Polyolefin weather-resistant adhesive film and its preparation method and application

Abstract

The present invention relates to the technical field of polymer composite films, and in particular to a polyolefin weather-resistant adhesive film, a preparation method thereof, and an application thereof. The polyolefin weather-resistant adhesive film comprises a protective layer, a weather-resistant layer, a barrier layer, a base layer, and an adhesive layer stacked in sequence; the protective layer comprises PET resin, PETG resin, and an opener; the weather-resistant layer comprises a thermoplastic polyolefin elastomer, an antioxidant, a light stabilizer, an acid absorber, and a masterbatch; the barrier layer comprises a polyolefin elastomer, an ultraviolet barrier filler, an antioxidant, and a light stabilizer; the base layer comprises a base resin; and the adhesive layer comprises a polyolefin adhesive resin grafted with maleic anhydride. The adhesive film of the present invention has a wide composite process window, good long-lasting bonding performance, good weather resistance, and acid and alkali corrosion resistance by setting a multi-layer structure and adjusting the composition of each layer.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer composite films, in particular to a polyolefin weather-resistant adhesive film and a preparation method and application thereof. Background Art

[0002] Metal structures exposed to media such as air and rain for extended periods outdoors are highly susceptible to electrochemical and chemical corrosion. This corrosion not only significantly shortens the building's service life, resulting in significant economic losses, but can also pose structural safety risks. Furthermore, the metal ions and corrosion products produced during the corrosion process can pollute the environment and accelerate the depletion of limited metal resources. Therefore, the development of new, efficient, and environmentally friendly metal corrosion protection technologies has become a critical and pressing issue in the field of building materials and corrosion protection.

[0003] Polymer coating technology, due to its excellent protective properties and environmental friendliness, is gradually replacing traditional metal paints and powder coatings, becoming a key solution for metal material and building protection. However, in harsh outdoor environments, polymer coating materials must possess higher weather resistance, chemical corrosion resistance, and long-term stable interfacial adhesion to ensure the durability and reliability of their protective effects.

[0004] In the prior art, Chinese patent application publication number CN220615132U proposes a fluorocarbon-coated metal composite panel comprising a fluorocarbon film, a first adhesive layer, an ink layer, a base layer, a second adhesive layer, an aluminum alloy layer, a third adhesive layer, a metal base layer, a fourth adhesive layer, and a backing film layer. This structural design imparts high weather resistance, decorative properties, and protective properties to the metal composite panel. Chinese patent application publication number CN118082315A proposes a film-coated metal panel comprising a polymer layer, an adhesive layer, and a metal layer stacked in sequence. The polymer layer comprises a surface layer, a middle layer, a glass fiber reinforced layer, and a bottom layer stacked in sequence. Roofs formed using this film-coated metal panel exhibit excellent wind-uplift resistance and durability.

[0005] However, existing solutions still face several key challenges that need to be addressed: First, the layers of these solutions require adhesive or hot-melt lamination, preventing the film from being formed into an integrated form. This not only complicates the production process but also severely restricts the implementation of continuous production. Second, during the high-temperature lamination process, the film material generally suffers from insufficient mechanical strength, prone to defects such as breakage and scratching, which significantly narrows the process parameter window. Furthermore, existing solutions often struggle to balance performance and cost. These issues have severely restricted the large-scale application of polymer coating technology in the field of metal protection.

[0006] In view of this, the present invention is proposed. Summary of the Invention

[0007] The purpose of the present invention is to provide a polyolefin weather-resistant adhesive film, a preparation method and an application thereof. The polyolefin weather-resistant adhesive film of the present invention has good mechanical properties, long-lasting interface bonding strength, and good weather resistance, etc., and can be applied to the field of metal composite building materials, which helps to improve the durability and environmental adaptability of metal composite building materials.

[0008] In order to achieve the above-mentioned object of the present invention, the first aspect of the present invention provides a polyolefin weather-resistant adhesive film, comprising a protective layer, a weather-resistant layer, a barrier layer, a base layer and an adhesive layer stacked in sequence;

[0009] The protective layer comprises the following components by weight: 65-85 parts of PET resin, 15-35 parts of PETG resin and 0.05-0.3 parts of opening agent;

[0010] The weather-resistant layer comprises the following components by weight: 85-98 parts of thermoplastic polyolefin elastomer, 0.1-3 parts of antioxidant, 0.1-3 parts of light stabilizer, 0.1-3 parts of acid absorbent and 0-10 parts of color masterbatch;

[0011] The barrier layer comprises the following components in parts by weight: 85-99 parts of polyolefin elastomer, 1-15 parts of UV barrier filler, 0.1-3 parts of antioxidant and 0.1-3 parts of light stabilizer;

[0012] The base layer includes a base resin;

[0013] The adhesive layer includes a polyolefin adhesive resin grafted with maleic anhydride.

[0014] In a specific embodiment of the present invention, the thickness of the protective layer is 6 to 10 μm.

[0015] In a specific embodiment of the present invention, the thickness ratio of the protective layer, the weather-resistant layer, the barrier layer, the base layer and the adhesive layer is 1: (3-5): (3-5): (2-6): (2-4).

[0016] In a specific embodiment of the present invention, the thickness of the polyolefin weather-resistant adhesive film is 0.1 to 0.3 mm.

[0017] In a specific embodiment of the present invention, the melting point of the PET resin is 230-250°C.

[0018] In a specific embodiment of the present invention, the melting point of the PETG resin is 180-210°C.

[0019] In a specific embodiment of the present invention, the opening agent includes silicon dioxide and / or oleamide.

[0020] In a specific embodiment of the present invention, the thermoplastic polyolefin elastomer has a melt index (230°C, 2.16 kg) of 0.5 to 1.5 g / 10 min and a melting point of 140 to 165°C.

[0021] In a specific embodiment of the present invention, the melt index (190° C., 2.16 kg) of the polyolefin elastomer is 1 to 5 g / 10 min.

[0022] In a specific embodiment of the present invention, the polyolefin elastomer includes a first polyolefin elastomer and a second polyolefin elastomer in a mass ratio of 1:(1.5-2.5); the melt index (190°C, 2.16kg) of the first polyolefin elastomer is 1-2.5g / 10min; the melt index (190°C, 2.16kg) of the second polyolefin elastomer is 3.5-5g / 10min.

[0023] In a specific embodiment of the present invention, the matrix resin is selected from polyethylene resin. Further, the matrix resin comprises LLDPE and LDPE in a mass ratio of (2-2.5) : 1.

[0024] In a specific embodiment of the present invention, the polyolefin adhesive resin grafted with maleic anhydride has a melt index (190°C, 2.16 kg) of 2 to 10 g / 10 min and a Vicat softening point of 65 to 85°C.

[0025] In a specific embodiment of the present invention, the acid scavenger includes at least one of aluminum hydroxide, calcium stearate and magnesium hydroxide.

[0026] In a specific embodiment of the present invention, the UV blocking filler includes at least one of zinc oxide, magnesium oxide and titanium dioxide.

[0027] In a specific embodiment of the present invention, the polyolefin weather-resistant adhesive film is integrally formed by multi-layer co-extrusion of raw materials of a protective layer, a weather-resistant layer, a barrier layer, a base layer and an adhesive layer.

[0028] The second aspect of the present invention provides a method for preparing the polyolefin weather-resistant adhesive film of the first aspect of the present invention, comprising the following steps: subjecting the protective layer raw material, weather-resistant layer raw material, barrier layer raw material, base layer raw material and adhesive layer raw material to multi-layer co-extrusion casting or film blowing to obtain the polyolefin weather-resistant adhesive film.

[0029] The third aspect of the present invention provides the use of the polyolefin weather-resistant adhesive film of the first aspect of the present invention in the field of metal composite building materials.

[0030] Compared with the prior art, the present invention has the following beneficial effects:

[0031] (1) The adhesive film of the present invention has a wide composite process window, good long-lasting bonding performance, good weather resistance and acid and alkali corrosion resistance by setting a multi-layer structure and adjusting the composition of each layer;

[0032] (2) The adhesive film of the present invention, through the regulation of the multi-layer structure and the composition of each layer, reduces the thickness of the adhesive film by more than 50% compared with the traditional weather-resistant polyolefin film while ensuring the weather resistance of the adhesive film, thereby significantly reducing the cost;

[0033] (3) The various layers of the adhesive film of the present invention have good compatibility with each other, and an integrated film can be obtained by multi-layer co-extrusion casting or blown film, without the need for additional gluing process, which simplifies the operation, enables continuous industrial production, and ensures the stability of product performance, which is conducive to its application in the field of metal composite building materials. DETAILED DESCRIPTION

[0034] The technical scheme of the present invention will be clearly and completely described below in conjunction with specific embodiments, but it will be understood by those skilled in the art that the following described embodiments are part of embodiments of the present invention, rather than all embodiments, and are only used to illustrate the present invention, and should not be considered as limiting the scope of the present invention. Based on the embodiments in the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative work premise belong to the scope of protection of the present invention. Those who do not specify specific conditions in the embodiments are carried out according to normal conditions or the conditions recommended by the manufacturer. Those whose reagents or instruments are not specified by the manufacturer are conventional products that can be purchased commercially.

[0035] The first aspect of the present invention provides a polyolefin weather-resistant adhesive film, comprising a protective layer, a weather-resistant layer, a barrier layer, a base layer and an adhesive layer stacked in sequence;

[0036] The protective layer comprises the following components in parts by weight: 65-85 parts of PET resin, 15-35 parts of PETG resin and 0.05-0.3 parts of opening agent;

[0037] The weather-resistant layer comprises the following components in parts by weight: 85-98 parts of thermoplastic polyolefin elastomer, 0.1-3 parts of antioxidant, 0.1-3 parts of light stabilizer, 0.1-3 parts of acid absorbent and 0-10 parts of color masterbatch;

[0038] The barrier layer comprises the following components in parts by weight: 85 to 99 parts of a polyolefin elastomer, 1 to 15 parts of a UV barrier filler, 0.1 to 3 parts of an antioxidant, and 0.1 to 3 parts of a light stabilizer;

[0039] The base layer includes a base resin;

[0040] The adhesive layer includes a polyolefin adhesive resin grafted with maleic anhydride.

[0041] The adhesive film of the present invention utilizes a multi-layer structure and tailored composition of each layer to achieve a wide lamination process window, excellent long-lasting bonding performance, and superior weather resistance and acid and alkali corrosion resistance. The adhesive film of the present invention can be securely bonded to metal substrates through high-temperature thermal lamination, and emits no VOCs during lamination or use.

[0042] Specifically, the adhesive film of the present invention includes a protective layer comprising a composite of PET resin, PETG resin, and an opening agent. The protective layer exhibits scratch resistance, heat resistance, and excellent processing properties, preventing film breakage and scratching during the thermal lamination process. Furthermore, the film can be easily removed after opening, thereby resolving the current narrow lamination process window for polyolefin films. For example, in various embodiments, the amounts of PET resin, PETG resin, and opening agent in the protective layer, by weight, may be as follows: PET resin may be in an amount of 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, or a range consisting of any two thereof; PETG resin may be in an amount of 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, or a range consisting of any two thereof; and the opening agent may be in an amount of 0.05 parts, 0.1 parts, 0.15 parts, 0.2 parts, 0.25 parts, 0.3 parts, or a range consisting of any two thereof. This improves both the lamination process window of the adhesive film and the compatibility between the layers.

[0043] In the weather-resistant layer, the amounts of each component, calculated by weight, can be as follows: the thermoplastic polyolefin elastomer can be 85 parts, 88 parts, 90 parts, 92 parts, 95 parts, 98 parts, or a range consisting of any two thereof; the antioxidant can be 0.1 part, 0.5 part, 1 part, 2 parts, 3 parts, or a range consisting of any two thereof; the light stabilizer can be 0.1 part, 0.5 part, 1 part, 2 parts, 3 parts, or a range consisting of any two thereof; the acid scavenger can be 0.1 part, 0.5 part, 1 part, 2 parts, 3 parts, or a range consisting of any two thereof; the color masterbatch can be 0 part, 2 parts, 5 parts, 8 parts, 10 parts, or a range consisting of any two thereof. The color masterbatch can be selected based on the actual color requirements of the film material. The type and amount of each component in the weather-resistant layer help improve the weather resistance and acid and alkali corrosion resistance of the adhesive film.

[0044] In the barrier layer, the amounts of each component, measured by weight, can be as follows: the polyolefin elastomer can be 85 parts, 88 parts, 90 parts, 92 parts, 95 parts, 99 parts, or any combination thereof; the UV-blocking filler can be 1 part, 3 parts, 5 parts, 8 parts, 10 parts, 12 parts, 15 parts, or any combination thereof; the antioxidant can be 0.1 part, 0.5 part, 1 part, 2 parts, 3 parts, or any combination thereof; and the light stabilizer can be 0.1 part, 0.5 part, 1 part, 2 parts, 3 parts, or any combination thereof. The types and amounts of each component in the barrier layer are designed to improve the UV-blocking properties of the adhesive film while also taking into account the barrier layer's processing performance and its role as a transitional connection between the weathering layer and the substrate layer, ensuring the overall processing and mechanical properties of the film.

[0045] The polyolefin adhesive resin grafted with maleic anhydride used in the adhesive layer can form a stable bond with the metal through surface chemical coordination bonds, and has no VOC emissions during use. It is more reliable and environmentally friendly than traditional adhesives.

[0046] Furthermore, the present invention regulates the composition of each layer to ensure good compatibility between them. This allows for the production of an integrated film through multi-layer co-extrusion cast or blown film production, eliminating the need for additional gluing processes. The polyolefin weather-resistant adhesive film of the present invention can be configured in various colors to meet specific needs, offering a decorative effect when applied to roofs or exterior walls, providing a novel solution for protecting metal roofs, curtain walls, and other structures.

[0047] In a specific embodiment of the present invention, the thickness of the protective layer is 6 to 10 μm. If the thickness of the protective layer is too small, the temperature resistance and protective effect of the adhesive film are not obvious; if the thickness of the protective layer is too large, it is not conducive to cost control.

[0048] In a specific embodiment of the present invention, the thickness ratio of the protective layer, the weather-resistant layer, the barrier layer, the base layer and the adhesive layer is 1: (3-5): (3-5): (2-6): (2-4).

[0049] For example, in different embodiments, the thickness ratio of the protective layer to the weathering layer can be 1:3, 1:3.5, 1:4, 1:4.5, 1:5, or a range consisting of any two thereof; the thickness ratio of the protective layer to the barrier layer can be 1:3, 1:3.5, 1:4, 1:4.5, 1:5, or a range consisting of any two thereof; the thickness ratio of the protective layer to the base layer can be 1:2, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:6, or a range consisting of any two thereof; and the thickness ratio of the protective layer to the adhesive layer can be 1:2, 1:2.5, 1:3, 1:3.5, 1:4, or a range consisting of any two thereof. By adjusting the thickness of each layer to meet the above conditions, a good balance can be achieved between mechanical properties, weathering resistance, bonding reliability, and cost control.

[0050] In a specific embodiment of the present invention, the thickness of the polyolefin weather-resistant adhesive film is 0.1-0.3 mm, for example, it can be 0.1 mm, 0.15 mm, 0.2 mm, 0.25 mm, 0.3 mm or a range consisting of any two thereof.

[0051] In a specific embodiment of the present invention, the melting point of the PET resin is 230-250° C. For example, the PET resin includes at least one of Yizheng Chemical Fiber SH701, Yizheng Chemical Fiber FG702, and Yizheng Chemical Fiber BG804.

[0052] For example, in different embodiments, the melting point of the PET resin of the present invention can be 230° C., 235° C., 240° C., 245° C., 250° C., or a range consisting of any two thereof.

[0053] In a specific embodiment of the present invention, the melting point of the PETG resin is 180-210° C. For example, the PETG resin includes at least one of Eastman AP007 and Eastman TX1001.

[0054] For example, in different embodiments, the melting point of the PETG resin of the present invention can be 180° C., 185° C., 190° C., 195° C., 200° C., 205° C., 210° C., or a range consisting of any two thereof.

[0055] In a specific embodiment of the present invention, the opening agent includes silicon dioxide and / or oleamide. Further, the particle size of the opening agent is 3 to 8 μm, for example, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm or any combination thereof.

[0056] In a specific embodiment of the present invention, the thermoplastic polyolefin elastomer has a melt index (230°C, 2.16 kg) of 0.5 to 1.5 g / 10 min, and a melting point of 140 to 165°C. For example, in different embodiments, the melt index of the thermoplastic polyolefin elastomer can be 0.5 g / 10 min, 0.8 g / 10 min, 1 g / 10 min, 1.2 g / 10 min, 1.5 g / 10 min, or a range consisting of any two thereof.

[0057] In a specific embodiment of the present invention, the thermoplastic polyolefin elastomer includes at least one of LyondellBasell Hifax CA10A, LyondellBasell Adflex Q 100F, and LyondellBasell Adflex C 200F.

[0058] In a specific embodiment of the present invention, the melt index (190°C, 2.16 kg) of the polyolefin elastomer is 1 to 5 g / 10 min. For example, in different embodiments, the melt index of the polyolefin elastomer can be 1 g / 10 min, 2 g / 10 min, 3 g / 10 min, 4 g / 10 min, 5 g / 10 min, or a range consisting of any two thereof.

[0059] In a specific embodiment of the present invention, the polyolefin elastomer is at least one selected from Dow VERSIFY 2300, Dow VERSIFY 3401, Dow VERSIFY 3200, Exxon Vistamaxx 3000 and Exxon Vistamaxx 6000.

[0060] In a specific embodiment of the present invention, the polyolefin elastomer includes a first polyolefin elastomer and a second polyolefin elastomer in a mass ratio of 1: (1.5 to 2.5); the melt index (190°C, 2.16 kg) of the first polyolefin elastomer is 1 to 2.5 g / 10 min, and the melt index (190°C, 2.16 kg) of the second polyolefin elastomer is 3.5 to 5 g / 10 min.

[0061] In a specific embodiment of the present invention, the first polyolefin elastomer includes at least one of Dow VERSIFY 2300 and Dow VERSIFY 3401, and the second polyolefin elastomer includes at least one of Exxon Vistamaxx 3000 and Exxon Vistamaxx 6000. In various embodiments, the mass ratio of the first polyolefin elastomer to the second polyolefin elastomer can be 1:1.5, 1:1.8, 1:2, 1:2.2, 1:2.5, or a range consisting of any two thereof. This helps achieve a good transition between the weather-resistant layer and the base layer, improving the overall processing performance and mechanical properties of the film.

[0062] In a specific embodiment of the present invention, the base resin is selected from polyethylene resin. Furthermore, the base resin comprises LLDPE and LDPE in a mass ratio of (2-2.5) : 1. For example, in various embodiments, the mass ratio of LLDPE to LDPE in the base resin can be 2:1, 2.1:1, 2.2:1, 2.3:1, 2.4:1, 2.5:1, or any combination thereof. A combination of the two improves the balance between the strength and processing properties of the adhesive film.

[0063] In a specific embodiment of the present invention, LLDPE is selected from Guangzhou Petrochemical 7042 and Yangzi Petrochemical 7050H; LDPE is selected from CNOOC Shell 2420H and CNOOC Shell 2426H.

[0064] In a specific embodiment of the present invention, the polyolefin adhesive resin grafted with maleic anhydride has a melt index (190° C., 2.16 kg) of 2 to 10 g / 10 min and a Vicat softening point of 65 to 85° C.

[0065] For example, in different embodiments, the polyolefin adhesive resin grafted with maleic anhydride can have a melt index of 2 g / 10 min, 4 g / 10 min, 6 g / 10 min, 8 g / 10 min, 10 g / 10 min, or a range consisting of any two thereof, and a Vicat softening point of 65°C, 70°C, 75°C, 80°C, 85°C, or a range consisting of any two thereof.

[0066] In a specific embodiment of the present invention, the polyolefin adhesive resin grafted with maleic anhydride is selected from at least one of Guangzhou Lushan TP101, Guangzhou Lushan VB770 and Guangzhou Lushan VB790.

[0067] In a specific embodiment of the present invention, the acid scavenger includes at least one of aluminum hydroxide, calcium stearate, and magnesium hydroxide. Furthermore, the particle size of the acid scavenger is 0.3 to 1.5 μm, for example, 0.3 μm, 0.5 μm, 0.8 μm, 1 μm, 1.2 μm, 1.5 μm, or any combination thereof.

[0068] In a specific embodiment of the present invention, the UV blocking filler includes at least one of zinc oxide, magnesium oxide, and titanium dioxide. Furthermore, the particle size of the UV blocking filler is 0.2 to 0.5 μm, for example, 0.2 μm, 0.25 μm, 0.3 μm, 0.35 μm, 0.4 μm, 0.45 μm, 0.5 μm, or any combination thereof.

[0069] In a specific embodiment of the present invention, the antioxidants in the weather-resistant layer and the barrier layer can be independently selected from at least one of antioxidant 1010, antioxidant 1076, antioxidant 1024, antioxidant 168, antioxidant 264 and antioxidant 245.

[0070] In a specific embodiment of the present invention, the light stabilizers in the weather-resistant layer and the barrier layer can be independently selected from at least one of hindered amine light stabilizers, benzophenone light stabilizers and benzotriazole light stabilizers.

[0071] In a specific embodiment of the present invention, the polyolefin weather-resistant adhesive film is integrally formed by multi-layer co-extrusion of raw materials of a protective layer, a weather-resistant layer, a barrier layer, a base layer and an adhesive layer.

[0072] The second aspect of the present invention provides a method for preparing the polyolefin weather-resistant adhesive film of the first aspect of the present invention, comprising the following steps: subjecting the protective layer raw material, weather-resistant layer raw material, barrier layer raw material, base layer raw material and adhesive layer raw material to multi-layer co-extrusion casting or film blowing to obtain a polyolefin weather-resistant adhesive film.

[0073] In a specific embodiment of the present invention, the preparation of the protective layer raw material, the weather-resistant layer raw material, the barrier layer raw material, and the base layer raw material includes: mixing and melt-extruding and granulating according to the composition ratio of the protective layer, the weather-resistant layer, the barrier layer, and the base layer, to obtain the protective layer raw material, the weather-resistant layer raw material, the barrier layer raw material, and the base layer raw material.

[0074] In a specific embodiment of the present invention, the protective layer raw materials, weathering layer raw materials, barrier layer raw materials, and base layer raw materials are prepared by melt extrusion granulation using a twin-screw extruder. Furthermore, the melt extrusion temperature is 180-260°C, the screw speed is 300-350 rpm, the feed rate is 5-7 Hz, and the twin-screw aspect ratio is (36-44):1.

[0075] In a specific embodiment of the present invention, a multi-layer co-extrusion casting machine or a multi-layer co-extrusion film blowing machine is used for multi-layer co-extrusion. Furthermore, the multi-layer co-extrusion processing temperature is 130-260°C.

[0076] The third aspect of the present invention provides the use of the polyolefin weather-resistant adhesive film of the first aspect of the present invention in the field of metal composite building materials.

[0077] Among them, metal composite building materials include but are not limited to metal structure building roofs, curtain walls, etc.

[0078] Example 1

[0079] This embodiment provides a polyolefin weather-resistant adhesive film, including a protective layer, a weather-resistant layer, a barrier layer, a base layer and an adhesive layer stacked in sequence from top to bottom, with the thickness of each layer being 0.01 mm, 0.04 mm, 0.04 mm, 0.03 mm and 0.02 mm, respectively.

[0080] The protective layer includes the following components in parts by weight: 65 parts of Yizheng Chemical Fiber SH701, 35 parts of Eastman AP007, and 0.1 part of oleamide (with an average particle size of 5 μm).

[0081] The weather-resistant layer includes the following components in parts by weight: 96 parts of LyondellBasell Adflex C 200F, 0.4 parts of antioxidant 1010, 0.2 parts of antioxidant 168, 0.4 parts of antioxidant 264, 0.7 parts of light stabilizer UV-622, 0.3 parts of light stabilizer UV-326, and 2 parts of magnesium hydroxide (average particle size of 1 μm).

[0082] The barrier layer includes the following components in parts by weight: 35 parts of Dow VERSIFY 2300, 54 parts of Exxon Vistamaxx 3000, 10 parts of titanium dioxide (average particle size of 0.4 μm), 0.4 parts of antioxidant 1010, 0.2 parts of antioxidant 168, and 0.4 parts of light stabilizer UV-622.

[0083] The matrix layer includes the following components by weight: 70 parts of Guangzhou Petrochemical 7042 and 30 parts of CNOOC Shell 2420H.

[0084] The bonding layer is Guangzhou Lushan bonding resin TP101, with a melt index of 3.5g / 10min and a Vicat softening point of 75°C.

[0085] The method for preparing the polyolefin weather-resistant adhesive film of this embodiment includes the following steps:

[0086] (1) The raw materials required for the protective layer, weather-resistant layer, barrier layer and base layer are mixed uniformly in their respective proportions through a high-speed mixer, and then extruded and granulated through a twin-screw extruder to obtain protective layer pellets, weather-resistant layer pellets, barrier layer pellets and base layer pellets respectively; wherein, the extrusion temperature of the twin-screw extruder for the protective layer pellets is 260°C, the extrusion temperature of the twin-screw extruder for the weather-resistant layer pellets, barrier layer pellets and base layer pellets is 190°C, the screw speed is 300rpm, the feeding rate is 7Hz, and the twin-screw aspect ratio L:D=40:1.

[0087] (2) The protective layer pellets, weather-resistant layer pellets, barrier layer pellets, base layer pellets, and adhesive layer pellets are subjected to multi-layer co-extrusion casting to obtain a polyolefin weather-resistant adhesive film; wherein, during the multi-layer co-extrusion casting, the corresponding processing temperatures of the protective layer, weather-resistant layer, barrier layer, base layer, adhesive layer, and die head are 260°C, 230°C, 230°C, 230°C, 180°C, and 260°C, respectively.

[0088] Example 2

[0089] This embodiment refers to the polyolefin weather-resistant adhesive film and preparation method thereof of Example 1, with the only difference being that the thicknesses of the protective layer, weather-resistant layer, barrier layer, base layer, and adhesive layer are different.

[0090] In the polyolefin weather-resistant adhesive film of this embodiment, the thickness of the protective layer is 0.004 mm, the thickness of the weather-resistant layer is 0.04 mm, the thickness of the barrier layer is 0.04 mm, the thickness of the base layer is 0.036 mm, and the thickness of the adhesive layer is 0.02 mm.

[0091] Example 3

[0092] This embodiment refers to the polyolefin weather-resistant adhesive film and preparation method thereof of Example 1, with the only difference being that the thicknesses of the protective layer, weather-resistant layer, barrier layer, base layer, and adhesive layer are different.

[0093] In the polyolefin weather-resistant adhesive film of this embodiment, the thickness of the protective layer is 0.01 mm, the thickness of the weather-resistant layer is 0.02 mm, the thickness of the barrier layer is 0.04 mm, the thickness of the base layer is 0.05 mm, and the thickness of the adhesive layer is 0.02 mm.

[0094] Example 4

[0095] This embodiment refers to the polyolefin weather-resistant adhesive film and preparation method thereof of Example 1, with the only difference being that the thicknesses of the protective layer, weather-resistant layer, barrier layer, base layer, and adhesive layer are different.

[0096] In the polyolefin weather-resistant adhesive film of this embodiment, the thickness of the protective layer is 0.01 mm, the thickness of the weather-resistant layer is 0.04 mm, the thickness of the barrier layer is 0.02 mm, the thickness of the base layer is 0.05 mm, and the thickness of the adhesive layer is 0.02 mm.

[0097] Example 5

[0098] This embodiment refers to the polyolefin weather-resistant adhesive film and preparation method thereof of Example 1, with the only difference being that the thicknesses of the protective layer, weather-resistant layer, barrier layer, base layer, and adhesive layer are different.

[0099] In the polyolefin weather-resistant adhesive film of this embodiment, the thickness of the protective layer is 0.01 mm, the thickness of the weather-resistant layer is 0.04 mm, the thickness of the barrier layer is 0.04 mm, the thickness of the base layer is 0.04 mm, and the thickness of the adhesive layer is 0.01 mm.

[0100] Example 6

[0101] This embodiment refers to the polyolefin weather-resistant adhesive film and preparation method thereof of Example 1, with the only difference being that the composition of the protective layer is different.

[0102] In the polyolefin weather-resistant adhesive film of this embodiment, the protective layer includes the following components in parts by weight: 85 parts of Yizheng Chemical Fiber SH701, 15 parts of Eastman AP007, and 0.1 parts of oleamide.

[0103] Example 7

[0104] This embodiment refers to the polyolefin weather-resistant adhesive film and preparation method thereof of Example 1, with the only difference being that the composition of the barrier layer is different.

[0105] In the polyolefin weather-resistant adhesive film of this embodiment, the barrier layer includes the following components in parts by weight: 41 parts of Dow VERSIFY 2300, 48 parts of Exxon Vistamaxx 3000, 10 parts of titanium dioxide, 0.4 parts of antioxidant 1010, 0.2 parts of antioxidant 168, and 0.4 parts of light stabilizer UV-622.

[0106] Example 8

[0107] This embodiment refers to the polyolefin weather-resistant adhesive film and preparation method thereof of Example 1, with the only difference being that the composition of the barrier layer is different.

[0108] In the polyolefin weather-resistant adhesive film of this embodiment, the barrier layer includes the following components in parts by weight: 26 parts of Dow VERSIFY 2300, 63 parts of Exxon Vistamaxx 3000, 10 parts of titanium dioxide, 0.4 parts of antioxidant 1010, 0.2 parts of antioxidant 168, and 0.4 parts of light stabilizer UV-622.

[0109] Example 9

[0110] This embodiment refers to the polyolefin weather-resistant adhesive film and preparation method thereof of Example 1, with the only difference being that the composition of the barrier layer is different.

[0111] In the polyolefin weather-resistant adhesive film of this embodiment, the barrier layer includes the following components in parts by weight: 89 parts of Exxon Vistamaxx 3000, 10 parts of titanium dioxide, 0.4 parts of antioxidant 1010, 0.2 parts of antioxidant 168, and 0.4 parts of light stabilizer UV-622.

[0112] Example 10

[0113] This embodiment refers to the polyolefin weather-resistant adhesive film and preparation method thereof of Example 1, with the only difference being that the composition of the base layer is different.

[0114] In the polyolefin weather-resistant adhesive film of this embodiment, the base layer is Guangzhou Petrochemical 7042.

[0115] Example 11

[0116] This embodiment refers to the polyolefin weather-resistant adhesive film and preparation method thereof of Example 1, with the only difference being that the composition of the adhesive layer is different.

[0117] In the polyolefin weather-resistant adhesive film of this embodiment, the adhesive layer is Guangzhou Lushan Adhesive Resin VB770, with a melt index of 5 g / 10 min and a Vicat softening point of 69°C.

[0118] Comparative Example 1

[0119] Comparative Example 1 refers to the polyolefin weather-resistant adhesive film and preparation method thereof of Example 1, except that no protective layer is included and the thickness of the base layer is different.

[0120] The thickness of the base layer in Comparative Example 1 was 0.04 mm.

[0121] Comparative Example 2

[0122] Comparative Example 2 refers to the polyolefin weather-resistant adhesive film and preparation method of Example 1, except that the weather-resistant layer is not included and the thickness of the base layer is different.

[0123] The thickness of the base layer in Comparative Example 2 was 0.07 mm.

[0124] Comparative Example 3

[0125] Comparative Example 3 refers to the polyolefin weather-resistant adhesive film and preparation method thereof of Example 1, except that no barrier layer is included and the thickness of the base layer is different.

[0126] The thickness of the base layer in Comparative Example 3 was 0.07 mm.

[0127] Comparative Example 4

[0128] Comparative Example 4 refers to the polyolefin weather-resistant adhesive film and preparation method of Example 1, except that no adhesive layer is included and the thickness of the base layer is different.

[0129] The thickness of the base layer in Comparative Example 4 was 0.05 mm.

[0130] Comparative Example 5

[0131] Comparative Example 5 refers to the polyolefin weather-resistant adhesive film and preparation method thereof of Example 1, except that the composition of the protective layer is different.

[0132] In the polyolefin weather-resistant adhesive film of Comparative Example 5, the protective layer includes the following components in parts by weight: 100 parts of Yizheng Chemical Fiber SH701 and 0.1 parts of oleamide.

[0133] Comparative Example 6

[0134] Comparative Example 6 refers to the polyolefin weather-resistant adhesive film and preparation method of Example 1, except that the composition of the weather-resistant layer is different.

[0135] In the polyolefin weather-resistant adhesive film of Comparative Example 6, the weather-resistant layer includes the following components in parts by weight: 96 parts of Guangzhou Petrochemical 7042, 0.4 parts of antioxidant 1010, 0.2 parts of antioxidant 168, 0.4 parts of antioxidant 264, 0.7 parts of light stabilizer UV-622, 0.3 parts of light stabilizer UV-326, and 2 parts of magnesium hydroxide.

[0136] Comparative Example 7

[0137] Comparative Example 7 refers to the polyolefin weather-resistant adhesive film and preparation method of Example 1, except that the composition of the barrier layer is different.

[0138] In the polyolefin weather-resistant adhesive film of Comparative Example 7, the barrier layer includes the following components in parts by weight: 89 parts of Guangzhou Petrochemical 7042, 10 parts of titanium dioxide, 0.4 parts of antioxidant 1010, 0.2 parts of antioxidant 168, and 0.4 parts of light stabilizer UV-622.

[0139] Experimental example

[0140] The performance tests were conducted on the polyolefin weather-resistant adhesive films of different embodiments and comparative examples. The specific test items are as follows, and the test results are shown in Table 1.

[0141] Mechanical properties test: tensile strength and elongation at break were measured according to method B in GB / T 328.9-2007; the tensile speed was 100 mm / min.

[0142] Preparation of composite metal structure: From top to bottom, the "polyolefin weather-resistant adhesive film / galvanized sheet" structure is sequentially bonded in a top-aligned manner, and then heated and pressurized on a flat-plate vulcanizer. The bonding temperature is 150°C, the pressure is 0.3 MPa, and the time is 5 seconds. After the bonding is completed, the protective layer is peeled off to obtain a composite metal structure (if there is no protective layer, there is no need to peel off the protective layer).

[0143] Appearance of the film and composite metal structure: Observe the appearance of the film and whether there are any abnormal phenomena such as deformation and scratches after the film is composited.

[0144] Peel strength test: Using a composite metal structure as a sample, the test was conducted in accordance with GB / T 2790-1995 standard, with a peeling speed of 100 mm / min.

[0145] Artificial climate accelerated aging appearance: Using composite metal structures as samples, the test was carried out in accordance with GB / T 18244-2022 standard. The cumulative radiation energy at a wavelength of 340nm should not be less than 5100kJ / (m 2 ·nm), the total xenon lamp aging time is 6000h; observe every 500h for delamination, powdering, peeling and shedding.

[0146] Table 1 Performance test results of different adhesive films

[0147]

[0148] From the above test results, it can be seen that the polyolefin weather-resistant adhesive film of the present invention is arranged through a multi-layer structure, and the composition of each layer is regulated so that the layers have good compatibility. An integrated film can be obtained by multi-layer co-extrusion casting or multi-layer co-extrusion blown film method, which meets the functions of high-temperature resistant composite, weather resistance, bonding, etc.

[0149] Comparing Example 1 and Comparative Example 1, it can be seen that when no protective layer is provided in the film, the temperature resistance of the film will be seriously affected. Comparing Example 1 and Comparative Example 2, it can be seen that when no weathering layer is provided in the film, the weathering resistance of the film material will be seriously affected. Comparing Example 1 and Comparative Example 3, it can be seen that when no barrier layer is provided in the film, the weathering resistance of the film will be affected, and the protective effect of the adhesive layer will be affected, resulting in phenomena such as falling off. Comparing Example 1 and Comparative Example 4, it can be seen that when no adhesive layer is provided in the film, it cannot be bonded to the galvanized sheet. Comparing Example 1 and Comparative Example 5, it can be seen that when the protective layer does not use the PETG resin described in the present invention, the processing performance of the film will be seriously affected, and then the mechanical properties of the film will be affected, and the thickness deviation of the film will be large, and there will be wrinkles. Comparing Example 1 and Comparative Example 6, it can be seen that when the weathering layer does not use a thermoplastic polyolefin elastomer, the weathering resistance of the film will be seriously affected. By comparing Example 1 and Comparative Example 7, it can be seen that when the barrier layer does not use polyolefin elastomer, the barrier layer cannot achieve the connection between the weather-resistant layer and the base layer, resulting in a significant decrease in the weather resistance and mechanical properties of the product, and delamination will occur after aging.

[0150] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the above embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. Polyolefin weather-resistant adhesive film, characterized in that: It includes a protective layer, a weather-resistant layer, a barrier layer, a base layer and an adhesive layer stacked in sequence; The protective layer comprises the following components by weight: 65-85 parts of PET resin, 15-35 parts of PETG resin and 0.05-0.3 parts of opening agent; The weather-resistant layer is made of the following components in parts by weight: 85-98 parts of thermoplastic polyolefin elastomer, 0.1-3 parts of antioxidant, 0.1-3 parts of light stabilizer, 0.1-3 parts of acid absorbent and 0-10 parts of color masterbatch; The barrier layer is made of the following components in parts by weight: 85-99 parts of polyolefin elastomer, 1-15 parts of UV barrier filler, 0.1-3 parts of antioxidant and 0.1-3 parts of light stabilizer; The base layer includes a base resin; the base resin includes LLDPE and LDPE in a mass ratio of (2-2.5) : 1; The adhesive layer includes a polyolefin adhesive resin grafted with maleic anhydride; The thickness of the polyolefin weather-resistant adhesive film is 0.1 to 0.3 mm.

2. The polyolefin weather-resistant adhesive film according to claim 1, characterized in that: Has at least one of the following characteristics: (1) The thickness of the protective layer is 6 to 10 μm; (2) The thickness ratio of the protective layer, the weather-resistant layer, the barrier layer, the base layer and the adhesive layer is 1: (3-5): (3-5): (2-6): (2-4).

3. The polyolefin weather-resistant adhesive film according to claim 1, characterized in that: The protective layer has at least one of the following characteristics: (1) The melting point of the PET resin is 230-250°C; (2) The melting point of the PETG resin is 180-210°C; (3) The opening agent includes silicon dioxide and / or oleamide.

4. The polyolefin weather-resistant adhesive film according to claim 1, characterized in that: The thermoplastic polyolefin elastomer has at least one of the following characteristics: (1) The melt index at 230°C and 2.16 kg is 0.5 to 1.5 g / 10 min; (2) The melting point is 140-165°C.

5. The polyolefin weather-resistant adhesive film according to claim 1, characterized in that: In the barrier layer, the polyolefin elastomer includes a first polyolefin elastomer and a second polyolefin elastomer in a mass ratio of 1:(1.5-2.5); the first polyolefin elastomer has a melt index of 1-2.5 g / 10 min at 190° C. and 2.16 kg; the second polyolefin elastomer has a melt index of 3.5-5 g / 10 min at 190° C. and 2.16 kg.

6. The polyolefin weather-resistant adhesive film according to claim 1, characterized in that: The polyolefin adhesive resin grafted with maleic anhydride has at least one of the following characteristics: (1) The melt index at 190°C and 2.16 kg is 2 to 10 g / 10 min; (2) The Vicat softening point is 65-85°C.

7. The polyolefin weather-resistant adhesive film according to claim 1, characterized in that: Has at least one of the following characteristics: (1) The acid scavenger includes at least one of aluminum hydroxide, calcium stearate and magnesium hydroxide; (2) The UV blocking filler includes at least one of zinc oxide, magnesium oxide and titanium dioxide; (3) The polyolefin weather-resistant adhesive film is integrally formed by multi-layer co-extrusion of raw materials of a protective layer, a weather-resistant layer, a barrier layer, a base layer and an adhesive layer.

8. The method for preparing a polyolefin weather-resistant adhesive film according to any one of claims 1 to 7, characterized in that: The method comprises the following steps: performing multi-layer co-extrusion casting or film blowing on raw materials of a protective layer, raw materials of a weather-resistant layer, raw materials of a barrier layer, raw materials of a base layer and raw materials of an adhesive layer to obtain the polyolefin weather-resistant adhesive film.

9. Use of the polyolefin weather-resistant adhesive film according to any one of claims 1 to 7 or the polyolefin weather-resistant adhesive film prepared by the preparation method according to claim 8 in the field of metal composite building materials.

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