Polyolefin weather-resistant adhesive film as well as preparation method and application thereof

Abstract

The invention relates to the technical field of polymer composite films, in particular to a polyolefin weather-resistant adhesive film as well as a preparation method and application thereof. The polyolefin weather-resistant adhesive film comprises a protective layer, a weather-resistant layer, a barrier layer, a matrix layer and an adhesive layer which are sequentially laminated, the protective layer comprises PET resin, PETG resin and an anti-blocking agent; the weather-proof layer comprises a thermoplastic polyolefin elastomer, an antioxidant, a light stabilizer, an acid acceptor and a color master batch; the blocking layer comprises a polyolefin elastomer, an ultraviolet blocking filler, an antioxidant and a light stabilizer; the matrix layer comprises matrix resin; the adhesive layer includes a polyolefin adhesive resin grafted with maleic anhydride. According to the adhesive film disclosed by the invention, by arranging a multi-layer structure and adjusting the composition of each layer, the adhesive film has the advantages of wide composite process window, good lasting adhesive property, good weather resistance and good acid and alkali corrosion resistance.

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 object of the present invention is to provide a polyolefin weather-resistant adhesive film, its preparation method and application. The polyolefin weather-resistant adhesive film of the present invention has good mechanical properties, lasting interfacial adhesion 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] To achieve the above object of the present invention, in the first aspect, the present invention provides a polyolefin weather-resistant adhesive film, which comprises a protective layer, a weather-resistant layer, a barrier layer, a matrix layer and an adhesive layer that are sequentially laminated; The protective layer comprises the following components by weight parts: 65-85 parts of PET resin, 15-35 parts of PETG resin and 0.05-0.3 part of an antiblocking agent; The weather-resistant layer comprises the following components by weight parts: 85-98 parts of a thermoplastic polyolefin elastomer, 0.1-3 parts of an antioxidant, 0.1-3 parts of a light stabilizer, 0.1-3 parts of an acid absorbent and 0-10 parts of a color masterbatch; The barrier layer comprises the following components by weight parts: 85-99 parts of a polyolefin elastomer, 1-15 parts of an ultraviolet barrier filler, 0.1-3 parts of an antioxidant and 0.1-3 parts of a light stabilizer; The matrix layer comprises a matrix resin; The adhesive layer comprises a polyolefin adhesive resin grafted with maleic anhydride.

[0009] In a specific embodiment of the present invention, the thickness of the protective layer is 6-10 μm.

[0010] In a specific embodiment of the present invention, the thickness ratio of the protective layer, the weather-resistant layer, the barrier layer, the matrix layer and the adhesive layer is 1﹕(3-5)﹕(3-5)﹕(2-6)﹕(2-4).

[0011] In a specific embodiment of the present invention, the thickness of the polyolefin weather-resistant adhesive film is 0.1-0.3 mm.

[0012] In a specific embodiment of the present invention, the melting point of the PET resin is 230-250 °C.

[0013] In a specific embodiment of the present invention, the melting point of the PETG resin is 180-210 °C.

[0014] In a specific embodiment of the present invention, the antiblocking agent comprises silica and / or oleic acid amide.

[0015] In a specific embodiment of the present invention, the melt index (230 °C, 2.16 kg) of the thermoplastic polyolefin elastomer is 0.5-1.5 g / 10 min, and the melting point is 140-165 °C.

[0016] 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.

[0017] In a specific embodiment of the present invention, the polyolefin elastomer comprises a first polyolefin elastomer and a second polyolefin elastomer in a mass ratio of 1﹕(1.5 - 2.5); the melt index (190 °C, 2.16 kg) of the first polyolefin elastomer is 1 to 2.5 g / 10 min; the melt index (190 °C, 2.16 kg) of the second polyolefin elastomer is 3.5 to 5 g / 10 min.

[0018] In a specific embodiment of the present invention, the matrix resin is selected from polyethylene resins. Further, the matrix resin comprises LLDPE and LDPE in a mass ratio of (2 - 2.5)﹕1.

[0019] 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.

[0020] In a specific embodiment of the present invention, the acid absorbent comprises at least one of aluminum hydroxide, calcium stearate, and magnesium hydroxide.

[0021] In a specific embodiment of the present invention, the ultraviolet barrier filler comprises at least one of zinc oxide, magnesium oxide, and titanium dioxide.

[0022] In a specific embodiment of the present invention, the polyolefin weather-resistant adhesive film is integrally formed by multi-layer co-extrusion of the raw materials of the protective layer, weather-resistant layer, barrier layer, matrix layer, and adhesive layer.

[0023] 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 raw materials of the protective layer, weather-resistant layer, barrier layer, matrix layer, and adhesive layer to multi-layer co-extrusion casting or blown film to obtain the polyolefin weather-resistant adhesive film.

[0024] The third aspect of the present invention provides the application of the polyolefin weather-resistant adhesive film of the first aspect of the present invention in the field of metal composite building materials.

[0025] Compared with the prior art, the beneficial effects of the present invention are as follows: (1) For the adhesive film of the present invention, through the multi-layer structure setting and adjustment of the composition of each layer, the adhesive film has a wide composite process window, good long-term bonding performance, good weather resistance, and acid and alkali corrosion resistance; (2) The adhesive film of the present invention, through the regulation of the multi-layer structure and the composition of each layer, while ensuring the weather resistance of the film, the thickness of the film is reduced by more than 50% compared with the traditional weather-resistant polyolefin film, significantly reducing the cost. (3) There is good compatibility between the layers of the adhesive film of the present invention. An integrated film can be obtained by means of multi-layer coextrusion casting or blown film, without additional gluing process, simplifying the operation, enabling continuous industrial production, and ensuring the stability of product performance, which is beneficial to its application in the field of metal composite building materials. Specific Embodiments

[0026] The technical solutions of the present invention will be clearly and completely described below in conjunction with specific embodiments. However, those skilled in the art will understand that the following described embodiments are some embodiments of the present invention, rather than all embodiments, and are only used to illustrate the present invention and should not be regarded as limiting the scope of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the scope of protection of the present invention. Those not specified in the embodiments are carried out under conventional conditions or conditions recommended by the manufacturer. Those reagents or instruments not specified by the manufacturer can be obtained as conventional products through commercial purchase.

[0027] The first aspect of the present invention provides a polyolefin weather-resistant adhesive film, which includes a protective layer, a weather-resistant layer, a barrier layer, a matrix layer, and an adhesive layer stacked in sequence. The protective layer includes the following components by weight: 65 - 85 parts of PET resin, 15 - 35 parts of PETG resin, and 0.05 - 0.3 parts of an antiblocking agent. The weather-resistant layer includes the following components by weight: 85 - 98 parts of a thermoplastic polyolefin elastomer, 0.1 - 3 parts of an antioxidant, 0.1 - 3 parts of a light stabilizer, 0.1 - 3 parts of an acid absorbent, and 0 - 10 parts of a color masterbatch. The barrier layer includes the following components by weight: 85 - 99 parts of a polyolefin elastomer, 1 - 15 parts of an ultraviolet barrier filler, 0.1 - 3 parts of an antioxidant, and 0.1 - 3 parts of a light stabilizer. The matrix layer includes a matrix resin. The adhesive layer includes a polyolefin adhesive resin grafted with maleic anhydride.

[0028] The adhesive film of the present invention, through the multi-layer structure setting and the adjustment of the composition of each layer, enables the film to have a wide composite process window, good persistent adhesion performance, good weather resistance, and acid and alkali corrosion resistance. The adhesive film of the present invention can be firmly adhered to a metal substrate by means of high-temperature thermal lamination, and there is no VOC emission during lamination and use.

[0029] Specifically, in the adhesive film of the present invention, a protective layer composed of a compound of PET resin, PETG resin and an antiblocking agent is provided, which has scratch resistance, temperature resistance and good processing performance, can prevent problems such as film breakage and scratching during the thermal lamination process, and can be easily peeled off after slitting, solving the problem of the narrow composite process window of the current polyolefin film. For example, in different embodiments, in the protective layer, by weight, the dosages of PET resin, PETG resin and the antiblocking agent can be respectively as follows: the dosage of PET resin can be 65 parts, 70 parts, 75 parts, 80 parts, 85 parts or the range composed of any two of them; the dosage of PETG resin can be 15 parts, 20 parts, 25 parts, 30 parts, 35 parts or the range composed of any two of them; the dosage of the antiblocking agent can be 0.05 parts, 0.1 parts, 0.15 parts, 0.2 parts, 0.25 parts, 0.3 parts or the range composed of any two of them; thus, it is more beneficial to balance the improvement of the composite process window of the adhesive film and the compatibility between layers.

[0030] In the weather-resistant layer, by weight, the dosages of each component can be respectively as follows: the dosage of the thermoplastic polyolefin elastomer can be 85 parts, 88 parts, 90 parts, 92 parts, 95 parts, 98 parts or the range composed of any two of them; the dosage of the antioxidant can be 0.1 part, 0.5 part, 1 part, 2 parts, 3 parts or the range composed of any two of them; the dosage of the light stabilizer can be 0.1 part, 0.5 part, 1 part, 2 parts, 3 parts or the range composed of any two of them; the dosage of the acid absorbent can be 0.1 part, 0.5 part, 1 part, 2 parts, 3 parts or the range composed of any two of them; the dosage of the color masterbatch can be 0 part, 2 parts, 5 parts, 8 parts, 10 parts or the range composed of any two of them, and the color masterbatch can be selected according to the actual color requirements of the film material. The setting of the types and dosages of each component in the weather-resistant layer helps to improve the weather resistance, acid and alkali corrosion resistance, etc. of the adhesive film.

[0031] In the barrier layer, by weight, the dosages of each component can be respectively as follows: the dosage of the polyolefin elastomer can be 85 parts, 88 parts, 90 parts, 92 parts, 95 parts, 99 parts or the range composed of any two of them; the dosage of the ultraviolet barrier filler can be 1 part, 3 part, 5 parts, 8 parts, 10 parts, 12 parts, 15 parts or the range composed of any two of them; the dosage of the antioxidant can be 0.1 part, 0.5 part, 1 part, 2 parts, 3 parts or the range composed of any two of them; the dosage of the light stabilizer can be 0.1 part, 0.5 part, 1 part, 2 parts, 3 parts or the range composed of any two of them. The setting of the types and dosages of each component in the barrier layer, on the one hand, improves the ultraviolet barrier property, etc. of the adhesive film, and on the other hand, balances the processing performance of the barrier layer and plays a role of connection and transition between the weather-resistant layer and the substrate layer, ensuring the overall processing performance and mechanical properties of the film.

[0032] The grafted polyolefin adhesive resin used in the adhesive layer can form a stable bond with the metal through surface chemical coordination bonds, and there is no VOC emission during use, which is more reliable and environmentally friendly than traditional adhesives.

[0033] Moreover, the present invention regulates the composition of each layer so that there is good compatibility between the layers. An integrated adhesive film can be obtained by means of multi-layer coextrusion casting or multi-layer coextrusion blowing, without additional gluing processes. The polyolefin weather-resistant adhesive film of the present invention can be set in different colors according to actual needs and has a good decorative effect when applied to roofs or exterior walls, providing a new solution for the protection of metal structure building roofs, curtain walls, etc.

[0034] In a specific embodiment of the present invention, the thickness of the protective layer is 6-10 μm. When the thickness of the protective layer is too small, the temperature resistance and protective effect on the adhesive film are not obvious; when the thickness of the protective layer is too large, it is not conducive to cost control.

[0035] In a specific embodiment of the present invention, the thickness ratio of the protective layer, weather-resistant layer, barrier layer, matrix layer and adhesive layer is 1:(3-5):(3-5):(2-6):(2-4).

[0036] For example, in different embodiments, the thickness ratio of the protective layer to the weather-resistant layer can be 1:3, 1:3.5, 1:4, 1:4.5, 1:5 or the range composed of any two of them; 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 the range composed of any two of them; the thickness ratio of the protective layer to the matrix layer can be 1:2, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:6 or the range composed of any two of them; 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 the range composed of any two of them. By regulating the thickness of each layer to meet the above conditions, a good balance can be achieved among mechanical properties, weather resistance, bonding reliability and cost control.

[0037] 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 the range composed of any two of them.

[0038] 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.

[0039] 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 composed of any two of them.

[0040] 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.

[0041] 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 composed of any two of them.

[0042] In a specific embodiment of the present invention, the antiblocking agent includes silica and / or oleic acid amide. Further, the particle size of the antiblocking agent is 3 - 8μm, and for example, it can be 3μm, 4μm, 5μm, 6μm, 7μm, 8μm, or a range composed of any two of them.

[0043] In a specific embodiment of the present invention, the melt index (230°C, 2.16 kg) of the thermoplastic polyolefin elastomer is 0.5 - 1.5 g / 10 min, and the melting point is 140 - 165°C. 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 composed of any two of them.

[0044] 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.

[0045] In a specific embodiment of the present invention, the melt index (190°C, 2.16 kg) of the polyolefin elastomer is 1 - 5 g / 10 min. 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 composed of any two of them.

[0046] In a specific embodiment of the present invention, the polyolefin elastomer is selected from at least one of Dow VERSIFY 2300, Dow VERSIFY3401, Dow VERSIFY 3200, ExxonMobil Vistamaxx 3000, and ExxonMobil Vistamaxx 6000.

[0047] In a specific embodiment of the present invention, the polyolefin elastomer comprises a first polyolefin elastomer and a second polyolefin elastomer with a mass ratio of 1﹕(1.5 - 2.5); the melt index (190 °C, 2.16 kg) of the first polyolefin elastomer is 1 - 2.5 g / 10 min, and the melt index (190 °C, 2.16 kg) of the second polyolefin elastomer is 3.5 - 5 g / 10 min.

[0048] In a specific embodiment of the present invention, the first polyolefin elastomer comprises at least one of Dow VERSIFY 2300 and Dow VERSIFY 3401, and the second polyolefin elastomer comprises at least one of ExxonMobil Vistamaxx 3000 and ExxonMobil Vistamaxx 6000. In different 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 composed of any two of them, which is more conducive to achieving a good transition between the weather-resistant layer and the substrate layer and improving the overall processing performance and mechanical properties of the adhesive film.

[0049] In a specific embodiment of the present invention, the matrix resin is selected from polyethylene resins. Further, the matrix resin comprises LLDPE and LDPE with a mass ratio of (2 - 2.5)﹕1. In different embodiments, in the matrix resin, the mass ratio of LLDPE to LDPE can be 2﹕1, 2.1﹕1, 2.2﹕1, 2.3﹕1, 2.4﹕1, 2.5﹕1 or a range composed of any two of them. The combination of the two is more beneficial to balancing the strength and processing performance of the adhesive film.

[0050] In a specific embodiment of the present invention, the LLDPE is selected from Guangzhou Petrochemical 7042 and Yangzi Petrochemical 7050H; the LDPE is selected from CNOOC Shell 2420H and CNOOC Shell 2426H.

[0051] In a specific embodiment of the present invention, the melt index (190 °C, 2.16 kg) of the polyolefin adhesive resin grafted with maleic anhydride is 2 - 10 g / 10 min, and the Vicat softening point is 65 - 85 °C.

[0052] In different embodiments, the melt index of the polyolefin adhesive resin grafted with maleic anhydride can be 2 g / 10 min, 4 g / 10 min, 6 g / 10 min, 8 g / 10 min, 10 g / 10 min or a range composed of any two of them, and the Vicat softening point can be 65 °C, 70 °C, 75 °C, 80 °C, 85 °C or a range composed of any two of them.

[0053] 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.

[0054] In a specific embodiment of the present invention, the acid absorbent includes at least one of aluminum hydroxide, calcium stearate, and magnesium hydroxide. Further, the particle size of the acid absorbent is 0.3 - 1.5 μm, for example, it can be 0.3 μm, 0.5 μm, 0.8 μm, 1 μm, 1.2 μm, 1.5 μm, or the range composed of any two of them.

[0055] In a specific embodiment of the present invention, the ultraviolet barrier filler includes at least one of zinc oxide, magnesium oxide, and titanium dioxide. Further, the particle size of the ultraviolet barrier filler is 0.2 - 0.5 μm, for example, it can be 0.2 μm, 0.25 μm, 0.3 μm, 0.35 μm, 0.4 μm, 0.45 μm, 0.5 μm, or the range composed of any two of them.

[0056] 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.

[0057] 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.

[0058] In a specific embodiment of the present invention, the polyolefin weather-resistant adhesive film is integrally formed by multi-layer co-extrusion of the raw materials of the protective layer, weather-resistant layer, barrier layer, matrix layer, and adhesive layer.

[0059] The second aspect of the present invention provides a preparation method of the polyolefin weather-resistant adhesive film of the first aspect of the present invention, including the following steps: subjecting the raw materials of the protective layer, weather-resistant layer, barrier layer, matrix layer, and adhesive layer to multi-layer co-extrusion casting or blown film to obtain the polyolefin weather-resistant adhesive film.

[0060] In a specific embodiment of the present invention, the preparation of the raw materials of the protective layer, weather-resistant layer, barrier layer, and matrix layer includes: mixing and melt-extruding and pelletizing respectively according to the composition ratios of the protective layer, weather-resistant layer, barrier layer, and matrix layer to obtain the raw materials of the protective layer, weather-resistant layer, barrier layer, and matrix layer.

[0061] In the specific embodiments of the present invention, in the preparation of the raw materials for the protective layer, weather-resistant layer, barrier layer, and matrix layer, a twin-screw extruder is used for melt extrusion granulation. Further, the melt extrusion temperature is 180 - 260 °C, the screw rotation speed is 300 - 350 rpm, the feeding speed is 5 - 7 Hz, and the aspect ratio of the twin-screw is (36 - 44):1.

[0062] In the specific embodiments of the present invention, multi-layer co-extrusion is carried out using a multi-layer co-extrusion casting machine or a multi-layer co-extrusion blown film machine. Further, the multi-layer co-extrusion processing temperature is 130 - 260 °C.

[0063] The third aspect of the present invention provides the application of the polyolefin weather-resistant adhesive film of the first aspect of the present invention in the field of metal composite building materials.

[0064] Among them, the metal composite building materials include but are not limited to metal-structured building roofs, curtain walls, etc.

[0065] Example 1 This example provides a polyolefin weather-resistant adhesive film, which includes a protective layer, a weather-resistant layer, a barrier layer, a matrix layer, and an adhesive layer stacked in sequence from top to bottom, and the thicknesses of each layer are 0.01 mm, 0.04 mm, 0.04 mm, 0.03 mm, and 0.02 mm in sequence.

[0066] The protective layer includes the following components by weight: 65 parts of Yizheng Chemical Fiber SH701, 35 parts of Eastman AP007, and 0.1 part of oleic acid amide (average particle size of 5 μm).

[0067] The weather-resistant layer includes the following components by weight: 96 parts of LyondellBasell Adflex C 200F, 0.4 part of antioxidant 1010, 0.2 part of antioxidant 168, 0.4 part of antioxidant 264, 0.7 part of light stabilizer UV-622, 0.3 part of light stabilizer UV-326, and 2 parts of magnesium hydroxide (average particle size of 1 μm).

[0068] The barrier layer includes the following components by weight: 35 parts of Dow VERSIFY 2300, 54 parts of ExxonMobil Vistamaxx 3000, 10 parts of titanium dioxide (average particle size of 0.4 μm), 0.4 part of antioxidant 1010, 0.2 part of antioxidant 168, and 0.4 part of light stabilizer UV-622.

[0069] The matrix layer includes the following components by weight: 70 parts of Guangzhou Petrochemical 7042 and 30 parts of CNOOC Shell 2420H.

[0070] The adhesive layer is Guangzhou Lushan adhesive resin TP101, with a melt index of 3.5 g / 10 min and a Vicat softening point of 75 °C.

[0071] The preparation method of the polyolefin weather-resistant adhesive film of this embodiment includes the following steps: (1) Mix the raw materials required for the protective layer, weather-resistant layer, barrier layer, and matrix layer evenly by a high-speed mixer according to their respective ratios, and then extrude and pelletize them through a twin-screw extruder to obtain the protective layer pellets, weather-resistant layer pellets, barrier layer pellets, and matrix layer pellets respectively; among them, the extrusion temperature of the twin-screw extruder for the protective layer pellets is 260 °C, and the extrusion temperatures of the twin-screw extruders for the weather-resistant layer pellets, barrier layer pellets, and matrix layer pellets are 190 °C, the screw speed is 300 rpm, the feeding speed is 7 Hz, and the ratio of the length to the diameter of the twin-screw is L﹕D = 40﹕1.

[0072] (2) Obtain the polyolefin weather-resistant adhesive film by means of multi-layer co-extrusion casting with the protective layer pellets, weather-resistant layer pellets, barrier layer pellets, matrix layer pellets, and adhesive layer pellets; among them, during multi-layer co-extrusion casting, the processing temperatures corresponding to the protective layer, weather-resistant layer, barrier layer, matrix layer, adhesive layer, and die head are 260 °C, 230 °C, 230 °C, 230 °C, 180 °C, and 260 °C respectively.

[0073] Example 2 This embodiment refers to the polyolefin weather-resistant adhesive film and its preparation method of Example 1, the difference is only that the thicknesses of the protective layer, weather-resistant layer, barrier layer, matrix layer, and adhesive layer are different.

[0074] 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 matrix layer is 0.036 mm, and the thickness of the adhesive layer is 0.02 mm.

[0075] Example 3 This embodiment refers to the polyolefin weather-resistant adhesive film and its preparation method of Example 1, the difference is only that the thicknesses of the protective layer, weather-resistant layer, barrier layer, matrix layer, and adhesive layer are different.

[0076] 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 matrix layer is 0.05 mm, and the thickness of the adhesive layer is 0.02 mm.

[0077] Example 4 This embodiment refers to the polyolefin weather-resistant adhesive film and its preparation method of Example 1, the difference is only that the thicknesses of the protective layer, weather-resistant layer, barrier layer, matrix layer, and adhesive layer are different.

[0078] 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 matrix layer is 0.05 mm, and the thickness of the adhesive layer is 0.02 mm.

[0079] Example 5 This embodiment refers to the polyolefin weather-resistant adhesive film and its preparation method of Example 1, with the only difference being that the thicknesses of the protective layer, weather-resistant layer, barrier layer, matrix layer, and adhesive layer are different.

[0080] 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 matrix layer is 0.04 mm, and the thickness of the adhesive layer is 0.01 mm.

[0081] Example 6 This embodiment refers to the polyolefin weather-resistant adhesive film and its preparation method of Example 1, with the only difference being that the composition of the protective layer is different.

[0082] In the polyolefin weather-resistant adhesive film of this embodiment, the protective layer includes the following components by weight: 85 parts of Yizheng Chemical Fiber SH701, 15 parts of Eastman AP007, and 0.1 part of oleic acid amide. [[ID=S18]]

[0083] Example 7 This embodiment refers to the polyolefin weather-resistant adhesive film and its preparation method of Example 1, with the only difference being that the composition of the barrier layer is different.

[0084] In the polyolefin weather-resistant adhesive film of this embodiment, the barrier layer includes the following components by weight: 41 parts of Dow VERSIFY 2300, 48 parts of ExxonMobil Vistamaxx 3000, 10 parts of titanium dioxide, 0.4 part of antioxidant 1010, 0.2 part of antioxidant 168, and 0.4 part of light stabilizer UV-622.

[0085] Example 8 This embodiment refers to the polyolefin weather-resistant adhesive film and its preparation method of Example 1, with the only difference being that the composition of the barrier layer is different.

[0086] In the polyolefin weather-resistant adhesive film of this embodiment, the barrier layer includes the following components by weight: 26 parts of Dow VERSIFY 2300, 63 parts of ExxonMobil Vistamaxx 3000, 10 parts of titanium dioxide, 0.4 part of antioxidant 1010, 0.2 part of antioxidant 168, and 0.4 part of light stabilizer UV-622.

[0087] Example 9 This example refers to the polyolefin weather-resistant adhesive film and its preparation method in Example 1, with the only difference being the composition of the barrier layer.

[0088] In the polyolefin weather-resistant adhesive film of this example, the barrier layer includes the following components by weight: 89 parts of ExxonMobil Vistamaxx 3000, 10 parts of titanium dioxide, 0.4 part of antioxidant 1010, 0.2 part of antioxidant 168, and 0.4 part of light stabilizer UV-622.

[0089] Example 10 This example refers to the polyolefin weather-resistant adhesive film and its preparation method in Example 1, with the only difference being the composition of the matrix layer.

[0090] In the polyolefin weather-resistant adhesive film of this example, the matrix layer is Guangzhou Petrochemical 7042.

[0091] Example 11 This example refers to the polyolefin weather-resistant adhesive film and its preparation method in Example 1, with the only difference being the composition of the adhesive layer.

[0092] In the polyolefin weather-resistant adhesive film of this example, 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.

[0093] Comparative Example 1 Comparative Example 1 refers to the polyolefin weather-resistant adhesive film and its preparation method in Example 1, with the difference being that it does not include a protective layer and the thickness of the matrix layer is different.

[0094] The thickness of the matrix layer in Comparative Example 1 is 0.04 mm.

[0095] Comparative Example 2 Comparative Example 2 refers to the polyolefin weather-resistant adhesive film and its preparation method in Example 1, with the difference being that it does not include a weather-resistant layer and the thickness of the matrix layer is different.

[0096] The thickness of the matrix layer in Comparative Example 2 is 0.07 mm.

[0097] Comparative Example 3 Comparative Example 3 refers to the polyolefin weather-resistant adhesive film and its preparation method in Example 1, with the difference being that it does not include a barrier layer and the thickness of the matrix layer is different.

[0098] The thickness of the matrix layer in Comparative Example 3 is 0.07 mm.

[0099] Comparative Example 4 Comparative Example 4 refers to the polyolefin weather-resistant adhesive film and its preparation method in Example 1, with the difference being that it does not include an adhesive layer and the thickness of the matrix layer is different.

[0100] The thickness of the substrate layer in Comparative Example 4 is 0.05 mm.

[0101] Comparative Example 5 Comparative Example 5 refers to the polyolefin weather-resistant adhesive film and its preparation method in Example 1, except that the composition of the protective layer is different.

[0102] In the polyolefin weather-resistant adhesive film of Comparative Example 5, the protective layer includes the following components by weight: 100 parts of Yizheng Chemical Fiber SH701 and 0.1 part of oleamide.

[0103] Comparative Example 6 Comparative Example 6 refers to the polyolefin weather-resistant adhesive film and its preparation method in Example 1, except that the composition of the weather-resistant layer is different.

[0104] In the polyolefin weather-resistant adhesive film of Comparative Example 6, the weather-resistant layer includes the following components by weight: 96 parts of Guangzhou Petrochemical 7042, 0.4 part of antioxidant 1010, 0.2 part of antioxidant 168, 0.4 part of antioxidant 264, 0.7 part of light stabilizer UV-622, 0.3 part of light stabilizer UV-326, and 2 parts of magnesium hydroxide.

[0105] Comparative Example 7 Comparative Example 7 refers to the polyolefin weather-resistant adhesive film and its preparation method in Example 1, except that the composition of the barrier layer is different.

[0106] In the polyolefin weather-resistant adhesive film of Comparative Example 7, the barrier layer includes the following components by weight: 89 parts of Guangzhou Petrochemical 7042, 10 parts of titanium dioxide, 0.4 part of antioxidant 1010, 0.2 part of antioxidant 168, and 0.4 part of light stabilizer UV-622.

[0107] Experimental Example Perform performance tests on the polyolefin weather-resistant adhesive films of different examples and comparative examples. The specific test items are as follows, and the test results are shown in Table 1.

[0108] Mechanical property test: The tensile strength and elongation at break are carried out according to Method B in GB / T 328.9-2007; the tensile speed is 100 mm / min.

[0109] Preparation of the composite metal structure: From top to bottom, sequentially laminate in the structure of "polyolefin weather-resistant adhesive film / galvanized steel sheet" in an end-to-end alignment manner, and then heat and press for lamination on a flat vulcanizer. The lamination temperature is 150 °C, the pressure is 0.3 MPa, and the time is 5 s. After lamination is completed, remove the protective layer to obtain the composite metal structure (if there is no protective layer, there is no need to remove the protective layer).

[0110] Appearance of the adhesive film and composite metal structure: Observe whether there are abnormal phenomena such as deformation and scratching on the appearance of the adhesive film and after the adhesive film is composite.

[0111] Peel strength test: Use the composite metal structure as the sample and test according to the standard of GB / T 2790-1995, with a peel speed of 100 mm / min.

[0112] Appearance of artificial climate accelerated aging: Use the composite metal structure as the sample and test according to the standard of GB / T 18244-2022. The cumulative radiation energy at a wavelength of 340 nm should not be less than 5100 kJ / (m 2 ·nm), and the total xenon lamp aging time is 6000 h; observe whether there are delamination, powdering, peeling, and falling off phenomena every 500 h.

[0113] Table 1 Performance test results of different adhesive films

[0114] It can be seen from the above test results that the polyolefin weather-resistant adhesive film of the present invention, through the multi-layer structure setting and the regulation of the composition of each layer, makes the layers have good compatibility. An integrated adhesive film can be obtained by the multi-layer coextrusion casting or multi-layer coextrusion blowing method, meeting the functions of high-temperature resistance composite, weather resistance, adhesion, etc.

[0115] Comparing Example 1 with Comparative Example 1, it can be seen that when the protective layer is not provided in the adhesive film, the temperature resistance performance of the adhesive film will be seriously affected. Comparing Example 1 with Comparative Example 2, it can be seen that when the weather-resistant layer is not provided in the adhesive film, the weather resistance performance of the film material will be seriously affected. Comparing Example 1 with Comparative Example 3, it can be seen that when the barrier layer is not provided in the adhesive film, the weather resistance performance of the adhesive film will be affected, and at the same time, the protection effect on the adhesive layer will be affected, resulting in phenomena such as falling off. Comparing Example 1 with Comparative Example 4, it can be seen that when the adhesive layer is not provided in the adhesive film, it cannot be bonded to the galvanized sheet. Comparing Example 1 with 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 adhesive film will be seriously affected, thereby affecting the mechanical properties of the adhesive film, and the adhesive film has a large thickness deviation and wrinkles. Comparing Example 1 with Comparative Example 6, it can be seen that when the weather-resistant layer does not use thermoplastic polyolefin elastomer, the weather resistance performance of the adhesive film will be seriously affected. Comparing Example 1 with Comparative Example 7, it can be seen that when the barrier layer does not use polyolefin elastomer, the barrier layer cannot realize the connection between the weather-resistant layer and the matrix layer, resulting in a significant decline in the weather resistance performance, mechanical properties, etc. of the product, and delamination will occur after aging.

[0116] 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 them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements on some or all of the technical features; and 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 matrix layer, and an adhesive layer which are sequentially laminated; The protective layer includes the following components by weight: 65-85 parts of PET resin, 15-35 parts of PETG resin, and 0.05-0.3 parts of an antiblocking agent; The weather-resistant layer includes the following components by weight: 85-98 parts of a thermoplastic polyolefin elastomer, 0.1-3 parts of an antioxidant, 0.1-3 parts of a light stabilizer, 0.1-3 parts of an acid absorbent, and 0-10 parts of a color masterbatch; The barrier layer includes the following components by weight: 85-99 parts of a polyolefin elastomer, 1-15 parts of an ultraviolet barrier filler, 0.1-3 parts of an antioxidant, and 0.1-3 parts of a light stabilizer; The matrix layer includes a matrix resin; The adhesive layer includes a polyolefin adhesive resin grafted with maleic anhydride.

2. The polyolefin weather-resistant adhesive film according to claim 1, characterized in that, It has at least one of the following characteristics: (1) The thickness of the protective layer is 6-10 μm; (2) The thickness ratio of the protective layer, the weather-resistant layer, the barrier layer, the matrix layer, and the adhesive layer is 1﹕(3-5)﹕(3-5)﹕(2-6)﹕(2-4); (3) The thickness of the polyolefin weather-resistant adhesive film is 0.1-0.3 mm.

3. The polyolefin weather-resistant adhesive film according to claim 1, wherein 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 antiblocking agent includes silica and / or oleic acid amide.

4. The polyolefin weather-resistant adhesive film according to claim 1, wherein The thermoplastic polyolefin elastomer has at least one of the following characteristics: (1) The melt index at 230 °C and 2.16 kg is 0.5-1.5 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, The polyolefin elastomer includes a first polyolefin elastomer and a second polyolefin elastomer with a mass ratio of 1﹕(1.5-2.5); the melt index of the first polyolefin elastomer at 190 °C and 2.16 kg is 1-2.5 g / 10 min; the melt index of the second polyolefin elastomer at 190 °C and 2.16 kg is 3.5-5 g / 10 min.

6. The polyolefin weather-resistant adhesive film according to claim 1, wherein The matrix resin includes LLDPE and LDPE with a mass ratio of (2-2.5)﹕1.

7. 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 2-10 g / 10 min; (2) The Vicat softening point is 65-85 °C.

8. The polyolefin weather-resistant adhesive film according to claim 1, wherein It has at least one of the following characteristics: (1) The acid absorbent includes at least one of aluminum hydroxide, calcium stearate, and magnesium hydroxide; (2) The ultraviolet barrier 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 the raw materials of the protective layer, the weather-resistant layer, the barrier layer, the matrix layer, and the adhesive layer.

9. The preparation method of the polyolefin weather-resistant adhesive film according to any one of claims 1 to 8, characterized in that, It includes the following steps: multi-layer co-extrusion casting or blown film of the raw materials of the protective layer, the weather-resistant layer, the barrier layer, the matrix layer, and the adhesive layer to obtain the polyolefin weather-resistant adhesive film.

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

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