Hot-melt adhesive film resistant to water boiling, preparation method therefor, and composite structure

Abstract

The present application relates to the technical field of hot-melt adhesives, and in particular to a hot-melt adhesive film resistant to water boiling, a preparation method therefor, and a composite structure. The hot-melt adhesive film resistant to water boiling comprises a first adhesive layer, an intermediate layer, and a second adhesive layer which are sequentially attached. The first adhesive layer comprises 60-90 parts of polyester TPU particles, 10-40 parts of an epoxy resin, 1-6 parts of tannic acid, and 0.05-1 part of an antioxidant. The intermediate layer comprises 60-90 parts of an ethylene-methyl acrylate copolymer, 1-10 parts of a multifunctional organic acid, and 5-35 parts of an ethylene-methyl acrylate-glycidyl methacrylate terpolymer. The second adhesive layer comprises a polyolefin adhesive resin. The hot-melt adhesive film of the present application enables effective bonding between a PVC waterproof sheet and a metal by means of a three-layer structure configuration and can not only effectively prevent the migration of a plasticizer in the PVC waterproof sheet but also offers excellent resistance to water boiling, thereby facilitating the outdoor application of the PVC waterproof sheet.

Description

Water boiling resistant hot melt adhesive film, preparation method thereof and composite structure TECHNICAL FIELD

[0001] The present application relates to the technical field of hot melt adhesive, in particular to a water boiling resistant hot melt adhesive film, a preparation method thereof and a composite structure. BACKGROUND

[0002] PVC waterproofing membrane is a new type of synthetic material produced by PVC resin, which has the characteristics of high tensile strength, high elongation, corrosion resistance, impermeability, small shrinkage, excellent puncture resistance and long service life, and is widely used in roofing repair engineering and steel structure roofing waterproof system. Mechanical fixing method and full bonding method are the traditional methods for combining PVC waterproofing membrane and metal roof, but each has the problems of poor fixing effect, uneven thickness of glue brushing and VOC emission.

[0003] Hot melt adhesive film is an environmentally friendly adhesive film. When used for the combination of PVC waterproofing membrane and metal roof, it not only solves the problems of difficult control of glue brushing amount and VOC emission of glue, but also greatly saves construction cost, improves construction quality and construction efficiency. The patent application with publication number CN109207073A discloses a three-layer composite hot melt adhesive film for bonding metal and polar functional plastic, but it cannot effectively solve the migration problem of plasticizer in PVC waterproofing membrane, resulting in insufficient bonding durability of PVC waterproofing membrane and metal. The patent application with publication number CN114479682A discloses a hot melt adhesive film for bonding metal and PVC and a preparation method thereof, which introduces high grafting rate maleic anhydride grafted C5 / C9 copolymer resin into the first adhesive layer to improve the peeling strength between the first adhesive layer and PVC, and form a firm barrier in the first adhesive layer to prevent the migration of plasticizer in PVC to the first adhesive layer, thereby improving the resistance of the hot melt adhesive film to plasticizer. However, the water boiling resistance of the hot melt adhesive film is poor, and there are still great hidden dangers when used in outdoor waterproof engineering.

[0004] Therefore, the present application is proposed. SUMMARY

[0005] The following is a summary of the subject matter of the detailed description herein. This summary is not intended to limit the scope of protection of the claims.

[0006] One object of the present application is to provide a water boiling resistant hot melt adhesive film which not only solves the migration problem of plasticizer in PVC waterproofing membrane, but also has good water boiling resistance, greatly promoting the outdoor application of PVC waterproofing membrane.

[0007] Another object of the present application is to provide a preparation method of the water boiling resistant hot melt adhesive film.

[0008] Another object of the present application is to provide a PVC waterproofing membrane and metal composite structure.

[0009] To achieve the above object, the present application provides in one aspect a water-resistant hot melt adhesive film, comprising sequentially attached first adhesive layer, intermediate layer and second adhesive layer.

[0010] The first adhesive layer comprises the following components by weight fraction: polyester TPU particles 60-90 parts, epoxy resin 10-40 parts, tannic acid 1-6 parts and antioxidant 0.05-1 part.

[0011] The intermediate layer comprises the following components by weight fraction: ethylene-methyl acrylate copolymer 60-90 parts, multifunctional organic acid 1-10 parts and ethylene-methyl acrylate-glycidyl methacrylate terpolymer 5-35 parts.

[0012] The second adhesive layer comprises polyolefin adhesive resin.

[0013] In the detailed description of the present application, the epoxy value of the epoxy resin is 0.1-0.5 eq / 100g.

[0014] In the detailed description of the present application, the melting point of the polyester TPU particles is 100-160℃, and the melt index under the test conditions of 190℃, 2.16kg is 15-50g / 10min.

[0015] In the detailed description of the present application, the multifunctional organic acid comprises at least one of malic acid and citric acid.

[0016] In the detailed description of the present application, the mass ratio of the epoxy resin to the tannic acid is (3-15) : 1, further optionally (4-12) : 1.

[0017] In the detailed description of the present application, in the ethylene-methyl acrylate-glycidyl methacrylate terpolymer, the content of GMA block is 3wt%-6wt%.

[0018] In the detailed description of the present application, the mass ratio of the multifunctional organic acid to GMA in the ethylene-methyl acrylate-glycidyl methacrylate terpolymer is 1:(0.06-0.36), further optionally 1:(0.08-0.32).

[0019] In the detailed description of the present application, the polyolefin adhesive resin is grafted with polar groups, and the polar groups comprise maleic anhydride and / or carboxyl group. Further, in the polyolefin adhesive resin, the grafting rate of polar groups is 0.1%-1.5%, further optionally 0.15%-1.0%.

[0020] In the detailed description of the present application, the thickness ratio of the first adhesive layer, the intermediate layer and the second adhesive layer is (1-2) : 1 : (1-2).

[0021] In the detailed description of the present application, the thickness of the water-boiling resistant hot melt adhesive film is 0.03-0.15 mm.

[0022] Another aspect of the present application provides a preparation method of any one of the water-boiling resistant hot melt adhesive films, comprising the following steps:

[0023] The first adhesive layer raw material, the intermediate layer raw material and the second adhesive layer raw material are subjected to multi-layer co-extrusion blown film or casting to obtain the water-boiling resistant hot melt adhesive film.

[0024] Another aspect of the present application provides a composite structure comprising a PVC waterproofing membrane, a water-boiling resistant hot melt adhesive film and a metal layer which are sequentially attached; the water-boiling resistant hot melt adhesive film is any one of the water-boiling resistant hot melt adhesive films.

[0025] In the detailed description of the present application, the first adhesive layer of the water-boiling resistant hot melt adhesive film is attached to the PVC waterproofing membrane, and the second adhesive layer of the water-boiling resistant hot melt adhesive film is attached to the metal layer.

[0026] Compared with the prior art, the present application has the following beneficial effects:

[0027] (1) The hot melt adhesive film of the present application is provided with a three-layer structure, which can effectively connect the PVC waterproofing membrane and the metal, and the substrate and the adhesive film, as well as the layers of the adhesive film, all present strong mutual interaction, which not only effectively prevents the migration of plasticizers in the PVC waterproofing membrane, but also has excellent water-boiling resistance, which helps to promote the outdoor application of the PVC waterproofing membrane.

[0028] (2) The preparation process of the hot melt adhesive film of the present application is simple and can be produced continuously.

[0029] Other aspects can be appreciated after reading and understanding the detailed description. DETAILED DESCRIPTION

[0030] The technical solutions of the present application will be clearly and completely described below in conjunction with specific embodiments, but those skilled in the art will understand that the following described embodiments are part of the embodiments of the present application, not all the embodiments, and are only used to illustrate the present application, and should not be regarded as limiting the scope of the present application. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative labor are within the scope of protection of the present application. If the specific conditions are not specified in the embodiments, the conventional conditions or the conditions recommended by the manufacturer are used. If the reagents or instruments used are not specified by the manufacturer, they are all conventional products that can be purchased on the market.

[0031] The present application provides a water-boiling-resistant hot melt adhesive film, comprising a first adhesive layer, an intermediate layer and a second adhesive layer sequentially attached;

[0032] The first adhesive layer comprises the following components by weight fraction: 60-90 parts of polyester TPU particles, 10-40 parts of epoxy resin, 1-6 parts of tannic acid and 0.05-1 parts of antioxidant;

[0033] The intermediate layer comprises the following components by weight fraction: 60-90 parts of ethylene-methyl acrylate copolymer, 1-10 parts of multifunctional organic acid and 5-35 parts of ethylene-methyl acrylate-glycidyl methacrylate terpolymer;

[0034] The second adhesive layer comprises a polyolefin adhesive resin.

[0035] The hot melt adhesive film of the present application is provided with a three-layer structure, which can effectively connect the PVC waterproofing membrane and the metal, and the substrate and the adhesive film, as well as the layers of the adhesive film, all show strong mutual interaction, which not only effectively prevents the migration of plasticizers in the PVC waterproofing membrane, but also has excellent water-boiling resistance, which helps to promote the outdoor application of PVC waterproofing membrane.

[0036] In the first adhesive layer, the hydrolysis resistance of polyester TPU is improved by the synergistic effect of epoxy resin and tannic acid. When polyester TPU hydrolyzes, the carboxyl or hydroxyl groups generated by hydrolysis will react with epoxy resin, thereby preventing further hydrolysis of polyester TPU. Moreover, tannic acid, epoxy resin and organic acid form a crosslinked network structure, which not only effectively prevents the migration of plasticizers in the PVC waterproofing membrane, but also significantly improves the adhesion strength of the first adhesive layer and the intermediate layer, and further improves the hydrolysis resistance of polyester TPU.

[0037] The component design of the intermediate layer can improve the bonding strength of the intermediate layer with the first bonding layer and the second bonding layer. The present application research finds that the ethylene-methyl acrylate copolymer in the intermediate layer has good initial bonding properties with the polyester TPU and the polyolefin bonding resin, and using ethylene-methyl acrylate copolymer as the base resin of the intermediate layer helps to improve the bonding between the layers. The addition of ethylene-methyl acrylate-glycidyl methacrylate terpolymer in the intermediate layer can improve the compatibility between the base and the organic acid on the one hand, and can chemically react with part of the polar groups such as maleic anhydride groups in the second bonding layer under the promotion of the organic acid on the other hand, further improving the bonding stability of the intermediate layer and the second bonding layer.

[0038] In the first bonding layer of the present application, the amount of each component can be as follows:

[0039] The amount of polyester TPU particles can be 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts, or a range formed by any two of them; according to the diffusion theory and experimental verification, TPU has good adhesion with PVC, and polyester TPU has higher cohesive strength than polyether TPU, and has stronger adhesion with polar substrates, so polyester TPU is selected as the base resin for bonding PVC waterproofing membrane.

[0040] The amount of epoxy resin can be 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, or a range formed by any two of them; although polyester TPU has good adhesion with PVC, the ester group in polyester TPU is prone to hydrolysis, which damages the TPU structure and further reduces the mechanical properties and adhesion reliability. The present application utilizes the reaction of epoxy resin with carboxyl or hydroxyl groups generated by hydrolysis of polyester TPU to prevent further hydrolysis of polyester TPU.

[0041] The amount of tannic acid can be 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, or a range formed by any two of them; tannic acid contains multiple phenolic hydroxyl groups, and tannic acid itself is difficult to chemically react with epoxy resin, but under the action of organic acid in the intermediate layer, the three form a crosslinked network structure, which not only further improves the hydrolysis resistance of polyester TPU, but also prevents the migration of plasticizers in PVC waterproofing membrane and improves the bonding strength of the first bonding layer and the intermediate layer.

[0042] The amount of antioxidant can be 0.05 parts, 0.1 parts, 0.2 parts, 0.5 parts, 0.8 parts, 1 part, or a range consisting of any two of them; the addition of antioxidant can avoid the thermal oxidative degradation of polyester TPU in the production and processing process, and maintain the mechanical strength of the base resin. Among them, the antioxidant includes but is not limited to at least one of antioxidant 1010, antioxidant 1076, antioxidant 1098, antioxidant 264, antioxidant B245, antioxidant TPP, and antioxidant TNP.

[0043] In the intermediate layer of the present application, the amount of each component can be as follows:

[0044] The amount of ethylene-methyl acrylate copolymer can be 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts, or a range consisting of any two of them.

[0045] The amount of multifunctional organic acid can be 1 part, 2 parts, 5 parts, 8 parts, 10 parts, or a range consisting of any two of them; the addition of multifunctional organic acid to the intermediate layer not only can act with the epoxy resin and tannic acid in the first adhesive layer to improve water resistance and form a crosslinked network structure to prevent plasticizer migration, but also can improve the adhesion strength of the first adhesive layer and the intermediate layer; and can also promote the components of the intermediate layer to act with the second adhesive layer to improve the adhesion strength of the intermediate layer and the second adhesive layer.

[0046] The amount of ethylene-methyl acrylate-glycidyl methacrylate terpolymer can be 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, or a range consisting of any two of them; ethylene-methyl acrylate-glycidyl methacrylate terpolymer.

[0047] In the specific embodiments of the present application, the epoxy value of the epoxy resin is 0.1-0.5 eq / 100g. Among them, the epoxy resin can be further selected as a bisphenol A type epoxy resin.

[0048] The epoxy group and hydroxyl group in the bisphenol A type epoxy resin give the resin good reactivity, and the resin cured product has strong cohesion and adhesion. When the epoxy value is too high, the epoxy resin curing is relatively violent, the reaction is not easy to control, and the processing performance of the hot melt adhesive film is affected; when the epoxy value is too low, the improvement effect on water boiling resistance and plasticizer migration resistance is insufficient. In different embodiments, the epoxy value of the epoxy resin can be 0.1 eq / 100g, 0.2 eq / 100g, 0.3 eq / 100g, 0.4 eq / 100g, 0.5 eq / 100g, or a range consisting of any two of them.

[0049] In the detailed description of the present application, the melting point of the polyester TPU particles is 100-160℃, and the melt index under the test conditions of 190℃, 2.16kg is 15-50g / 10min.

[0050] The polyester TPU particles are used as the base resin in the first adhesive layer, which has certain temperature resistance and moderate fluidity to meet the outdoor application scenarios and processing filmability. For example, in different embodiments, the melting point of the polyester TPU particles can be 100℃, 120℃, 140℃, 160℃, or a range formed by any two of them; and the melt index under the test conditions of 190℃, 2.16kg can be 15g / 10min, 20g / 10min, 25g / 10min, 35g / 10min, 45g / 10min, 50g / 10min, or a range formed by any two of them.

[0051] In the detailed description of the present application, the multifunctional organic acid includes at least one of malic acid and citric acid.

[0052] In the detailed description of the present application, the mass ratio of the epoxy resin to tannic acid is (3-15) : 1, and further optionally (4-12) : 1.

[0053] For example, in different embodiments, the mass ratio of the epoxy resin to tannic acid can be 3:1, 4:1, 5:1, 6:1, 8:1, 10:1, 12:1, 15:1, or a range formed by any two of them. Controlling the mass ratio of the epoxy resin to tannic acid within the above range is more conducive to improving the performance of water boiling resistance and peel strength.

[0054] In the detailed description of the present application, the content of the GMA block in the ethylene-methyl acrylate-glycidyl methacrylate terpolymer is 3wt%-6wt%.

[0055] The ethylene-methyl acrylate-glycidyl methacrylate terpolymer can improve the compatibility of the organic acid in the middle layer on the one hand, and on the other hand, the ethylene-methyl acrylate-glycidyl methacrylate terpolymer with a certain GMA content can chemically react with the polar groups such as maleic anhydride in the second adhesive layer under the promotion of the organic acid, thereby improving the adhesion stability. However, when the GMA content is too high, the reactivity of the polar groups in the polyolefin adhesive resin and the metal will be deteriorated, thereby affecting the adhesion of the second adhesive layer and the metal. For example, in different embodiments, the content of the GMA block in the ethylene-methyl acrylate-glycidyl methacrylate terpolymer can be 3wt%, 3.5wt%, 4wt%, 4.5wt%, 5wt%, 5.5wt%, 6wt%, or a range formed by any two of them.

[0056] In the detailed description of the present application, the mass ratio of the multifunctional organic acid to GMA in the ethylene-methyl acrylate-glycidyl methacrylate terpolymer is 1:(0.06-0.36), and further optionally 1:(0.08-0.32).

[0057] As in different embodiments, the mass ratio of the multifunctional organic acid to GMA in the ethylene-methyl acrylate-glycidyl methacrylate terpolymer can be 1:0.06, 1:0.09, 1:0.1, 1:0.12, 1:0.15, 1:0.18, 1:0.2, 1:0.22, 1:0.25, 1:0.28, 1:0.3, 1:0.32, 1:0.35, 1:0.36, or a range consisting of any two of them. Controlling the mass ratio of the organic acid to GMA in the copolymer within the above range is more conducive to improving the boiling water resistance of the hot melt adhesive film and the bonding strength between the layers. Among them, the mass of GMA in the ethylene-methyl acrylate-glycidyl methacrylate terpolymer refers to the amount of GMA block in the terpolymer.

[0058] In the detailed description of the present application, the melt index of the ethylene-methyl acrylate copolymer under the test conditions of 190°C and 2.16kg is 1-10g / 10min.

[0059] As in different embodiments, the melt index of the ethylene-methyl acrylate copolymer under the test conditions of 190°C and 2.16kg can be 1g / 10min, 2g / 10min, 5g / 10min, 8g / 10min, 10g / 10min, or a range consisting of any two of them, to further ensure good processing filmability.

[0060] In the detailed description of the present application, the melt index of the polyolefin bonding resin under the test conditions of 190°C and 2.16kg is 1-5g / 10min.

[0061] As in different embodiments, the melt index of the polyolefin bonding resin under the test conditions of 190°C and 2.16kg can be 1g / 10min, 2g / 10min, 3g / 10min, 4g / 10min, 5g / 10min, or a range consisting of any two of them.

[0062] In the detailed description of the present application, the polyolefin bonding resin is grafted with a polar group, and the polar group includes maleic anhydride and / or carboxyl. Further, in the polyolefin bonding resin, the grafting rate of the polar group is 0.1%-1.5%, and further optionally 0.15%-1.0%.

[0063] The grafting rate of the polar group in the polyolefin bonding resin can be 0.1%, 0.2%, 0.5%, 0.8%, 1%, 1.2%, 1.5%, or a range consisting of any two of them, in different embodiments. In actual operation, at least one of the VB grades of polyolefin bonding resins produced by Guangzhou Lushan New Material Co., Ltd., such as VB550, VB530, VB770, and VB760, can be used, which can on the one hand chemically react with the ethylene-methyl acrylate-glycidyl methacrylate terpolymer in the intermediate layer under the promotion of organic acid to improve the interlayer bonding stability, and on the other hand has good adhesion to metal, meeting the requirements of outdoor engineering applications.

[0064] In the specific embodiments of the present application, the thickness ratio of the first bonding layer, the intermediate layer, and the second bonding layer is (1-2): 1: (1-2).

[0065] Controlling the thickness of each layer within the above range is more conducive to effectively forming a crosslinked network structure in the first bonding layer that can prevent the migration of plasticizers and effectively improving water resistance, while ensuring the bonding strength between the layers. For example, in different embodiments, the thickness ratio of the first bonding layer, the intermediate layer, and the second bonding layer can be 1:1:1, 1.5:1:1, 2:1:1, 1:1:1.5, 1:1:2, 1.5:1:1.5, 2:1:1.5, etc., but is not limited thereto.

[0066] In the specific embodiments of the present application, the thickness of the water-resistant boiling hot melt adhesive film is 0.03-0.15 mm.

[0067] For example, in different embodiments, the thickness of the water-resistant boiling hot melt adhesive film can be 0.03 mm, 0.05 mm, 0.08 mm, 0.1 mm, 0.12 mm, 0.15 mm, or a range consisting of any two of them.

[0068] Another aspect of the present application provides a preparation method of any one of the above water-resistant boiling hot melt adhesive films, comprising the following steps:

[0069] The first bonding layer raw material, the intermediate layer raw material, and the second bonding layer raw material are subjected to multi-layer co-extrusion blown film or casting to obtain the water-resistant boiling hot melt adhesive film.

[0070] The co-extrusion blown film can be performed using a blown film machine, and the co-extrusion casting can be performed using a casting machine. The extrusion temperature of the first bonding layer, the intermediate layer, and the second bonding layer co-extrusion blown film or casting is 140-170°C, 150-190°C, and 140-190°C, respectively, and the co-extrusion die temperature is 140-160°C.

[0071] In the detailed description of the present application, the preparation of the first adhesive layer raw material comprises: allocating components of the first adhesive layer, and then mixing and extruding and granulating; wherein the twin-screw extruder has 11 temperature zones, and the temperature of each temperature zone is as follows: 40℃, 80℃, 120℃, 140-170℃, 140-170℃, 140-170℃, 140-170℃, 140-170℃, 140-170℃, 140-170℃, 140-170℃, and the die temperature is 140-170℃.

[0072] In the detailed description of the present application, the preparation of the intermediate layer raw material comprises: allocating components of the intermediate layer, and then mixing and extruding and granulating; wherein the twin-screw extruder has 11 temperature zones, and the temperature of each temperature zone is as follows: 40℃, 80℃, 120℃, 150-190℃, 150-190℃, 150-190℃, 150-190℃, 150-190℃, 150-190℃, 150-190℃, 150-190℃, and the die temperature is 150-190℃.

[0073] In actual operation, the mixing operation can be performed in a high-speed mixer, and the extruding and granulating operation can be performed in a twin-screw extruder.

[0074] Another aspect of the present application provides a composite structure comprising a PVC waterproofing membrane, a water-boiling-resistant hot melt adhesive film and a metal layer sequentially attached.

[0075] In the detailed description of the present application, the first adhesive layer of the water-boiling-resistant hot melt adhesive film is attached to the PVC waterproofing membrane, and the second adhesive layer of the water-boiling-resistant hot melt adhesive film is attached to the metal layer.

[0076] When the water-boiling-resistant hot melt adhesive film of the present application is combined with the PVC waterproofing membrane and the galvanized sheet, the 180° room temperature peel strength can be ≥135N / 25mm, such as 138N / 25mm, 140N / 25mm, 145N / 25mm, 150N / 25mm, 155N / 25mm, 160N / 25mm, etc.; the 180° room temperature peel strength after boiling for 4h can be ≥127N / 25mm, such as 130N / 25mm, 140N / 25mm, 145N / 25mm, 150N / 25mm, 155N / 25mm, 160N / 25mm, etc.; the peel strength retention rate after boiling for 4h is >90%, such as 92%, 95%, 98%, 100%, etc.

[0077] Example 1

[0078] The embodiment provides a hot melt adhesive film resistant to boiling water, which comprises a first adhesive layer, an intermediate layer and a second adhesive layer sequentially attached.

[0079] The raw material of the first adhesive layer comprises the following components in parts by weight: polyester TPU particles 80 parts, epoxy resin 18 parts, tannic acid 2 parts, antioxidant 0.3 parts. The melting point of the polyester TPU particles is 130-140 DEG C, the melt index is 40 g / 10 min (190 DEG C / 2.16 kg), and the polyester TPU particles are purchased from Zhejiang Huafeng Thermoplastic Polyurethane Co., Ltd. and the model number is HF-3H80A-6; the epoxy resin is bisphenol A type epoxy resin E-44, and the epoxy value is 0.44 eq / 100 g; the tannic acid has a CAS number of 1401-55-4; and the antioxidant is antioxidant 1010.

[0080] The raw material of the intermediate layer comprises the following components in parts by weight: ethylene-methyl acrylate copolymer (EMA) 70 parts, organic acid 5 parts, ethylene-methyl acrylate-glycidyl methacrylate terpolymer (EMA-GMA) 25 parts. The EMA has a model number of Optema TC 111, and the melt index is 2 g / 10 min (190 DEG C / 2.16 kg); the organic acid is selected to be malic acid, and the CAS number is 6915-15-7; and the EMA-GMA has a GMA content of 6 wt%, and the model number is Japan Sumitomo BF-7M.

[0081] The raw material of the second adhesive layer is hot melt adhesive particles VB550 (Guangzhou Lushan New Material Co., Ltd.).

[0082] The preparation method of the hot melt adhesive film resistant to boiling water in the embodiment comprises the following steps:

[0083] (a) First, the raw materials of the first adhesive layer and the intermediate layer are uniformly mixed in a high-speed mixer according to the mixing ratio, and then are melt-extruded and granulated in a double-screw extruder to obtain the granules of the first adhesive layer and the granules of the intermediate layer. When the first adhesive layer is extruded and granulated, the double-screw extruder comprises 11 temperature zones, and the temperatures of the temperature zones are 40 DEG C, 80 DEG C, 120 DEG C, 150 DEG C, 150 DEG C, 150 DEG C, 150 DEG C, 150 DEG C, 150 DEG C, 150 DEG C and 150 DEG C respectively, and the die temperature is 150 DEG C; when the intermediate layer is extruded and granulated, the double-screw extruder comprises 11 temperature zones, and the temperatures of the temperature zones are 40 DEG C, 80 DEG C, 120 DEG C, 160 DEG C, 160 DEG C, 160 DEG C, 160 DEG C, 160 DEG C, 160 DEG C, 160 DEG C and 160 DEG C respectively, and the die temperature is 160 DEG C.

[0084] (b) the granules of the first adhesive layer, the granules of the intermediate layer and the granules of the second adhesive layer are blown into films on a three-layer co-extrusion film blowing machine to obtain corresponding hot melt adhesive films, the thickness of the first adhesive layer is 0.03 mm, the thickness of the intermediate layer is 0.02 mm, and the thickness of the second adhesive layer is 0.03 mm. In the co-extrusion film blowing, the extrusion section temperature of the first adhesive layer is 150°C, the extrusion section temperature of the intermediate layer is 160°C, the extrusion section temperature of the second adhesive layer is 150°C, and the temperature of the co-extrusion die is 150°C.

[0085] Example 2

[0086] This example refers to the water-resistant hot melt adhesive film and the preparation method thereof of Example 1, the only difference being that the type of epoxy resin in the first adhesive layer is different.

[0087] In this example, the epoxy resin is bisphenol A type epoxy resin E-12, and the epoxy value is 0.10 eq / 100 g.

[0088] Example 3

[0089] This example refers to the water-resistant hot melt adhesive film and the preparation method thereof of Example 1, the only difference being that the type of epoxy resin in the first adhesive layer is different.

[0090] In this example, the epoxy resin is bisphenol A type epoxy resin E-51, and the epoxy value is 0.50 eq / 100 g.

[0091] Example 4

[0092] This example refers to the water-resistant hot melt adhesive film and the preparation method thereof of Example 1, the only difference being that the type of epoxy resin in the first adhesive layer is different.

[0093] In this example, the epoxy resin is bisphenol A type epoxy resin E-55, and the epoxy value is 0.55 eq / 100 g.

[0094] Example 5

[0095] This example refers to the water-resistant hot melt adhesive film and the preparation method thereof of Example 1, the only difference being that the amount of epoxy resin and tannic acid in the first adhesive layer is different.

[0096] In this example, the amount of epoxy resin is 15 parts and the amount of tannic acid is 5 parts.

[0097] Example 6

[0098] This example refers to the water-resistant hot melt adhesive film and the preparation method thereof of Example 1, the only difference being that the amount of epoxy resin and tannic acid in the first adhesive layer is different.

[0099] In this example, the amount of epoxy resin is 19 parts and the amount of tannic acid is 1 part.

[0100] Example 7

[0101] This example refers to the water-resistant hot melt adhesive film and the preparation method thereof of Example 1, the only difference being that the type of EMA-GMA in the intermediate layer is different.

[0102] In this example, the GMA content of EMA-GMA is 8wt%, and the brand is AX 8900 from Arkema, France.

[0103] Example 8

[0104] This example refers to the water-resistant hot melt adhesive film and the preparation method thereof of Example 1, the only difference being that the amount of each component in the intermediate layer is different.

[0105] In this example, the raw materials of the intermediate layer include the following components by weight fraction: ethylene-methyl acrylate copolymer (EMA) 90 parts, organic acid 5 parts, ethylene-methyl acrylate-glycidyl methacrylate terpolymer (EMA-GMA) 5 parts.

[0106] Example 9

[0107] This example refers to the water-resistant hot melt adhesive film and the preparation method thereof of Example 1, the only difference being that the amount of each component in the intermediate layer is different.

[0108] In this example, the raw materials of the intermediate layer include the following components by weight fraction: ethylene-methyl acrylate copolymer (EMA) 65 parts, organic acid 5 parts, ethylene-methyl acrylate-glycidyl methacrylate terpolymer (EMA-GMA) 30 parts.

[0109] Example 10

[0110] This example refers to the water-resistant hot melt adhesive film and the preparation method thereof of Example 1, the difference being that the components and amounts of each layer and the thickness are different.

[0111] In this example, the thickness of the first adhesive layer is 0.02mm, the thickness of the intermediate layer is 0.02mm, and the thickness of the second adhesive layer is 0.02mm.

[0112] The raw materials of the first adhesive layer include the following components by weight fraction: polyester TPU particles 70 parts, epoxy resin 26 parts, tannic acid 4 parts, antioxidant 0.5 parts. The melting point of the polyester TPU particles is 118-128℃, and the melt index is 32g / 10min (190℃ / 2.16kg), which is purchased from Wanhua Chemical Group Co., Ltd. and the brand is WHT-6229; the epoxy resin is bisphenol A type epoxy resin NPES-901 with an epoxy value of 0.22 eq / 100g; the tannic acid has a CAS number of 1401-55-4; and the antioxidant is antioxidant B245.

[0113] The raw materials of the intermediate layer include the following components by weight fraction: ethylene-methyl acrylate copolymer (EMA) 80 parts, organic acid 3 parts, ethylene-methyl acrylate-glycidyl methacrylate terpolymer (EMA-GMA) 17 parts. The EMA brand is Optema TC 220, and the melt index is 5 g / 10 min (190℃ / 2.16 kg); the organic acid is selected as malic acid, and the CAS number is 6915-15-7; the GMA content of the EMA-GMA is 3wt%, and the brand is Japan Sumitomo BF-7L.

[0114] The raw materials of the second adhesive layer are hot melt adhesive particles VB530 (Guangzhou Lushan New Materials Co., Ltd.).

[0115] Example 11

[0116] This example refers to the water-resistant hot melt adhesive film of Example 1 and the preparation method thereof, with the difference being that the components and amounts of each layer and the thicknesses are different.

[0117] In this example, the thickness of the first adhesive layer is 0.04 mm, the thickness of the intermediate layer is 0.02 mm, and the thickness of the second adhesive layer is 0.03 mm.

[0118] The raw materials of the first adhesive layer include the following components by weight fraction: polyester TPU particles 85 parts, epoxy resin 12 parts, tannic acid 3 parts, antioxidant 0.6 parts. The melting point of the polyester TPU particles is 100-110℃, and the melt index is 25 g / 10 min (190℃ / 2.16 kg), which is purchased from Wanhua Chemical Group Co., Ltd., and the brand is WHT-6232B; the epoxy resin is bisphenol A type epoxy resin NPES-904, and the epoxy value is 0.12 eq / 100 g; the tannic acid CAS number is 1401-55-4; and the antioxidant is selected as antioxidant 1098.

[0119] The raw materials of the intermediate layer include the following components by weight fraction: ethylene-methyl acrylate copolymer (EMA) 65 parts, organic acid 8 parts, ethylene-methyl acrylate-glycidyl methacrylate terpolymer (EMA-GMA) 27 parts. The EMA brand is Optema TC 121, and the melt index is 65 g / 10 min (190℃ / 2.16 kg); the organic acid is selected as malic acid, and the CAS number is 6915-15-7; the GMA content of the EMA-GMA is 3wt%, and the brand is Japan Sumitomo BF-7L.

[0120] The raw materials of the second adhesive layer are hot melt adhesive particles VB550 (Guangzhou Lushan New Materials Co., Ltd.).

[0121] Example 12

[0122] This example refers to the water-resistant boiling hot melt adhesive film and the preparation method thereof of Example 1, except that the components and amounts of each layer and the thicknesses are different.

[0123] In this example, the thickness of the first adhesive layer is 0.05 mm, the thickness of the intermediate layer is 0.03 mm, and the thickness of the second adhesive layer is 0.04 mm.

[0124] The raw materials of the first adhesive layer include the following components by weight fraction: polyester TPU particles 65 parts, epoxy resin 29 parts, tannic acid 6 parts, antioxidant 0.2 parts. The melting point of the polyester TPU particles is 110-120℃, the melt index is 45g / 10min (190℃ / 2.16kg), and it is purchased from Wanhua Chemical Group Co., Ltd., with the brand name WHT-6232B; the epoxy resin is bisphenol A type epoxy resin E-35, with an epoxy value of 0.35 eq / 100g; the tannic acid has a CAS number of 1401-55-4; and the antioxidant is antioxidant TPP.

[0125] The raw materials of the intermediate layer include the following components by weight fraction: ethylene-methyl acrylate copolymer (EMA) 75 parts, organic acid 6 parts, ethylene-methyl acrylate-glycidyl methacrylate terpolymer (EMA-GMA) 19 parts. The EMA has a brand name of Optema TC 114, with a melt index of 3.2g / 10min (190℃ / 2.16kg); the organic acid is citric acid, with a CAS number of 77-92-9; and the EMA-GMA has a GMA content of 6wt%, with a brand name of Japan Sumitomo BF-7M.

[0126] The raw materials of the second adhesive layer are hot melt adhesive particles VB770 (Guangzhou Lushan New Materials Co., Ltd.).

[0127] Example 13

[0128] This example refers to the water-resistant boiling hot melt adhesive film and the preparation method thereof of Example 1, except that the components and amounts of each layer and the thicknesses are different.

[0129] In this example, the thickness of the first adhesive layer is 0.02 mm, the thickness of the intermediate layer is 0.01 mm, and the thickness of the second adhesive layer is 0.01 mm.

[0130] The raw materials of the first adhesive layer include the following components in parts by weight: polyester TPU particles 75 parts, epoxy resin 23 parts, tannic acid 2 parts, antioxidant 0.4 part. The polyester TPU particles have a melting point of 145-155℃ and a melt index of 35g / 10min (190℃ / 2.16kg), and are purchased from Zhejiang Huafeng Thermoplastic Polyurethane Co., Ltd. with the trade name of WHT-6235B; the epoxy resin is bisphenol A type epoxy resin E-20 with an epoxy value of 0.20 eq / 100g; the tannic acid has a CAS number of 1401-55-4; and the antioxidant is antioxidant TNP.

[0131] The raw materials of the intermediate layer include the following components in parts by weight: ethylene-methyl acrylate copolymer (EMA) 85 parts, organic acid 5 parts, ethylene-methyl acrylate-glycidyl methacrylate terpolymer (EMA-GMA) 10 parts. The EMA has a trade name of Optema TC 120 and a melt index of 6g / 10min (190℃ / 2.16kg); the organic acid is citric acid with a CAS number of 77-92-9; and the EMA-GMA has a GMA content of 6wt% and a trade name of Japan Sumitomo BF-7M.

[0132] The raw materials of the second adhesive layer are hot melt adhesive particles VB770 (Guangzhou Lushan New Materials Co., Ltd.).

[0133] Example 14

[0134] This example refers to the water-resistant hot melt adhesive film of Example 1 and the preparation method thereof, with the difference that the components and amounts of the layers and the thicknesses are different.

[0135] In this example, the thickness of the first adhesive layer is 0.03mm, the thickness of the intermediate layer is 0.02mm, and the thickness of the second adhesive layer is 0.02mm.

[0136] The raw materials of the first adhesive layer include the following components in parts by weight: polyester TPU particles 75 parts, epoxy resin 23 parts, tannic acid 2 parts, antioxidant 0.4 part. The polyester TPU particles have a melting point of 145-155℃ and a melt index of 35g / 10min (190℃ / 2.16kg), and are purchased from Zhejiang Huafeng Thermoplastic Polyurethane Co., Ltd. with the trade name of WHT-6235B; the epoxy resin is bisphenol A type epoxy resin E-20 with an epoxy value of 0.20 eq / 100g; the tannic acid has a CAS number of 1401-55-4; and the antioxidant is antioxidant TNP.

[0137] The raw materials of the intermediate layer include the following components by weight fraction: ethylene-methyl acrylate copolymer (EMA) 60 parts, organic acid 9 parts, ethylene-methyl acrylate-glycidyl methacrylate terpolymer (EMA-GMA) 31 parts. The EMA brand is Optema TC 110, and the melt index is 2 g / 10 min (190℃ / 2.16 kg); the organic acid is selected as citric acid, and the CAS number is 77-92-9; the GMA content of EMA-GMA is 3wt%, and the brand is Japan Sumitomo BF-7L.

[0138] The raw materials of the second adhesive layer are hot melt adhesive particles VB530 (Guangzhou Lushan New Materials Co., Ltd.).

[0139] Comparative Example 1

[0140] Comparative Example 1 refers to the water-boiling-resistant hot melt adhesive film and the preparation method thereof of Example 1, and the difference lies in that the component amounts of the first adhesive layer are different.

[0141] In Comparative Example 1, the raw materials of the first adhesive layer are polyester TPU particles; the raw materials of the intermediate layer are ethylene-methyl acrylate copolymer (EMA); and the raw materials of the second adhesive layer are hot melt adhesive particles VB550.

[0142] Comparative Example 2

[0143] Comparative Example 2 refers to the water-boiling-resistant hot melt adhesive film and the preparation method thereof of Example 1, and the difference lies in that the component amounts of the first adhesive layer are different.

[0144] In Comparative Example 2, the raw materials of the first adhesive layer include the following components by weight fraction: polyester TPU particles 98 parts, tannic acid 2 parts, and antioxidant 0.3 parts.

[0145] Comparative Example 3

[0146] Comparative Example 3 refers to the water-boiling-resistant hot melt adhesive film and the preparation method thereof of Example 1, and the difference lies in that the component amounts of the first adhesive layer are different.

[0147] In Comparative Example 3, the raw materials of the first adhesive layer include the following components by weight fraction: polyester TPU particles 80 parts, epoxy resin 18 parts, and antioxidant 0.3 parts.

[0148] Comparative Example 4

[0149] Comparative Example 4 refers to the water-boiling-resistant hot melt adhesive film and the preparation method thereof of Example 1, and the difference lies in that the component amounts of the intermediate layer are different.

[0150] In Comparative Example 4, the raw materials of the intermediate layer include the following components by weight fraction: ethylene-methyl acrylate copolymer (EMA) 75 parts, and ethylene-methyl acrylate-glycidyl methacrylate terpolymer (EMA-GMA) 25 parts.

[0151] Comparative Example 5

[0152] Comparative Example 5 refers to the water boiling resistant hot melt adhesive film and the preparation method thereof of Example 1, except that the component amount of the intermediate layer is different.

[0153] In Comparative Example 5, the raw materials of the intermediate layer include the following components by weight fraction: ethylene-methyl acrylate copolymer (EMA) 95 parts, organic acid 5 parts.

[0154] Experimental Example

[0155] The hot melt adhesive films obtained in each example and comparative example are compounded with PVC waterproofing membrane and galvanized sheet, and the compounding process is as follows: the PVC waterproofing membrane is first pre-stuck with the first adhesive layer of the hot melt adhesive film, and then the second adhesive layer of the hot melt adhesive film is stuck on the heated galvanized sheet, wherein the compounding temperature is 170°C, the compounding time is 20s, and the compounding pressure is 0.2MPa, to obtain the adhesive structure of PVC waterproofing membrane / first adhesive layer / intermediate layer / second adhesive layer / galvanized sheet, and the 180° room temperature peeling strength and water boiling resistance of the adhesive structure are investigated, and the test results are shown in Table 1. Among them, the 180° room temperature peeling strength refers to the 180° peeling strength test after cooling to room temperature after compounding is completed; the water boiling resistance refers to the 180° peeling strength test after cooling to room temperature after the adhesive structure of PVC waterproofing membrane / first adhesive layer / intermediate layer / second adhesive layer / galvanized sheet is placed in water for boiling (temperature is 100°C, time is 4h), and then the sample is taken out after boiling, and then cooled to room temperature.

[0156] Table 1 180° room temperature peeling strength and water boiling resistance test results of different adhesive structures

[0157] As can be seen from the test results of Comparative Example 1 and Comparative Examples 1-5, the addition of epoxy resin can greatly improve the hydrolysis resistance of polyester TPU, and the crosslinked network formed by epoxy resin, tannic acid and organic acid greatly improves the adhesion strength of the first adhesive layer and the intermediate layer and the water boiling resistance between the layers; EMA-GMA improves the compatibility between EMA and organic acid, and improves the adhesion strength of the intermediate layer and the second adhesive layer and the water boiling resistance between the layers.

[0158] As can be seen from the examples of the present application, the hot melt adhesive film prepared by the preferred formula of the present application has a peeling strength of more than 135N / 25mm after compounding with PVC waterproofing membrane and galvanized sheet, and the peeling strength retention rate after water boiling for 4h is higher than 90%, which shows that the hot melt adhesive film of the present application has excellent peeling strength and water boiling resistance. Moreover, the preparation process of the hot melt adhesive film of the present application is simple, and can be produced continuously, which can greatly promote the outdoor application of PVC waterproofing membrane.

[0159] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application, and are not intended to limit the same; although the present application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that they can still modify the technical solutions recorded in the foregoing embodiments, or make equivalent replacements for part or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present application.

Claims

1. A water-boiling resistant hot melt adhesive film, comprising a first adhesive layer, an intermediate layer and a second adhesive layer sequentially attached; the first adhesive layer comprises, by weight fraction, 60-90 parts of polyester TPU particles, 10-40 parts of an epoxy resin, 1-6 parts of tannic acid and 0.05-1 parts of an antioxidant; the intermediate layer comprises, by weight fraction, 60-90 parts of an ethylene-methyl acrylate copolymer, 1-10 parts of a multifunctional organic acid and 5-35 parts of an ethylene-methyl acrylate-glycidyl methacrylate terpolymer; the second adhesive layer comprises a polyolefin adhesive resin.

2. The water-resistant boil hot melt adhesive film according to claim 1, wherein, The epoxy resin has an epoxy value of 0.1-0.5 eq / 100 g.

3. The water-resistant boil hot melt adhesive film according to claim 1, wherein, The polyester TPU particles have a melting point of 100-160℃ and a melt index of 15-50 g / 10 min under a test condition of 190℃, 2.16 kg.

4. The water-resistant boil hot melt adhesive film according to claim 1, wherein, The multifunctional organic acid comprises at least one of malic acid and citric acid.

5. The water-resistant boil hot melt adhesive film according to claim 1, wherein, The mass ratio of the epoxy resin to the tannic acid is (3-15) :

1.

6. The water-resistant boil hot melt adhesive film according to claim 1, wherein, In the ethylene-methyl acrylate-glycidyl methacrylate terpolymer, the content of GMA blocks is 3wt%-6wt%.

7. The water-resistant boil hot melt adhesive film according to claim 1, wherein, The mass ratio of the multifunctional organic acid to GMA in the ethylene-methyl acrylate-glycidyl methacrylate terpolymer is 1 : (0.06-0.36).

8. The water-resistant boil hot melt adhesive film according to claim 1, wherein, The polyolefin adhesive resin is grafted with polar groups, which include maleic anhydride and / or carboxyl groups; In the polyolefin adhesive resin, the grafting rate of polar groups is 0.1%-1.5%. 9.A method for preparing the water-boiling resistant hot melt adhesive film according to any one of claims 1-8, comprising the following steps: multilayer co-extrusion blowing or casting the first adhesive layer raw material, the intermediate layer raw material and the second adhesive layer raw material to obtain the water-boiling resistant hot melt adhesive film.

10. A composite structure comprising a PVC waterproofing membrane, a water- resistant boil-resistant hot-melt adhesive film and a metal layer sequentially attached, wherein, The water-boiling resistant hot melt adhesive film is the water-boiling resistant hot melt adhesive film according to any one of claims 1-8 or prepared by the method according to claim 9.

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