Hot melt adhesive suitable for water-based coating waterproofing coiled materials and preparation method and application thereof

Abstract

The present invention discloses a hot melt adhesive suitable for water-based coating waterproofing coiled materials, wherein the waterproofing coiled materials sequentially include a substrate, a connecting layer and an anti-sticking coating, wherein the connecting layer is formed by the hot melt adhesive, and the anti-sticking coating is formed by a water-based resin emulsion, wherein the hot melt adhesive includes a plasticizer, a tackifying resin, a functional resin, and a thermoplastic elastomer, wherein the functional resin contains one or more of abietic acid, palustric acid, and pimaric acid, wherein the carboxyl content in the functional resin is 0.90 mmol / g to 2.80 mmol / g, and the carboxyl group in the hot melt adhesive is used to form a chemical bond with an amino group in the water-based resin emulsion. The hot melt adhesive of the present invention has a low surface contact angle and high surface energy, and the resin emulsion of the anti-sticking coating can be well wetted on the surface, and at the same time has a stable bonding force with the coating, thereby ensuring that a full bonding structure is formed after pouring concrete for water-based coating waterproofing coiled materials.

Description

Technical Field

[0001] The present invention belongs to the technical field of adhesives and is applied to waterproof coiled materials. The present invention particularly relates to a hot melt adhesive suitable for water-based coating waterproof coiled materials, a preparation method of the hot melt adhesive and the application of the hot melt adhesive in waterproof coiled materials. Background Art

[0002] Pre-laid waterproofing membrane generally refers to pouring concrete directly on the surface of the membrane after the waterproof layer is constructed in advance. The membrane is mainly composed of the main material, the connection layer, the surface anti-(reducing) adhesion protection layer (except the overlap area of ​​the membrane), and the isolation material (when necessary). The connection layer can be well bonded to the concrete layer after pouring the concrete, which fundamentally prevents the risk of water leakage. Pre-laid waterproofing membrane has low requirements for the construction base surface, does not require leveling, is convenient to construct, can be directly overlapped, and has reliable bonding. At present, pre-laid waterproofing membrane has become one of the main materials for underground waterproofing, and has been widely used in various building floors, basement roofs and other locations at home and abroad.

[0003] The anti-adhesion (anti-sticking) protective layer on the surface of waterproofing membranes usually uses cement sand, artificial sand, quartz sand or membrane-type silicone oil isolation materials. The use of membrane-type silicone oil release materials will cause secondary plastic pollution during the construction and application process, bringing unnecessary garbage disposal problems. Various types of sand layer surface isolation materials are prone to fall off during production and transportation. At the same time, there is sand falling during the construction process, which is easy to affect the construction of the overlapped edges, thereby affecting the final waterproofing construction effect. In addition, the rolls of isolation sand protective layers are heavy in weight.

[0004] To solve this problem, there are currently coated waterproof membranes that use coating materials to replace isolation sand or release film materials to achieve the purpose of anti-adhesion (reducing) protective layers. Coating anti-adhesion protective layers can effectively reduce the weight of waterproof membranes and greatly improve construction convenience.

[0005] The product structure of coated waterproof membrane mainly consists of three layers: substrate, connecting layer and coating anti-sticking layer. It is bonded with the post-poured concrete to form a fully bonded waterproof structure. It mainly relies on the effective bonding between the surface coating and the concrete, and the coating and the substrate are connected together through the intermediate connecting layer. The bonding between the self-adhesive and the substrate is currently at a very good level. Therefore, the cohesive force of the self-adhesive and the bonding force between the self-adhesive and the coating determine the waterproof effect of the coated waterproof membrane.

[0006] At the same time, the coating is often adhered by roller coating, spraying and transfer in the production process. How to evenly and stably apply the coating on the self-adhesive surface determines the overall bonding performance of the subsequent roll material. Common coating waterproof roll materials are all made of water-based materials, making the above-mentioned problems more difficult to solve.

[0007] The hot melt adhesive for waterproof membrane currently available in the market is mainly used for bonding surface isolation sand. It has good initial adhesion, but the surface tension of this type of hot melt adhesive is small and the surface contact angle is large, which makes it difficult for the water-based emulsion to be well coated on the surface. Roller marks and shrinkage marks are likely to appear after coating. During spraying and other production processes, droplets are easily formed on the surface and cannot be well wetted to form a coating film. This will cause glue leakage on the surface of the pre-laid finished product, affecting the appearance of the coating membrane and the peeling from the poured concrete, ultimately resulting in poor product construction application and waterproofing effect.

[0008] For example, the patent with publication number CN116496714A and titled "A double-sided composite polymer waterproofing membrane, preparation method and application" discloses a polymer pressure-sensitive adhesive, which introduces a fluorosilicone adhesion promoter, which can not only be cold-bonded with polymer sheets to form a full adhesion without water leakage between the two waterproof layers, but also the two waterproof layers belong to the same polymer material, there is no incompatibility between the materials, and the long-term reliability of underground waterproofing can be guaranteed; the double-sided composite polymer waterproofing membrane in the patent can be more firmly bonded to substrates such as cement mortar and cement concrete, with higher peel strength and better water resistance. However, the polymer pressure-sensitive adhesive mentioned in the patent is mainly for improving the bonding with the substrate and concrete, and does not mention the wetting effect of the water-based material on its surface, and the improvement of the bonding effect comes from the fluorosilicone adhesion promoter. The polymer pressure-sensitive adhesive has a firm bond with cement mortar and cement concrete, high peel strength, water resistance, and can be well coated on the substrate by heating coating, which are all basic requirements for adhesives for waterproofing membranes.

[0009] Another example is the patent with publication number CN117285879A, entitled A pre-laid waterproofing membrane and its preparation method. The waterproofing membrane includes a substrate layer, an adhesive layer and a protective coating layer stacked in sequence. The focus is on adjusting the emulsion formula to improve the wetting on the coated surface, the bonding strength with concrete, etc. However, the adhesive layer is an ordinary hot-melt pressure-sensitive adhesive. The surface tension of ordinary hot-melt pressure-sensitive adhesive is small, and the surface contact angle is large, which is not friendly to the protective coating of the water-based substrate. The protective coating of the water-based substrate cannot be completely wetted by the surface of the hot-melt pressure-sensitive adhesive, and shrinkage and coating leakage occur, thereby causing the hot-melt pressure-sensitive adhesive to leak under the protective coating. Therefore, after drying, the position where the protective coating is not spread will adhere to the substrate layer when it is rolled up, and the protective coating needs to be quickly cured by ultraviolet light after roller coating to be fully coated and formed into a film, which has higher requirements on the process.

[0010] The disclosure of the above background technology content is only used to assist in understanding the inventive concept and technical solution of the present invention. It does not necessarily belong to the prior art of this patent application. In the absence of clear evidence that the above content has been disclosed before the filing date of this patent application, the above background technology should not be used to evaluate the novelty and creativity of the present application. Summary of the invention

[0011] In view of this, in order to overcome the defects of the prior art, the purpose of the present invention is to provide an improved hot melt adhesive, which can be suitable for water-based coating waterproof roll materials, has strong adhesion to the anti-stick coating and the substrate, and has a lower surface contact angle, which is more conducive to the coating of the anti-stick coating.

[0012] In order to achieve the above object, the present invention adopts the following technical solutions:

[0013] A hot melt adhesive suitable for water-based coating waterproof coiled materials, the waterproof coiled materials sequentially comprising a substrate, a connecting layer and an anti-sticking coating, the connecting layer being formed by the hot melt adhesive, the anti-sticking coating being formed by a water-based resin emulsion, the hot melt adhesive comprising a plasticizer, a tackifying resin, a functional resin, and a thermoplastic elastomer, the functional resin containing one or more of abietic acid (such as neoabietic acid, dehydroabietic acid, dihydroabietic acid, tetrahydroabietic acid), palustric acid, and pimaric acid (such as levorotatory pimaric acid and isopimaric acid), the carboxyl content of the hot melt adhesive being 0.90 mmol / g to 2.80 mmol / g, the carboxyl group in the hot melt adhesive being used to form a chemical bond with an amino group in the water-based resin emulsion. The method for measuring the carboxyl content is referred to EN 1240:2011 "Determination of hydroxyl value and / or hydroxyl content of adhesives". The carboxyl content is low, and the surface contact angle (water) of the hot melt adhesive is large after the film is formed. The surface shrinks greatly after the emulsion is rolled on the surface. The emulsion cannot completely cover the bottom hot melt adhesive after the film is formed. In addition, the carboxyl content is low, and the bonding force between the connecting layer and the anti-sticking coating is low, resulting in low peel strength with the post-cast concrete. A high carboxyl content will cause the performance of the post-cast concrete-immersion treatment to fail to meet the standard, and in more serious cases, the adhesive will delaminate after immersion.

[0014] The hot melt adhesive of the present invention has a small surface contact angle, has a better wetting effect on the water-based resin emulsion, can achieve full coating of the water-based resin emulsion, and achieves the application conditions of the waterproof coiled material. The resin containing a certain carboxyl content is selected to achieve a predetermined surface contact angle; at the same time, the hot melt adhesive is applied to the waterproof coiled material and used in conjunction with the water-based anti-stick coating emulsion. The various properties of the hot melt adhesive, the bonding with the anti-stick coating, and the bonding with the concrete can all meet the corresponding application conditions, and the surface wetting and film-forming bonding of the hot melt adhesive have excellent effects.

[0015] According to some preferred implementation aspects of the present invention, the surface contact angle of the connecting layer is ≤90°, preferably 65°~90°.

[0016] According to some preferred implementation aspects of the present invention, the aqueous resin emulsion contains amino groups, and the pH of the aqueous resin emulsion is 6-9.

[0017] According to some preferred embodiments of the present invention, the functional resin is one or more of rosin resin or its modified resin, terpene resin or its modified resin such as terpene phenolic resin. The modification is carried out by maleic anhydride grafting, alkylation modification, hydroxylation modification, copolymerization modification, etc., to adjust the softening point of the resin, add functional groups, and improve the heat resistance, initial adhesion and other properties.

[0018] According to some preferred implementation aspects of the present invention, the softening point of the functional resin is 100° C. to 130° C. The functional resin with this softening point makes the overall performance of the hot melt adhesive better, and the product performance after being applied to the waterproof material is better.

[0019] According to some preferred embodiments of the present invention, the plasticizer is naphthenic oil and / or polyisobutylene.

[0020] According to some preferred embodiments of the present invention, the tackifying resin is one or more selected from C5 petroleum resin, hydrogenated petroleum resin, C9 petroleum resin, and C5 / C9 copolymerized petroleum resin.

[0021] According to some preferred embodiments of the present invention, the thermoplastic elastomer is one or more selected from styrene-isoprene-styrene triblock copolymer, styrene-butadiene-styrene triblock copolymer, and butyl rubber.

[0022] According to some preferred embodiments of the present invention, the thermoplastic elastomer is a styrene-isoprene-styrene triblock copolymer with a diblock content of 35%-45%. The SIS within this diblock content makes the overall strength of the hot melt adhesive better, which is reflected in the better peel strength in the waterproof membrane.

[0023] According to some preferred implementation aspects of the present invention, the hot melt adhesive comprises the following raw material components in parts by weight:

[0024] Plasticizer 16~25 parts

[0025] 10~15 parts of tackifying resin

[0026] Functional resin 28-33 parts

[0027] Thermoplastic elastomer 26~30 parts.

[0028] According to some preferred embodiments of the present invention, the hot melt adhesive includes an antioxidant, and the antioxidant is one or more selected from hindered phenols, phosphites, and thiophenols, preferably one or more of antioxidant 1010, antioxidant 168, and antioxidant 1076.

[0029] According to some preferred implementation aspects of the present invention, the hot melt adhesive includes a UV absorber, and the UV absorber is one or more selected from benzotriazole, benzophenone, and hindered amine UV absorbers.

[0030] According to some preferred implementation aspects of the present invention, the hot melt adhesive includes a filler, and the filler is one or more selected from calcium carbonate, rutile titanium dioxide or its modified substance, and kaolin inorganic filler.

[0031] In some embodiments, the hot melt adhesive suitable for water-based coating waterproof roll materials includes a plasticizer, a tackifying resin, a functional resin, a thermoplastic elastomer, an antioxidant, an ultraviolet absorber and a filler.

[0032] Preferably, the hot melt adhesive comprises the following raw material components by weight:

[0033] Plasticizer 16~25 parts

[0034] 10~15 parts of tackifying resin

[0035] Functional resin 28-33 parts

[0036] Thermoplastic elastomer 26~30 parts

[0037] Antioxidant 0~3 parts

[0038] Ultraviolet absorber 0~3 parts

[0039] Filler 0~2 parts.

[0040] According to some preferred embodiments of the present invention, the aqueous resin emulsion includes a photocrosslinkable silicone resin emulsion; the silicone resin emulsion is prepared by first subjecting a silicone polymerization monomer to a hydrolysis and condensation reaction in the presence of a solvent, then subjecting the silicone polymerization 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.

[0041] According to some preferred embodiments of the present invention, the aqueous resin emulsion includes a room temperature self-crosslinking acrylic resin emulsion; the room temperature self-crosslinking acrylic resin emulsion is 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, and the shell layer monomer includes a room temperature self-crosslinking monomer, a soft monomer, a hard monomer and a hydrophilic monomer.

[0042] The aqueous resin emulsion prepared by compounding the photocrosslinkable silicone resin emulsion and the room temperature self-crosslinking acrylic resin emulsion is applied to the hot melt adhesive of the present invention, and has good wettability and adhesion. The coating emulsion contains functional group structures such as amino, siloxane structure, isocyanate, hydroxyl, etc. The pH range of the aqueous anti-stick coating emulsion is 6~9, and it mainly adjusts the overall pH value of the emulsion and the hydrophilicity and powder dispersibility characteristics by introducing amino-containing alkaline substances. The pH value can reflect the concentration or content of the main functional group amino group. In addition to the reaction between the carboxyl group in the hot melt adhesive and the amino group in the emulsion coating, a small part of the isocyanate in the emulsion coating will also react with the carboxyl group contained in the hot melt adhesive to form an amide, which further increases the bonding strength between the hot melt adhesive and the coating.

[0043] The present invention also provides a method for preparing the hot melt adhesive as described above, comprising the following steps: heating and melting a substance and evacuating the substance to obtain the hot melt adhesive.

[0044] In some embodiments, the method for preparing the hot melt adhesive comprises the following steps:

[0045] After adding plasticizer and filler into the reaction vessel, start stirring and heating, and set the temperature of the reaction vessel to 160-180°C;

[0046] After the materials in the reaction container are mixed evenly and the material temperature reaches 175-185°C, add thermoplastic elastomer, antioxidant, and ultraviolet absorber, continue stirring and draw vacuum, and set the vacuum degree ≤-0.08MPa;

[0047] After the thermoplastic elastomer is completely melted and mixed uniformly, a tackifying resin and a functional resin are added thereto, and the vacuum state is maintained;

[0048] After all materials are melted and mixed evenly, a hot melt adhesive suitable for water-based coating waterproof membranes is obtained.

[0049] In the present invention, the plasticizer, the auxiliary agent and the elastomer are first melted, and the resin is added after being stabilized, and a vacuum is drawn throughout the process to ensure that the raw materials are less affected by thermal aging and the strength of the glue is guaranteed; while the existing conventional preparation process is to stir and melt the plasticizer, the auxiliary agent and the resin and then add the elastomer for preparation; the preparation time is long, and the colloid is easily thermally aged when heated for a long time, which affects the overall strength of the glue.

[0050] The present invention also provides an application of the hot melt adhesive as described above in a waterproof roll, such as obtaining a water-based coating waterproof roll, which comprises a substrate, a connecting layer and an anti-sticking coating in sequence, the connecting layer is formed by the hot melt adhesive described above, the anti-sticking coating is formed by an aqueous resin emulsion, and the substrate is preferably polyethylene (HDPE), polyolefin material (TPO) or polyvinyl chloride (PVC).

[0051] In some embodiments, the method for preparing a water-based coating waterproof membrane comprises the following steps:

[0052] Heat and melt the hot melt adhesive. When the material temperature reaches 160-165°C, place it in the coating equipment for coating. The coating thickness of the hot melt adhesive is 0.30mm~0.33mm;

[0053] After the hot melt adhesive is applied, the water-based resin emulsion is applied after passing through the heat preservation equipment. The coating thickness of the water-based resin emulsion is controlled at 80-150μm of wet film. The heat preservation equipment is used to maintain the surface temperature of the hot melt adhesive at 70~80℃ to promote the combination between the hot melt adhesive and the water-based resin emulsion.

[0054] After the water-based resin emulsion is applied, it is dried with hot air, and the temperature is maintained at 60℃~80℃; this promotes the reaction and combination of carboxyl and amino groups, and accelerates the volatilization of water in the anti-stick coating, and the time is 5-10 minutes;

[0055] After passing through the drying equipment, the coating surface is completely dry, and a water-based coating waterproof membrane is obtained.

[0056] Compared with the existing traditional technology, the advantages of the present invention are: the hot melt adhesive of the present invention is used for water-based coating waterproof materials, has a low surface contact angle and high surface energy, and the water-based resin emulsion of the anti-stick coating can be well wetted on its surface, and at the same time has a stable bonding force with the coating, ensuring that the water-based coating waterproof membrane forms a full adhesion structure after pouring concrete, avoiding the occurrence of water seepage. BRIEF DESCRIPTION OF THE DRAWINGS

[0057] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the following briefly introduces the drawings required for use in the description of the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work.

[0058] Figure 1 It is a schematic diagram of the cross-sectional structure of a water-based coating waterproofing coiled material in a preferred embodiment of the present invention;

[0059] Figure 2 Figure (a) is an enlarged view of the hot melt adhesive surface after being coated with water-based resin emulsion in Comparative Example 3 of the present invention;

[0060] Figure 2 Figure (b) is an enlarged view of the hot melt adhesive surface after being coated with water-based resin emulsion in Example 3 of the present invention;

[0061] Among them, the figures are marked as: concrete structure layer-1, anti-stick coating-2, connecting layer-3, substrate-4. DETAILED DESCRIPTION

[0062] In order to enable those skilled in the art to better understand the technical solution of the present invention, the technical solution in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work should fall within the scope of protection of the present invention.

[0063] The sources of the raw materials used in the following examples are as shown in Table 1:

[0064] Table 1 Raw materials

[0065] name Brand factory Naphthenic Oil 4010 PetroChina Karamay Petrochemical Co., Ltd. Ordinary C5 petroleum resin HHC-1100 Henghe Materials Technology Co., Ltd. C5 Hydrogenated Petroleum Resin H5-1001 Henghe Materials Technology Co., Ltd. Rosin terpene phenol resin T-105, T-901 Japan Arakawa Chemical Dimerized rosin Poly-pale Eastman Chemical Company Antioxidants 1076、168 Tianjin Lianlong New Materials Co., Ltd. Titanium dioxide R-105 Chemours Chemicals Titanium dioxide Tryruti AQ51 Jiangxi Liankai Chemical Co., Ltd. Thermoplastic elastomer JH-9163 Ningbo Jinhai Chenguang Chemical Co., Ltd. Thermoplastic elastomer VECTOR 4116ND TSRC (Nantong) Industrial Co., Ltd. Thermoplastic elastomer SIS-1170 Shandong Jusheng Technology Co., Ltd. UV absorber UV-P Tianjin Lianlong New Materials Co., Ltd.

[0066] Common hot melt adhesives mainly contain polyisobutylene, petroleum resin, thermoplastic elastomer and additives. The raw materials are mainly isobutylene, C5 aliphatic structure, butadiene, styrene, isoprene, etc., all of which are weakly polar. Therefore, the surface polarity is poor, the surface energy is low, and the surface is not easy to spread when the water-based emulsion material is coated on the surface. The present invention improves the hot melt adhesive formula material of the connecting layer, so that it has better wettability to the water-based resin emulsion of the anti-stick coating, and the water-based resin emulsion coating can be better coated on the surface of the hot melt adhesive. The carboxyl group in the hot melt adhesive is used to form a chemical bond with the amino group in the water-based resin emulsion. The anti-stick coating and the hot melt adhesive have excellent adhesion. After the coating is formed into a film, the hot melt adhesive can well bond the coating and the substrate to form a fully adhered anti-stick coating.

[0067] The water-based coating waterproof coiled material in this embodiment includes a substrate, a connecting layer and an anti-sticking coating in sequence, wherein the connecting layer is formed by hot melt adhesive, and the anti-sticking coating is formed by curing a water-based resin emulsion, and the substrate is polyethylene (HDPE), polyolefin material (TPO) or polyvinyl chloride (PVC), and the thickness is 1 mm. The water-based resin emulsion contains a large amount of amino groups, and its pH is 6 to 9. The surface contact angle of the connecting layer is ≤90°.

[0068] The aqueous resin emulsion of the anti-stick coating includes a photo-crosslinkable silicone resin emulsion and a room temperature self-crosslinking acrylate resin emulsion. Among them, the photo-crosslinkable silicone resin emulsion is prepared by first subjecting the silicone polymerization monomer to a hydrolysis and polycondensation 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 mix, removing the solvent and emulsifying with water; the room temperature self-crosslinking acrylate resin emulsion is a core-shell structure, the core layer structure is obtained by polymerizing the core layer monomer, the shell layer is obtained by polymerizing the shell layer monomer, and the shell layer monomer includes a room temperature self-crosslinking monomer, a soft monomer, a hard monomer and a hydrophilic monomer. The composition and preparation method of the aqueous resin emulsion of the anti-stick coating in this embodiment refer to the record of the protective coating in the CN202311577350.X patent.

[0069] The hot melt adhesive suitable for water-based coating waterproof coiled materials in this embodiment includes a plasticizer, a tackifying resin, a functional resin, a thermoplastic elastomer, and preferably, also includes one or more of an antioxidant, a UV absorber, and a filler.

[0070] Among them, the functional resin is one or more of rosin resin or its modified resin, terpene resin or its modified resin such as terpene phenolic resin. The functional resin contains one or more of abietic acid (such as neoabietic acid, dehydroabietic acid, dihydroabietic acid, tetrahydroabietic acid), palustric acid, pimaric acid (such as levorotatory pimaric acid, isopimaric acid), and its carboxyl content is 0.90mmol / g~2.80mmol / g. The carboxyl group in the hot melt adhesive is used to form a chemical bond with the amino group in the aqueous emulsion. The measurement method of the carboxyl content refers to EN 1240:2011 "Determination of hydroxyl value and / or hydroxyl content of adhesives". The softening point of the functional resin is 100℃~130℃.

[0071] The plasticizer is naphthenic oil and / or polyisobutylene.

[0072] The tackifying resin is one or more selected from C5 petroleum resin, hydrogenated petroleum resin, C9 petroleum resin, and C5 / C9 copolymerized petroleum resin.

[0073] The thermoplastic elastomer is one or more of styrene-isoprene-styrene triblock copolymer, styrene-butadiene-styrene triblock copolymer, and butyl rubber. Preferably, the thermoplastic elastomer is a styrene-isoprene-styrene triblock copolymer with a diblock content of 35%-45%.

[0074] The antioxidant is one or more selected from hindered phenols, phosphites, and thiophenols, preferably one or more of antioxidant 1010, antioxidant 168, and antioxidant 1076.

[0075] The ultraviolet absorber is one or more selected from benzotriazole, benzophenone and hindered amine ultraviolet absorbers.

[0076] The filler is one or more selected from calcium carbonate, rutile titanium dioxide or its modified substance, and kaolin inorganic filler.

[0077] Preferably, the hot melt adhesive comprises the following raw material components by weight:

[0078] Plasticizer 16~25 parts

[0079] 10~15 parts of tackifying resin

[0080] Functional resin 28-33 parts

[0081] Thermoplastic elastomer 26~30 parts

[0082] Antioxidant 0~3 parts

[0083] Ultraviolet absorber 0~3 parts

[0084] Filler 0~2 parts.

[0085] The method for preparing the water-based coating waterproof coiled material of this embodiment comprises the following steps:

[0086] After adding plasticizer and filler into the reaction vessel, start stirring and heating, and set the temperature of the reaction vessel to 160-180°C;

[0087] After the materials in the reaction container are mixed evenly and the material temperature reaches 180°C, add the thermoplastic elastomer, antioxidant and ultraviolet absorber, continue stirring and draw vacuum, and set the vacuum degree ≤-0.08MPa;

[0088] After the thermoplastic elastomer is completely melted and mixed evenly, slowly add the tackifying resin and the functional resin thereto while maintaining the vacuum state;

[0089] After all materials are melted and mixed evenly, a hot melt adhesive suitable for water-based coating waterproof membrane is obtained;

[0090] Heat and melt the hot melt adhesive. When the material temperature reaches 160°C, place it in the coating equipment for coating. The coating thickness of the hot melt adhesive is 0.30mm~0.33mm;

[0091] After the hot melt adhesive is applied, the water-based resin emulsion is applied after passing through the heat preservation equipment. The coating thickness of the water-based resin emulsion is controlled at 80-150μm of wet film. The heat preservation equipment is used to maintain the surface temperature of the hot melt adhesive at 70~80℃ to promote the combination between the hot melt adhesive and the water-based resin emulsion.

[0092] After the water-based resin emulsion is applied, it is dried with hot air, and the temperature is maintained at 60℃~80℃; this promotes the reaction and combination of carboxyl and amino groups, and accelerates the volatilization of water in the anti-stick coating, and the time is 5-10 minutes;

[0093] After passing through the drying equipment, the coating surface is completely dry, and a water-based coating waterproof membrane is obtained.

[0094] The hot melt adhesive for coating coil prepared in this embodiment has a large number of polar groups such as carboxyl, hydroxyl, epoxy, ether bond, acyl, sulfonic acid, phosphoric acid, and sulfinic acid in its functional resin. The presence of multiple polar groups improves the surface polarity of the hot melt adhesive and helps reduce the surface contact angle. At the same time, the presence of carboxyl, hydroxyl and other groups can improve the surface energy of the hot melt adhesive, have better hydrophilicity, and have a smaller surface contact angle, so that the water-based resin emulsion of the anti-stick coating has better wettability on the surface of the hot melt adhesive. At the same time, the presence of polar groups and monomer groups in the water-based resin emulsion can synergistically form a stable chemical bond bonding structure. Example 1

[0095] Referring to Table 2, the hot melt adhesive suitable for water-based coating waterproof coiled materials in this embodiment includes the following raw material components by weight:

[0096] 18 parts of naphthenic oil

[0097] 15 parts of tackifying resin

[0098] 31 parts of functional resin

[0099] 3 parts antioxidant

[0100] 3 parts of UV absorber

[0101] 2 parts of titanium dioxide

[0102] Thermoplastic elastomer 28 parts.

[0103] Among them, the tackifying resin is ordinary C5 petroleum resin HHC-1100. The functional resin is rosin terpene phenol resin T-105, with a carboxyl content of 0.963mmol / g and a softening point of 106℃. The antioxidant is 1076 and 168 compounded in a ratio of 1:1. The filler is Chemours titanium dioxide R-105. The thermoplastic elastomer is Jinhai Chenguang's JH-9163, with a diblock content of 38%.

[0104] The hot melt adhesive is subsequently coated on a substrate, and then coated with a water-based resin emulsion and dried to obtain a waterproof roll. Example 2

[0105] Referring to Table 2, the hot melt adhesive suitable for water-based coating waterproof membrane in this embodiment is different from that in Embodiment 1 in that the rosin terpene phenol resin in this embodiment is T-901, which has a carboxyl content of 1.43 mmol / g and a softening point of 124°C. Example 3

[0106] Referring to Table 2, the hot melt adhesive suitable for water-based coating waterproof coiled materials in this embodiment includes the following raw material components by weight:

[0107] 21 parts of naphthenic oil

[0108] 10 parts of tackifying resin

[0109] 32 parts of functional resin

[0110] 3 parts antioxidant

[0111] 3 parts of UV absorber

[0112] 2 parts of titanium dioxide

[0113] Thermoplastic elastomer 29 parts.

[0114] Among them, the tackifying resin is C5 hydrogenated petroleum resin H5-1001, and the softening point is 103°C. The functional resin is Eastman Poly-pale dimerized rosin, with a carboxyl content of 2.763mmol / g and a softening point of 103°C. The filler is Liankai Chemical's rutile titanium dioxide Tryruti AQ51. The thermoplastic elastomer is VECTOR 4116ND, and its diblock content is 42%. Tryruti AQ51 is a rutile titanium dioxide with a hydrophilic surface modification. The hydrophilic modification of titanium dioxide has an auxiliary effect on improving the overall surface contact angle. The anti-stick coating is a water-based resin emulsion, and the hydrophilic modified powder helps to apply the water-based emulsion on the surface of the hot melt adhesive.

[0115] The hot melt adhesive is subsequently coated on a substrate, and then coated with a water-based resin emulsion and dried to obtain a waterproof roll.

[0116] After the hot melt adhesive of this embodiment is formed into a film, its surface contact angle (water) is 65°, and the water-based resin emulsion can completely wet and spread on the surface of the hot melt adhesive without any glue leakage. Figure 2 As shown in Figure (b). Example 4

[0117] Referring to Table 2, the hot melt adhesive suitable for water-based coating waterproof membrane in this embodiment is different from that in Embodiment 3 in that the thermoplastic elastomer in this embodiment is Jinhai Chenguang JH-9163, and its diblock content is 38%. Example 5

[0118] Referring to Table 2, the hot melt adhesive for water-based coating waterproof coiled materials in this embodiment is different from that in Embodiment 3 in that the filler is different. The filler in this embodiment is R-105, which is common rutile titanium dioxide. Comparative Example 1

[0119] Referring to Table 2, the hot melt adhesive in this comparative example includes the following raw material components by weight:

[0120] Naphthenic oil 4010 29 parts

[0121] Ordinary C5 petroleum resin HHC-1100 42 parts

[0122] Thermoplastic elastomer SIS-1170 28 parts

[0123] Antioxidant (1076, 168 in 1:1 ratio) 1 part.

[0124] This comparative example uses conventional hot melt adhesive. After the conventional hot melt adhesive is coated on the substrate, a sample is taken and the surface contact angle is tested using water. After the test, a water-based resin emulsion is roller-coated on the surface. After the coating is completed, the water-based coating waterproof membrane is prepared by air drying.

[0125] After the hot melt adhesive in this comparative example is formed into a film, its surface contact angle is 120°. When the water-based resin emulsion is roller-coated on its surface, the roller shrinks during coating and causes the hot melt adhesive at the bottom to leak out. The wettability of the water-based resin emulsion on the surface of the hot melt adhesive is poor. The waterproof roll is rolled up after drying. After the simulated transportation test at 80°C and 5kg load, the roll cannot be unrolled. The hot melt adhesive surface coating shrinks during drying, resulting in glue leakage, which causes adhesion and cannot be unrolled for use normally. Comparative Example 2

[0126] The waterproof membrane in this comparative example is the waterproof membrane disclosed in Example 1 in CN202311577350.X. Comparative Example 3

[0127] The difference between this comparative example and Example 1 is that the functional resin in this comparative example is rosin terpene phenol resin T-105, the manufacturer is Arakawa Chemical of Japan, the carboxyl content is 0.855 mmol / g, and the softening point is 104°C.

[0128] The surface contact angle (water) of the hot melt adhesive in this comparative example after film formation is 115°. The surface shrinks greatly after the water-based resin emulsion is roller-coated, and the bottom hot melt adhesive cannot be completely covered after film formation. Figure 2 As shown in Figure (a), when the roll is unrolled and used again after being rolled up, it becomes stuck and cannot be unrolled. Comparative Example 4

[0129] The difference between this comparative example and Example 1 is that the functional resin in this comparative example is the polymerized rosin resin ARDYME R-115 produced by Arakawa Chemical of Japan, which has a carboxyl content of 3.1 mmol / g and a softening point of 115°C.

[0130] Table 2 Recipe

[0131] Example 6

[0132] This embodiment provides a method for preparing a hot melt adhesive and water-based coating waterproof roll based on the above embodiment, which specifically includes the following steps:

[0133] (1) After adding plasticizer and filler into the reaction vessel, start stirring and heating, and set the temperature of the reaction vessel to 160-180℃.

[0134] (2) After the materials in the reaction container are mixed evenly and the material temperature reaches 180°C, add the thermoplastic elastomer, antioxidant, and ultraviolet light absorber, increase the stirring speed, and draw the vacuum to set the vacuum degree ≤-0.08MPa.

[0135] (3) After the thermoplastic elastomer is completely melted and mixed evenly, slowly add the tackifying resin and functional resin into it, and keep the vacuum state turned on.

[0136] (4) After 2 hours, wait for the material temperature to reach 160°C and then place the coating equipment to apply the hot melt adhesive. The thickness of the hot melt adhesive coating is 0.30mm~0.33mm.

[0137] (5) After the hot melt adhesive coating is completed, it passes through the heat preservation equipment to maintain the surface temperature of the hot melt adhesive at 70~80℃; then the water-based resin emulsion is coated, and the coating thickness of the water-based resin emulsion is controlled at 80-150μm of wet film.

[0138] (6) After the emulsion coating is completed, it enters the hot air drying, maintaining the temperature at 60℃~80℃. After passing through the drying equipment, the coating surface is completely dry to obtain the finished water-based coating waterproof membrane.

[0139] Tests and Results

[0140] The hot melt adhesive of the embodiment and the comparative example was coated on the substrate, and the surface contact angle was tested by sampling. After the test, the aqueous emulsion was roller coated at a wet film thickness of 120 μm per square meter. After the roller coating, the film was dried with hot air and then rolled up. Subsequently, a peeling test with the post-cast concrete was performed, including no treatment, immersion treatment, heat treatment, UV treatment, and peeling test after immersion. The test results are shown in Table 3. Among them, the peeling test was performed according to the method in GB / T 23457-2017, and the contact angle test was performed according to the method for measuring the contact angle of plastic film with water in GB / T 30693-2014.

[0141] Table 3 Test results

[0142]

[0143] It can be seen from the results of the embodiments and comparative examples that increasing the use of functional resins within a certain range of carboxyl content can effectively reduce the surface water contact angle, so that the water-based resin emulsion can be better wetted and spread on its surface. After the comparison of the coiled materials, they can be unrolled and constructed normally after being placed at 80°C and 5kg load test. The acid value of the functional resin gradually increases within a certain range, and its peeling strength with the post-cast concrete after immersion in water will gradually decrease, affecting its performance. And the carboxyl content is high, the post-cast concrete is immersed in water and the peeling strength with the post-cast concrete after immersion in water will be lower than the standard value or the bonding surface will be warped. At the same time, the surface contact angle corresponding to the hot melt adhesive prepared by the rutile titanium dioxide with hydrophilic surface modification in Example 4 is significantly smaller than the surface contact angle corresponding to the hot melt adhesive prepared by the ordinary rutile titanium dioxide in Example 5. The surface wettability of the hot melt adhesive of the aqueous emulsion in Comparative Example 3 is poor, and the shrinkage after coating is large and cannot completely cover the bottom hot melt adhesive. After drying and rolling, adhesion will occur and it cannot be unrolled.

[0144] The anti-stick coating in the present invention is located between the connecting layer of the hot melt adhesive and the concrete. Ideally, the aqueous emulsion coating is completely spread on the surface of the hot melt adhesive to form a full coating, and is dried to form a film to protect the intermediate hot melt adhesive. At the same time, it is non-adhesive and can still be bonded to the concrete after pouring the concrete. The anti-stick coating plays a role in connecting the waterproofing membrane and the concrete. If the anti-stick coating cannot be well spread on the conventional hot melt adhesive and cannot form a full coating, firstly, after the waterproofing membrane is rolled up, the hot melt adhesive adheres to the substrate, causing the membrane to be unable to be unrolled and unusable, and secondly, it will cause a gap between the waterproofing membrane and the concrete and a weak bond.

[0145] The hot melt adhesive in the waterproof coiled material of the present invention contains polar groups such as carboxyl and hydroxyl groups, so that the aqueous anti-stick coating emulsion can better wet its surface, and the surface contact angle is lower. The contact angle θ with the water surface is ≤90°, and the anti-stick coating emulsion reacts to form a chemical bond structure for bonding. The hot melt adhesive suitable for water-based coating waterproof coiled materials of the present invention is extruded and coated on the substrate at 150°C-180°C, and then the aqueous resin emulsion of the anti-stick coating is roller-coated on the surface of the hot melt adhesive. After the anti-stick coating emulsion is roller-coated, hot air drying is performed to accelerate the condensation reaction rate of the amino and carboxyl groups, accelerate the volatilization of the water in the emulsion and the water produced by the condensation reaction, and the moisture in the anti-stick coating dried by hot air is completely volatilized to achieve solid drying without the need for ultraviolet curing. The surface anti-stick coating forms a dry film, which forms a chemical bond link with the hot melt adhesive under the action of chemical bonds, which is different from traditional physical bonding and has more excellent bonding strength and peeling force. The water-based coating waterproof coiled material of the present invention realizes that the surface water-based vertical emulsion has good wettability on the hot melt adhesive surface, conveniently and quickly forms a good waterproof layer, forms a fully sticky structure with the post-cast concrete, makes the surface water-based resin emulsion better coated, has better wettability to the water-based resin emulsion, and is more suitable for the water-based resin emulsion to be coated on the hot melt adhesive layer by roller coating and spraying. The hot melt adhesive of the present invention contains a specific content of carboxyl groups, improves the wetting of the anti-stick coating emulsion of various water-based substrates on their surfaces, and the subsequent process is simpler and can be directly dried without ultraviolet irradiation and other processes.

[0146] The above embodiments are only for illustrating the technical concept and features of the present invention, and their purpose is to enable people familiar with this technology to understand the contents of the present invention and implement them accordingly. They cannot be used to limit the protection scope of the present invention. Any equivalent changes or modifications made according to the spirit of the present invention should be included in the protection scope of the present invention.

[0147] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the 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 as specifically disclosed in this article.

Claims

1. A waterproof roll material, comprising a substrate, a connecting layer and an anti-sticking coating in sequence, wherein the connecting layer is formed by a hot melt adhesive, and the anti-sticking coating is formed by an aqueous resin emulsion, characterized in that: The hot melt adhesive comprises a plasticizer, a tackifying resin, a functional resin, and a thermoplastic elastomer. The functional resin contains one or more of abietic acid, palustric acid, and pimaric acid. The carboxyl content of the functional resin is 0.90 mmol / g to 2.80 mmol / g. The carboxyl group in the hot melt adhesive is used to form a chemical bond with the amino group in the water-based resin emulsion and to make the hot melt adhesive reach a predetermined surface contact angle. The surface contact angle of the connecting layer is ≤90°. The aqueous resin emulsion contains amino groups; the pH of the aqueous resin emulsion is 6-9; and the aqueous resin emulsion includes a photo-crosslinkable silicone resin emulsion and / or a room temperature self-crosslinking acrylic resin emulsion.

2. The waterproof coiled material according to claim 1, characterized in that: The functional resin is one or more of rosin resin or modified resin thereof, terpene resin or modified resin thereof.

3. The waterproof coiled material according to claim 1, characterized in that: The softening point of the functional resin is 100°C to 130°C.

4. The waterproof coiled material according to claim 1, characterized in that: The plasticizer is naphthenic oil and / or polyisobutylene.

5. The waterproof coiled material according to claim 1, characterized in that: The tackifying resin is one or more selected from C5 petroleum resin, hydrogenated petroleum resin, C9 petroleum resin, and C5 / C9 copolymerized petroleum resin.

6. The waterproof coiled material according to claim 1, characterized in that: The thermoplastic elastomer is one or more selected from styrene-isoprene-styrene triblock copolymer, styrene-butadiene-styrene triblock copolymer and butyl rubber.

7. The waterproof coiled material according to claim 6, characterized in that: The thermoplastic elastomer is a styrene-isoprene-styrene triblock copolymer with a diblock content in the range of 35%-45%.

8. The waterproof coiled material according to claim 1, characterized in that: The hot melt adhesive comprises the following raw material components by weight: Plasticizer 16~25 parts 10~15 parts of tackifying resin Functional resin 28-33 parts Thermoplastic elastomer 26~30 parts.

9. The waterproof coiled material according to claim 1, characterized in that: The hot melt adhesive includes an antioxidant, and the antioxidant is one or more selected from hindered phenols, phosphites, and thiophenols.

10. The waterproof coiled material according to claim 1, characterized in that: The hot melt adhesive includes an ultraviolet absorber, and the ultraviolet absorber is one or more selected from benzotriazole, benzophenone, and hindered amine ultraviolet absorbers.

11. The waterproof coiled material according to claim 1, characterized in that: The hot melt adhesive includes a filler, and the filler is one or more selected from calcium carbonate, rutile titanium dioxide or its modified substance, and kaolin inorganic filler.

12. The waterproof coiled material according to claim 1, characterized in that: The organosilicon resin emulsion is prepared by first subjecting an organosilicon polymerizable 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 mix, removing the solvent, and emulsifying with water.

13. The waterproof coiled material according to claim 1, characterized in that: The room temperature self-crosslinking acrylic resin emulsion is 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.

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