethane waterproof coating, whose composition and preparation process are similar to those of Example 1, except that the organosilicon diol in Example 1 is removed and replaced by an equal weight portion of polyether diol DL-2000D, which has a functionality of 2 and a number average molecular weight of 2000 and is purchased from Shandong Bluestar Dongda Co., Ltd.

[0137] Comparative Example 3

[0138] A one-component polyurethane waterproof coating, whose composition and preparation process are similar to those of Example 1, except that the terminal hydroxyl polybutadiene acrylonitrile and silicone diol in Example 1 are removed and replaced by an equal weight portion of polyether diol DL-2000D, which has a functionality of 2 and a number average molecular weight of 2000 and is purchased from Shandong Bluestar Dongda Co., Ltd.

[0139] Comparative Example 4

[0140] A one-component polyurethane waterproof coating, whose composition and preparation process are similar to those of Example 1, except that the oxazolidine-terminated modified resin in Example 1 is removed and replaced by an equal weight portion of aldimine XY-401 (purchased from Suzhou Xiangyuan New Materials Co., Ltd.), and the plasticizer is replaced by an equal weight portion of 52# chlorinated paraffin (purchased from Jiangxi Oriental Julong Chemical Co., Ltd.).

[0141] Comparative Example 5

[0142] A one-component polyurethane waterproof coating, whose composition and preparation process are similar to those of Example 1, except that the oxazolidine end-capped modified resin in Example 1 is removed and replaced by an equal weight portion of bisphenol A type epoxy resin E44 (purchased from Baling Petrochemical Company).

[0143] Comparative Example 6

[0144] A one-component polyurethane waterproof coating, whose composition and preparation process are similar to those of Example 1, except that it does not contain plasticizer epoxy linseed oil.

[0145] Performance Testing

[0146] The performance of the one-component polyurethane waterproof coating for bonding asphalt coils prepared in each embodiment and comparative example was tested, and the test performance is shown in Table 1.

[0147] (1) Except for the peel strength test, the other performance test methods in Table 1 are carried out in accordance with JC / T2435-2018.

[0148] (2) The test method of the composite peel strength of the roll material is as follows: the prepared coating layer is overlapped with the asphalt waterproofing roll material, and the 180° peel strength is tested after the overlap. Specifically, the polyurethane waterproofing coating is applied to the base surface by cold construction, and the coating thickness is 1.5±0.2mm. After the coating is completed, the asphalt waterproofing roll material is laid on the coating layer during the coating adaptation period, and the roll material is rolled tightly so that the roll material and the coating are in a fully adhered state. After curing for 168 hours, the 180° peel strength is tested. The specific test steps are as follows:

[0149] The size and preparation method of the test piece: 1. Cut the asphalt waterproofing membrane and keep its bonding surface size at the preset size, which is 70*50mm; 2. Apply the polyurethane waterproof coating to the base surface; 3. Then directly lay the cut asphalt membrane on the polyurethane waterproof coating and compact it to make it fully adhered; 4. Cure the prepared test piece under standard curing conditions for 168 hours.

[0150] Test method: Install the cement mortar block surface in the above test piece on the fixture at one end of the electronic tensile tester, and bend the non-bonded surface of the coiled material in the above test piece opposite to the bonding surface by 180° and clamp it in the fixture at the other end of the tester. Pay attention to accurately position the test piece between the chucks to ensure that the applied tensile force is evenly distributed over the width of the test piece. Start the testing equipment and set the tensile speed to 100mm / min.

[0151]

[0152] From the data in the table, it can be seen from the comparison between Examples 1 to 4 and Comparative Examples 1 to 4 that the coatings in Examples 1 to 4 have better performance in terms of bonding performance, composite peeling strength with coils, peeling failure forms, etc.; the bonding performance of the coatings in Comparative Examples 1 to 4 and the composite peeling strength of the coils are significantly lower than those in Examples 1 to 4. The composite peeling strength (N / mm) data with asphalt coils and the failure form clearly show that the introduction of reactant C improves the composite peeling strength with asphalt coils, and the co-use of terminal hydroxyl polybutadiene acrylonitrile and organosilicon diol can play a certain synergistic role and jointly improve the bonding effect on waterproof coils. The molecular weight of the oxazolidine-terminated modified resin in Example 5 is too large, which affects the reaction activity of the modified resin, the crosslinking density of the system decreases, the drying time is longer, and the strength decreases. Tensile strength, tear strength and bonding strength; Example 6 uses an oxazolidine-terminated modified resin whose skeleton resin is an alicyclic epoxy resin with a rigid structure that does not contain bisphenol. It can be clearly seen that the reaction activity is also reduced, and the strength is also reduced, such as tensile strength, tear strength and bonding strength, but it has little effect on the composite peel strength of the asphalt coil; Comparative Example 5 uses a resin that does not contain an oxazolidine end group, so the peel strength, bonding strength and other properties are reduced; Comparative Example 6 does not contain plasticizer epoxy linseed oil, so the tensile strength / bonding strength is significantly improved, but the elongation at break is significantly reduced, and the composite peel strength with the asphalt coil is also significantly reduced. This may be due to the lack of the toughening effect of the epoxy plasticizer, the coating layer is obviously rigid, and the rigid layer and the flexible coil layer have a reduced peel strength due to the difference in interface stress.

[0153] The above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the embodiments here. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the claims of the present invention.

Claims

1. A polyurethane waterproof coating, characterized in that: The polyurethane waterproof coating comprises the following raw materials in parts by weight: Polyurethane prepolymer, 206 parts; the polyurethane prepolymer is formed by reacting hydroxy-terminated polybutadiene acrylonitrile, silicone diol, polyether polyol and polyisocyanate; and all based on 206 parts of polyurethane prepolymer: Oxazolidine end-capped modified resin, 3 to 7 parts; Latent curing agent, 6 to 12 parts; Epoxy plasticizer, 40-85 parts; Additives, 130-300 parts.

2. The polyurethane waterproof coating according to claim 1, characterized in that: One oxazolidine-terminated modified resin molecule in the oxazolidine-terminated modified resin further comprises at least two epoxy groups; and / or; the number average molecular weight of the oxazolidine-terminated modified resin is 1000 to 3000; and / or; the epoxy equivalent of the oxazolidine-terminated modified resin is 330 g / mol to 380 g / mol.

3. The polyurethane waterproof coating according to claim 1, characterized in that: The oxazolidine-terminated modified resin comprises a structure as shown in Formula 1: In Formula 1, n is an integer of 1 to 2, X is an integer of 1 to 3, R is an alkyl group or a phenyl group, R1 is selected from H, an alkyl group or a phenyl group, and m is an integer of 1 to 5.

4. The polyurethane waterproof coating according to claim 1, characterized in that: The number average molecular weight of the hydroxyl-terminated polybutadiene acrylonitrile is 2000-3500; optionally, the hydroxyl value of the hydroxyl-terminated polybutadiene acrylonitrile is 0.50 mmol / g-0.70 mmol / g; and / or; The polyurethane prepolymer comprises the following raw materials in parts by weight: 100 parts of terminal hydroxyl polybutadiene acrylonitrile; and based on 100 parts of terminal hydroxyl polybutadiene acrylonitrile: 14-35 parts of organosilicon diol; 30-50 parts of polyether polyol; and 16-32 parts of polyisocyanate.

5. The polyurethane waterproof coating according to claim 1, characterized in that: The number average molecular weight of the organosilicon diol is 1000 to 4000; optionally, the organosilicon diol includes a structure as shown in Formula 2 or Formula 3 below: Wherein, R1 and R2 are each independently an alkyl group, and n and m are each independently 8 to 50.

6. The polyurethane waterproof coating according to claim 1, characterized in that: The epoxy plasticizer comprises one or more of epoxidized soybean oil, epoxidized linseed oil, epoxidized cottonseed oil, epoxidized rice bran oil and epoxidized sunflower oil; and / or, The latent curing agent includes one or more of aldimines, ketimines and oxazolidines.

7. The polyurethane waterproof coating according to claim 1, characterized in that: The polyurethane waterproof coating meets at least one of the following characteristics: a. The polyether polyol comprises one or a combination of a polyether diol and a polyether triol; b. The polyisocyanate comprises one or a combination of an aromatic diisocyanate and an aliphatic diisocyanate; Optionally, the polyisocyanate includes one or more of toluene diisocyanate, diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, xylylene diisocyanate and tetramethyl-m-xylylene diisocyanate; c. The additives include one or more of petroleum asphalt, pigments, fillers and catalysts; Optionally, the petroleum asphalt includes one or more of 50# asphalt, 70# asphalt, 90# asphalt, 110# asphalt and 200# asphalt; Optionally, the pigment filler includes one or more of fumed silica, titanium dioxide, kaolin, heavy calcium, talc, barium sulfate, silicon micropowder, nano calcium carbonate, calcium oxide, magnesium oxide, carbon black and wollastonite; Optionally, the catalyst includes one or more of dibutyltin dilaurate, stannous octoate, lead isooctanoate, bismuth isooctanoate and zinc neodecanoate.

8. The method for preparing the polyurethane waterproof coating according to any one of claims 1 to 7, characterized in that: include: Allowing predetermined weight portions of hydroxy-terminated polybutadiene acrylonitrile, silicone diol, polyether polyol, polyisocyanate, epoxy plasticizer and additive to react under a first condition to obtain a first reactant; allowing the first reactant and the oxazolidine-terminated modified resin to react under a second condition to obtain a second reactant; The second reactant and the latent curing agent are reacted under catalytic conditions to obtain the polyurethane waterproof coating.

9. The method for preparing the polyurethane waterproof coating according to claim 8, characterized in that: In the step of reacting the first reactant and the oxazolidine-terminated modified resin under the second condition to obtain the second reactant, the preparation of the oxazolidine-terminated modified resin includes: Bisphenol A epoxy resin and glyceryl methacrylate or 3,4-epoxyhexyl methacrylate are subjected to free radical polymerization reaction to obtain reactant A; reactant A is reacted with polyisocyanate to obtain reactant B; reactant B is reacted with hydroxy oxazolidine to obtain the oxazolidine-terminated modified resin.

10. A waterproof product comprising: A waterproof coating and an asphalt waterproof coiled material covering the waterproof coating, wherein the waterproof coating is formed by the polyurethane coating according to any one of claims 1 to 7.

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