Acid-resistant protective film adhesive tape

Abstract

The invention discloses an acid-resistant protective film adhesive tape, and relates to the technical field of protective film adhesive tapes, the acid-resistant protective film adhesive tape comprises a base material layer, a composite adhesive layer and a nano modified release layer, and the composite adhesive layer is located between the base material layer and the nano modified release layer; the composite adhesive layer is prepared from the following raw materials in parts by weight: 40-50 parts of fluorosilicone polyurethane acrylic resin, 3-5 parts of N-(4-cyano-3-trifluoromethylphenyl) methacrylamide, 3-5 parts of (perfluoropropane-2, 2-diyl) bis (4, 4 '-difluoro-1, 3, 4-trimethyl-1, 3, 4-trimethyl-1, 3, 4-trimethyl-1, 3, 4-trimethyl-1, 3, 4-trimethyl-1, 3, 4-trimethyl-1, 3, 4- The invention relates to a UV (ultraviolet) photoinitiator, which is prepared from the following components in parts by weight: 1 to 3 parts of 1, 1-phenylene) diacrylate, 2 to 4 parts of N-vinylcarbazole, 5 to 8 parts of nano silicon dioxide, 1 to 3 parts of coupling agent, 0.8 to 1.2 parts of photoinitiator and 30 to 40 parts of diluent. The acid-resistant protective film adhesive tape has the advantages of excellent acid-resistant effect, good adhesion and no acid liquid pollution, and can effectively make up the segment difference.

Description

Technical Field

[0001] This invention relates to the field of protective film tape technology, and more particularly to an acid-resistant protective film tape. Background Technology

[0002] In many industrial production and product processing processes, such as electronic component manufacturing and glass substrate processing, it is often necessary to protect the surface of materials or products to prevent damage during subsequent processing steps. However, in certain specific environments, such as those involving acid etching or acid cleaning, ordinary protective film tapes are insufficient to meet acid resistance requirements. It is under these circumstances that acid-resistant protective film tapes have emerged, attracting widespread attention within the industry.

[0003] Currently, acid-resistant protective film tapes on the market have significant shortcomings. Some products use a single substrate, making it difficult to balance acid resistance and adhesion performance. In acid etching processes, the edges of the protected material are easily corroded, resulting in a high product scrap rate. Some tapes, although claiming to be acid-resistant, release harmful substances in acid solutions due to unstable adhesive composition, contaminating the processing solution and affecting subsequent processes. At the same time, most tapes have poor adaptability to surface variations of the object being applied to, allowing acid to easily seep into gaps and failing to achieve effective protection.

[0004] To address the aforementioned issues, Chinese invention patent CN103666307B discloses an acid-resistant protective film tape made of PET and CPP composite materials. The tape includes a PET substrate, an acrylic adhesive layer A, a CPP substrate, an acrylic adhesive layer B, and a release film. Acrylic adhesive layer A is positioned above the PET substrate, the upper CPP substrate is positioned above acrylic adhesive layer A, acrylic adhesive layer B is positioned below the PET substrate, and the release film is positioned below acrylic adhesive layer B. The PET substrate is bonded to the CPP substrate via acrylic adhesive layer A, forming a single composite material. The PET substrate is then bonded to the release film via acrylic adhesive layer B. This patent's technical solution effectively combines CPP and PET, with a specially designed and limited thickness to maximize their respective characteristics. This results in a perfect combination of toughness and flexibility, facilitating the coordination of die-cutting and etching processes, improving product yield. The resulting product exhibits good toughness and superior adhesion performance. However, the specific composition of the acrylic adhesive used was not disclosed. Traditional acrylic adhesives have a wide molecular weight distribution and a high Tg, resulting in insufficient flexibility that allows acid to penetrate into the substrate interface. Furthermore, when the degree of cross-linking is low, the adhesive layer is prone to swelling and cracking.

[0005] In view of this, the present invention provides an acid-resistant protective film tape with excellent acid resistance, good adhesion, no acid contamination, and effective compensation for step differences. Summary of the Invention

[0006] The main objective of this invention is to provide an acid-resistant protective film tape with excellent acid resistance, good adhesion, no acid contamination, and the ability to effectively compensate for step differences.

[0007] To achieve the above objectives, the present invention provides an acid-resistant protective film tape, comprising a substrate layer, a composite adhesive layer, and a nano-modified release layer, wherein the composite adhesive layer is located between the substrate layer and the nano-modified release layer; the composite adhesive layer comprises the following raw materials in parts by weight: 40-50 parts of fluorosilicone polyurethane acrylic resin, 3-5 parts of N-(4-cyano-3-trifluoromethylphenyl)methacrylamide, 1-3 parts of (perfluoropropane-2,2-diyl)bis(4,1-phenylene)diacrylate, 2-4 parts of N-vinylcarbazole, 5-8 parts of nano-silica, 1-3 parts of coupling agent, 0.8-1.2 parts of photoinitiator, and 30-40 parts of diluent.

[0008] Preferably, the total thickness of the substrate layer is 100μm-200μm; the thickness of the composite adhesive layer is 15μm-40μm; and the thickness of the nano-modified release layer is 25μm-75μm.

[0009] Preferably, the substrate layer is a multilayer co-extruded modified PBT base film, consisting of an inner layer, a middle layer, and an outer layer from the inside out; the inner layer is a blend of PBT and EVA, wherein the EVA content is 10wt%-20wt%, the compatibilizer content is 2wt%-4wt%, and the thickness is 30-50μm.

[0010] Preferably, the PBT is PBT 4012G RESIN; and the EVA is Hanwha Chemical EVA1828.

[0011] Preferably, the intermediate PBT and nano-montmorillonite composite layer has a nano-montmorillonite content of 5wt%-10wt% and a thickness of 40-80μm; the average particle size of the nano-montmorillonite is 20-50nm.

[0012] Preferably, the outer layer is a PBT and fluoropolymer composite layer, wherein the fluoropolymer content is 8wt%-15wt% and the compatibilizer content is 2wt%-4wt%.

[0013] Preferably, the fluororesin is perfluoroethylene propylene copolymer FEP N3180; and the compatibilizer is Sumitomo BF-7M compatibilizer.

[0014] Preferably, there are no special requirements regarding the source of the fluorosilicone polyurethane acrylic resin. In one embodiment of the present invention, the fluorosilicone polyurethane acrylic resin is prepared according to the method of Example 1 of Chinese Invention Patent No. CN111057203B.

[0015] Preferably, the average particle size of the nano-silica is 10-80 nm.

[0016] Preferably, the coupling agent is at least one of silane coupling agent KH550, silane coupling agent KH560, and silane coupling agent KH570.

[0017] Preferably, the photoinitiator is benzoin ether.

[0018] Preferably, the diluent is a mixture of isooctyl acrylate, methyl methacrylate, and 2-hydroxyethyl acrylate in a mass ratio of 1:(0.8-1.2):1.

[0019] Preferably, the preparation method of the nano-modified release layer includes the following steps: uniformly dispersing nano-titanium dioxide and silane coupling agent KH560 in ethanol, then immersing the PET release film in it at an immersion speed of 2-3 m / min, and drying it at 120°C for 3-5 minutes after removal to obtain the nano-modified release layer.

[0020] Preferably, the mass ratio of the nano-titanium dioxide, silane coupling agent KH560, and ethanol is (5-10):(0.5-0.8):100; and the average particle size of the nano-titanium dioxide is 10-80 nm.

[0021] Another object of the present invention is to provide a method for preparing the acid-resistant protective film tape, comprising the following steps: Step S1, Substrate layer preparation: The inner, middle and outer layer materials are melt-co-extruded using a three-layer co-extrusion equipment, and then shaped after biaxial stretching to obtain the substrate layer; Step S2, Preparation of composite adhesive: After mixing the raw materials of the composite adhesive layer evenly according to the weight parts, the composite adhesive is obtained; Step S3, Composite Molding: Coat the composite adhesive onto the nano-modified release layer at a coating speed of 2-4 m / min, pre-cur it under ultraviolet light with a wavelength of 220-260 nm for 10-15 min, then dry it at 60-70℃ for 3-5 min, and then bond it to the substrate layer by hot pressing. After winding, let it stand at 40℃ for 5 days to obtain the acid-resistant protective film tape.

[0022] Preferably, the hot pressing temperature is 60-80℃ and the pressure is 0.3-0.5MPa.

[0023] Preferably, the temperature of the melt co-extrusion is 230-260°C.

[0024] Due to the application of the above technical solution, the present invention has the following beneficial effects: (1) The method for preparing acid-resistant protective film tape disclosed in this invention has a simple preparation process, convenient operation and control, low dependence on equipment, high preparation efficiency and high finished product qualification rate, and is suitable for continuous large-scale production. It has high promotion and application value.

[0025] (2) The acid-resistant protective film tape disclosed in this invention is composed of a substrate layer, a composite adhesive layer, and a nano-modified release layer, with the composite adhesive layer located between the substrate layer and the nano-modified release layer. The composite adhesive layer is made from the following raw materials in parts by weight: 40-50 parts of fluorosilicone polyurethane acrylic resin, 3-5 parts of N-(4-cyano-3-trifluoromethylphenyl)methacrylamide, 1-3 parts of (perfluoropropane-2,2-diyl)bis(4,1-phenylene)diacrylate, 2-4 parts of N-vinylcarbazole, 5-8 parts of nano-silica, 1-3 parts of coupling agent, 0.8-1.2 parts of photoinitiator, and 30-40 parts of diluent. Through this structure and the synergistic effect of the various raw materials, the resulting tape has excellent acid resistance, good adhesion, no acid contamination, and can effectively compensate for step differences.

[0026] (3) The acid-resistant protective film tape disclosed in this invention uses fluorosilicone polyurethane acrylic resin as the main component, which combines the high chemical resistance of fluorine with the stability of silicon-oxygen bonds. The strong electronegativity of fluorine atoms enables the molecular chain to form a dense water- and acid-repellent layer, while the silicon-oxygen bonds (-Si-O-Si-) construct a three-dimensional network structure through cross-linking, thereby improving the acid penetration resistance of the adhesive layer. The trifluoromethyl group (-CF3) in N-(4-cyano-3-trifluoromethylphenyl)methacrylamide forms a strong polar group with the cyano group (-CN), which inhibits the attack of acid molecules on the ester group through steric hindrance effect, while enhancing the polar interaction with the substrate. The introduction of rigid aromatic rings and perfluoroalkyl chains into (perfluoropropane-2,2-diyl)bis(4,1-phenylene)diacrylate not only improves the heat resistance of the adhesive layer, but also further reduces the acid penetration rate through the synergistic arrangement of fluorine segments. The carbazole ring of N-vinylcarbazole has a large π-conjugated structure, which forms a π-π stacking effect with fluorosilicone resin, enhancing the rigidity of the molecular chain. Its nitrogen atom can form coordination bonds with nano-silica, reducing the aggregation of nanoparticles and enabling the adhesive layer to maintain its mechanical properties in an acidic environment.

[0027] (4) The acid-resistant protective film tape disclosed in this invention uses nano-silica (5-8 parts) modified by a coupling agent to uniformly disperse in the adhesive layer to form physical cross-linking points. This, in conjunction with the chemical cross-linking network initiated by the photoinitiator, enhances the elastic modulus of the adhesive layer after acid etching. The photocuring system (0.8-1.2 parts photoinitiator) can shorten the curing time, and the cured adhesive layer has no small molecule volatiles, avoiding acid contamination. 30-40 parts of diluent, while ensuring coating fluidity, participate in the cross-linking reaction, avoiding the decrease in acid resistance caused by solvent residue in traditional solvent-based adhesives, thus significantly improving the acid resistance of the adhesive layer.

[0028] (5) The acid-resistant protective film tape disclosed in this invention has an inner PBT / EVA blend layer that improves the brittleness of PBT through the flexible segments of EVA, preventing cracking during curved surface bonding and solving the problem of edge warping in traditional rigid substrates. The middle PBT / nano-montmorillonite composite layer utilizes the layered barrier structure of montmorillonite to form a "maze effect" with the crystalline regions of PBT, significantly reducing the permeation rate of hydrofluoric acid and significantly improving acid resistance. The outer PBT / fluororesin composite layer forms an acid-resistant barrier through the enrichment of fluorine segments on the surface, synergistically with the fluorine element in the adhesive layer to construct a "dual acid-resistant protection system," significantly improving the corrosion resistance of the substrate. The flexibility of the inner layer, the barrier properties of the middle layer, and the corrosion resistance of the outer layer complement each other, enabling the substrate to meet the dimensional stability requirements under extreme working conditions. The fluorosilicone groups in the adhesive form a compatible interface with the outer fluororesin of the substrate, and the coupling agent promotes the chemical bonding between the adhesive layer and the substrate, resulting in high peel strength of the tape after acid etching. Meanwhile, the low peel strength of the nano-modified release layer ensures no adhesive residue during use, preventing contamination of the protected object's surface. The nano-modification of the release layer guarantees excellent release performance while avoiding the impact of release agent migration on adhesive properties. Detailed Implementation

[0029] The following description is intended to disclose the invention and enable those skilled in the art to implement it. The preferred embodiments described below are merely examples, and other obvious variations will occur to those skilled in the art. Example 1

[0030] An acid-resistant protective film tape comprises a substrate layer, a composite adhesive layer, and a nano-modified release layer, wherein the composite adhesive layer is located between the substrate layer and the nano-modified release layer; the composite adhesive layer is made of the following raw materials in parts by weight: 40 parts of fluorosilicone polyurethane acrylic resin, 3 parts of N-(4-cyano-3-trifluoromethylphenyl)methacrylamide, 1 part of (perfluoropropane-2,2-diyl)bis(4,1-phenylene)diacrylate, 2 parts of N-vinylcarbazole, 5 parts of nano silica, 1 part of coupling agent, 0.8 parts of photoinitiator, and 30 parts of diluent.

[0031] The total thickness of the substrate layer is 100 μm; the thickness of the composite adhesive layer is 15 μm; and the thickness of the nano-modified release layer is 25 μm.

[0032] The substrate layer is a multilayer co-extruded modified PBT base film, consisting of an inner layer, a middle layer, and an outer layer from the inside out. The inner layer is a blend of PBT and EVA, with EVA content of 10wt%, compatibilizer content of 2wt%, and a thickness of 30μm. The PBT is PBT4012G RESIN, and the EVA is Hanwha Chemical EVA1828. The middle layer is a composite layer of PBT and nano-montmorillonite, with nano-montmorillonite content of 5wt% and a thickness of 40μm. The average particle size of the nano-montmorillonite is 20nm. The outer layer is a composite layer of PBT and fluoropolymer, with fluoropolymer content of 8wt% and compatibilizer content of 2wt%. The fluoropolymer is perfluoroethylene propylene copolymer FEPN3180, and the compatibilizer is Sumitomo BF-7M compatibilizer.

[0033] The fluorosilicone polyurethane acrylic resin is prepared according to the method of Example 1 of Chinese Invention Patent No. CN111057203B; the average particle size of the nano-silica is 10 nm; the coupling agent is silane coupling agent KH550; the photoinitiator is benzoin ether; and the diluent is a mixture of isooctyl acrylate, methyl methacrylate, and 2-hydroxyethyl acrylate in a mass ratio of 1:0.8:1.

[0034] The preparation method of the nano-modified release layer includes the following steps: uniformly dispersing nano-titanium dioxide and silane coupling agent KH560 in ethanol, then immersing a PET release film in it at an immersion speed of 2 m / min, and drying it at 120°C for 3 minutes after removal to obtain the nano-modified release layer; the mass ratio of nano-titanium dioxide, silane coupling agent KH560 and ethanol is 5:0.5:100; the average particle size of the nano-titanium dioxide is 10 nm.

[0035] A method for preparing the acid-resistant protective film tape includes the following steps: Step S1, Substrate layer preparation: The inner, middle and outer layer materials are melt-co-extruded using a three-layer co-extrusion equipment, and then shaped after biaxial stretching to obtain the substrate layer; Step S2, Preparation of composite adhesive: After mixing the raw materials of the composite adhesive layer evenly according to the weight parts, the composite adhesive is obtained; Step S3, Composite Molding: Coat the composite adhesive onto the nano-modified release layer at a coating speed of 2m / min, pre-cur it under ultraviolet light with a wavelength of 220nm for 10min, then dry it at 60℃ for 3min, and then bond it to the substrate layer by hot pressing. After winding, let it stand at 40℃ for 5 days to obtain the acid-resistant protective film tape.

[0036] The hot pressing temperature is 60℃ and the pressure is 0.3MPa; the melt co-extrusion temperature is 230-260℃. Example 2

[0037] An acid-resistant protective film tape comprises a substrate layer, a composite adhesive layer, and a nano-modified release layer, wherein the composite adhesive layer is located between the substrate layer and the nano-modified release layer; the composite adhesive layer is made of the following raw materials in parts by weight: 43 parts of fluorosilicone polyurethane acrylic resin, 3.5 parts of N-(4-cyano-3-trifluoromethylphenyl)methacrylamide, 1.5 parts of (perfluoropropane-2,2-diyl)bis(4,1-phenylene)diacrylate, 2.5 parts of N-vinylcarbazole, 6 parts of nano silica, 1.5 parts of coupling agent, 0.9 parts of photoinitiator, and 33 parts of diluent.

[0038] The total thickness of the substrate layer is 100 μm; the thickness of the composite adhesive layer is 15 μm; and the thickness of the nano-modified release layer is 25 μm.

[0039] The substrate layer is a multilayer co-extruded modified PBT base film, consisting of an inner layer, a middle layer, and an outer layer from the inside out. The inner layer is a blend of PBT and EVA, with EVA content of 13wt%, compatibilizer content of 2.5wt%, and a thickness of 30μm. The PBT is PBT 4012G RESIN, and the EVA is Hanwha Chemical EVA1828. The middle layer is a composite layer of PBT and nano-montmorillonite, with nano-montmorillonite content of 6wt% and a thickness of 40μm. The average particle size of the nano-montmorillonite is 30nm. The outer layer is a composite layer of PBT and fluoropolymer, with fluoropolymer content of 10wt% and compatibilizer content of 2.5wt%. The fluoropolymer is perfluoroethylene propylene copolymer FEP N3180, and the compatibilizer is Sumitomo BF-7M compatibilizer.

[0040] The fluorosilicone polyurethane acrylic resin is prepared according to the method of Example 1 of Chinese Invention Patent No. CN111057203B; the average particle size of the nano-silica is 20 nm; the coupling agent is silane coupling agent KH560; the photoinitiator is benzoin ether; and the diluent is a mixture of isooctyl acrylate, methyl methacrylate, and 2-hydroxyethyl acrylate in a mass ratio of 1:0.9:1.

[0041] The preparation method of the nano-modified release layer includes the following steps: uniformly dispersing nano-titanium dioxide and silane coupling agent KH560 in ethanol, then immersing a PET release film in it at an immersion speed of 2.3 m / min, removing it and drying it at 120°C for 3.5 minutes to obtain the nano-modified release layer; the mass ratio of nano-titanium dioxide, silane coupling agent KH560 and ethanol is 6:0.6:100; the average particle size of the nano-titanium dioxide is 30 nm.

[0042] A method for preparing the acid-resistant protective film tape includes the following steps: Step S1, Substrate layer preparation: The inner, middle and outer layer materials are melt-co-extruded using a three-layer co-extrusion equipment, and then shaped after biaxial stretching to obtain the substrate layer; Step S2, Preparation of composite adhesive: After mixing the raw materials of the composite adhesive layer evenly according to the weight parts, the composite adhesive is obtained; Step S3, Composite Molding: Coat the composite adhesive onto the nano-modified release layer at a coating speed of 2.5 m / min, pre-cur it under ultraviolet light with a wavelength of 230 nm for 12 min, then dry it at 63℃ for 3.5 min, and then bond it to the substrate layer by hot pressing. After winding, let it stand at 40℃ for 5 days to obtain the acid-resistant protective film tape.

[0043] The hot pressing temperature is 65℃ and the pressure is 0.35MPa; the melt co-extrusion temperature is 230-260℃. Example 3

[0044] An acid-resistant protective film tape is composed of a substrate layer, a composite adhesive layer, and a nano-modified release layer, wherein the composite adhesive layer is located between the substrate layer and the nano-modified release layer; the composite adhesive layer is made of the following raw materials in parts by weight: 45 parts of fluorosilicone polyurethane acrylic resin, 4 parts of N-(4-cyano-3-trifluoromethylphenyl)methacrylamide, 2 parts of (perfluoropropane-2,2-diyl)bis(4,1-phenylene)diacrylate, 3 parts of N-vinylcarbazole, 6.5 parts of nano silica, 2 parts of coupling agent, 1 part of photoinitiator, and 35 parts of diluent.

[0045] The total thickness of the substrate layer is 100 μm; the thickness of the composite adhesive layer is 15 μm; and the thickness of the nano-modified release layer is 25 μm.

[0046] The substrate layer is a multilayer co-extruded modified PBT base film, consisting of an inner layer, a middle layer, and an outer layer from the inside out. The inner layer is a blend of PBT and EVA, with EVA content of 15wt%, compatibilizer content of 3wt%, and a thickness of 30μm. The PBT is PBT4012G RESIN, and the EVA is Hanwha Chemical EVA1828. The middle layer is a composite layer of PBT and nano-montmorillonite, with nano-montmorillonite content of 7wt% and a thickness of 40μm. The average particle size of the nano-montmorillonite is 35nm. The outer layer is a composite layer of PBT and fluoropolymer, with fluoropolymer content of 11wt% and compatibilizer content of 3wt%. The fluoropolymer is perfluoroethylene propylene copolymer FEPN3180, and the compatibilizer is Sumitomo BF-7M compatibilizer.

[0047] The fluorosilicone polyurethane acrylic resin is prepared according to the method of Example 1 of Chinese Invention Patent No. CN111057203B; the average particle size of the nano-silica is 50 nm; the coupling agent is silane coupling agent KH570; the photoinitiator is benzoin ether; and the diluent is a mixture of isooctyl acrylate, methyl methacrylate, and 2-hydroxyethyl acrylate in a mass ratio of 1:1:1.

[0048] The preparation method of the nano-modified release layer includes the following steps: uniformly dispersing nano-titanium dioxide and silane coupling agent KH560 in ethanol, then immersing a PET release film in it at an immersion speed of 2.5 m / min, removing it and drying it at 120°C for 4 minutes to obtain the nano-modified release layer; the mass ratio of nano-titanium dioxide, silane coupling agent KH560 and ethanol is 7:0.65:100; the average particle size of the nano-titanium dioxide is 50 nm.

[0049] A method for preparing the acid-resistant protective film tape includes the following steps: Step S1, Substrate layer preparation: The inner, middle and outer layer materials are melt-co-extruded using a three-layer co-extrusion equipment, and then shaped after biaxial stretching to obtain the substrate layer; Step S2, Preparation of composite adhesive: After mixing the raw materials of the composite adhesive layer evenly according to the weight parts, the composite adhesive is obtained; Step S3, Composite Molding: Coat the composite adhesive onto the nano-modified release layer at a coating speed of 3 m / min, pre-cur it under ultraviolet light with a wavelength of 240 nm for 13 min, then dry it at 65 °C for 4 min, and then bond it to the substrate layer by hot pressing. After winding, let it stand at 40 °C for 5 days to obtain the acid-resistant protective film tape.

[0050] The hot pressing temperature is 70℃ and the pressure is 0.4MPa; the melt co-extrusion temperature is 230-260℃. Example 4

[0051] An acid-resistant protective film tape comprises a substrate layer, a composite adhesive layer, and a nano-modified release layer, wherein the composite adhesive layer is located between the substrate layer and the nano-modified release layer; the composite adhesive layer is made of the following raw materials in parts by weight: 48 parts of fluorosilicone polyurethane acrylic resin, 4.5 parts of N-(4-cyano-3-trifluoromethylphenyl)methacrylamide, 2.5 parts of (perfluoropropane-2,2-diyl)bis(4,1-phenylene)diacrylate, 3.5 parts of N-vinylcarbazole, 7.5 parts of nano-silica, 2.5 parts of coupling agent, 1.1 parts of photoinitiator, and 38 parts of diluent.

[0052] The total thickness of the substrate layer is 100 μm; the thickness of the composite adhesive layer is 15 μm; and the thickness of the nano-modified release layer is 25 μm.

[0053] The substrate layer is a multilayer co-extruded modified PBT base film, consisting of an inner layer, a middle layer, and an outer layer from the inside out. The inner layer is a blend of PBT and EVA, with EVA content of 18wt%, compatibilizer content of 3.5wt%, and a thickness of 30μm. The PBT is PBT 4012G RESIN, and the EVA is Hanwha Chemical EVA1828. The middle layer is a composite layer of PBT and nano-montmorillonite, with nano-montmorillonite content of 9wt% and a thickness of 40μm. The average particle size of the nano-montmorillonite is 40nm. The outer layer is a composite layer of PBT and fluoropolymer, with fluoropolymer content of 13wt% and compatibilizer content of 3.5wt%. The fluoropolymer is perfluoroethylene propylene copolymer FEP N3180, and the compatibilizer is Sumitomo BF-7M compatibilizer.

[0054] The fluorosilicone polyurethane acrylic resin is prepared according to the method of Example 1 of Chinese Invention Patent No. CN111057203B; the average particle size of the nano-silica is 70 nm; the coupling agent is a mixture of silane coupling agent KH550, silane coupling agent KH560 and silane coupling agent KH570 in a mass ratio of 1:2:1; the photoinitiator is benzoin ether; the diluent is a mixture of isooctyl acrylate, methyl methacrylate and 2-hydroxyethyl acrylate in a mass ratio of 1:1.1:1.

[0055] The preparation method of the nano-modified release layer includes the following steps: uniformly dispersing nano-titanium dioxide and silane coupling agent KH560 in ethanol, then immersing a PET release film in it at an immersion speed of 2.8 m / min, and drying it at 120°C for 4.5 minutes after removal to obtain the nano-modified release layer; the mass ratio of nano-titanium dioxide, silane coupling agent KH560 and ethanol is 9:0.75:100; the average particle size of the nano-titanium dioxide is 70 nm.

[0056] A method for preparing the acid-resistant protective film tape includes the following steps: Step S1, Substrate layer preparation: The inner, middle and outer layer materials are melt-co-extruded using a three-layer co-extrusion equipment, and then shaped after biaxial stretching to obtain the substrate layer; Step S2, Preparation of composite adhesive: After mixing the raw materials of the composite adhesive layer evenly according to the weight parts, the composite adhesive is obtained; Step S3, Composite Molding: Coat the composite adhesive onto the nano-modified release layer at a coating speed of 3.5 m / min, pre-cur it under ultraviolet light with a wavelength of 250 nm for 14 min, then dry it at 68℃ for 3-5 min, and then bond it to the substrate layer by hot pressing. After winding, let it stand at 40℃ for 5 days to obtain the acid-resistant protective film tape.

[0057] The hot pressing temperature is 75℃ and the pressure is 0.45MPa; the melt co-extrusion temperature is 230-260℃. Example 5

[0058] An acid-resistant protective film tape comprises a substrate layer, a composite adhesive layer, and a nano-modified release layer, wherein the composite adhesive layer is located between the substrate layer and the nano-modified release layer; the composite adhesive layer is made of the following raw materials in parts by weight: 50 parts of fluorosilicone polyurethane acrylic resin, 5 parts of N-(4-cyano-3-trifluoromethylphenyl)methacrylamide, 3 parts of (perfluoropropane-2,2-diyl)bis(4,1-phenylene)diacrylate, 4 parts of N-vinylcarbazole, 8 parts of nano silica, 3 parts of coupling agent, 1.2 parts of photoinitiator, and 40 parts of diluent.

[0059] The total thickness of the substrate layer is 100 μm; the thickness of the composite adhesive layer is 15 μm; and the thickness of the nano-modified release layer is 25 μm.

[0060] The substrate layer is a multilayer co-extruded modified PBT base film, consisting of an inner layer, a middle layer, and an outer layer from the inside out. The inner layer is a blend of PBT and EVA, with EVA content of 20wt%, compatibilizer content of 4wt%, and a thickness of 30μm. The PBT is PBT4012G RESIN, and the EVA is Hanwha Chemical EVA1828. The middle layer is a composite layer of PBT and nano-montmorillonite, with nano-montmorillonite content of 10wt% and a thickness of 40μm. The average particle size of the nano-montmorillonite is 50nm. The outer layer is a composite layer of PBT and fluoropolymer, with fluoropolymer content of 15wt% and compatibilizer content of 4wt%. The fluoropolymer is perfluoroethylene propylene copolymer FEPN3180, and the compatibilizer is Sumitomo BF-7M compatibilizer.

[0061] The fluorosilicone polyurethane acrylic resin is prepared according to the method of Example 1 of Chinese Invention Patent No. CN111057203B; the average particle size of the nano-silica is 80 nm; the coupling agent is silane coupling agent KH550; the photoinitiator is benzoin ether; and the diluent is a mixture of isooctyl acrylate, methyl methacrylate, and 2-hydroxyethyl acrylate in a mass ratio of 1:1.2:1.

[0062] The preparation method of the nano-modified release layer includes the following steps: uniformly dispersing nano-titanium dioxide and silane coupling agent KH560 in ethanol, then immersing a PET release film in it at an immersion speed of 3 m / min, and drying it at 120°C for 5 minutes to obtain the nano-modified release layer; the mass ratio of nano-titanium dioxide, silane coupling agent KH560 and ethanol is 10:0.8:100; the average particle size of the nano-titanium dioxide is 80 nm.

[0063] A method for preparing the acid-resistant protective film tape includes the following steps: Step S1, Substrate layer preparation: The inner, middle and outer layer materials are melt-co-extruded using a three-layer co-extrusion equipment, and then shaped after biaxial stretching to obtain the substrate layer; Step S2, Preparation of composite adhesive: After mixing the raw materials of the composite adhesive layer evenly according to the weight parts, the composite adhesive is obtained; Step S3, Composite Molding: Coat the composite adhesive onto the nano-modified release layer at a coating speed of 4 m / min, pre-cur it under ultraviolet light with a wavelength of 260 nm for 15 min, then dry it at 70 °C for 5 min, and then bond it to the substrate layer by hot pressing. After winding, let it stand at 40 °C for 5 days to obtain the acid-resistant protective film tape.

[0064] The hot pressing temperature is 80℃ and the pressure is 0.5MPa; the melt co-extrusion temperature is 230-260℃.

[0065] Comparative Example 1 An acid-resistant protective film tape is basically the same as that in Example 1, except that an equal amount of N-(4-cyano-3-trifluoromethylphenyl)methacrylamide is used instead of (perfluoropropane-2,2-diyl)bis(4,1-phenylene)diacrylate; and the substrate layer is made of PBT.

[0066] Comparative Example 2 An acid-resistant protective film tape is basically the same as that in Example 1, except that an equal amount of N-(4-cyano-3-trifluoromethylphenyl)methacrylamide is used instead of N-vinylcarbazole; and the nano-modified release layer is a PET release film.

[0067] To further illustrate the beneficial technical effects of the acid-resistant protective film tapes involved in the various embodiments of the present invention, relevant performance tests were conducted on the acid-resistant protective film tapes involved in Examples 1-5 and Comparative Examples 1-2. The test results are shown in Table 1, and the test methods are as follows: (1) Acid resistance: The test shall be conducted in accordance with GB / T 1763-1979 "Test Method for Chemical Resistance of Coating Film". Prepare a 60% HF solution, and attach the acid-resistant protective film tape of each example to the standard glass substrate, completely covering the surface of the glass substrate, ensuring that there are no bubbles or gaps. Then immerse the glass substrate with the tape in the HF solution and keep it at 40°C for 12 hours. If the tape does not show any signs of peeling, wrinkling, or leakage, and the surface of the glass substrate is not corroded by the acid, the acid resistance is passed; otherwise, it is unqualified.

[0068] (2) Peel performance test: Refer to GB / T 2792-2014 to test the peel strength of the tape at 23° and 180° on a stainless steel plate and the residual adhesive.

[0069] (3) Step difference compensation and acid contamination test: Prepare a test plate with a step difference of 0.2-1.2mm, attach tape and soak it in 50% sulfuric acid solution for 10h, observe whether acid seeps into the step difference; at the same time, test the organic matter content in the acid solution after soaking.

[0070] Table 1 project Acid resistance 180° peel strength Residual adhesive Segment compensation Organic matter content unit — N / cm — — mg / L Example 1 pass 10.9 No residue Acid-free liquid ≤0.01 Example 2 pass 11.3 No residue Acid-free liquid ≤0.007 Example 3 pass 11.5 No residue Acid-free liquid ≤0.005 Example 4 pass 11.7 No residue Acid-free liquid ≤0.004 Example 5 pass 12.0 No residue Acid-free liquid ≤0.001 Comparative Example 1 Unqualified 10.2 Residual glue There is acid ≥0.07 Comparative Example 2 Unqualified 10.5 Residual glue There is acid ≥0.05 As can be seen from Table 1, the acid-resistant protective film tape disclosed in the embodiments of the present invention has better acid resistance, adhesion, step compensation and anti-pollution performance than the comparative product; the combined use of (perfluoropropane-2,2-dimethyl)bis(4,1-phenylene)diacrylate, N-vinylcarbazole, multilayer co-extruded modified PBT base film and nano-modified release layer is beneficial to improving the above performance.

[0071] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely principles of the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the claimed invention. The scope of protection claimed by the appended claims and their equivalents is defined.

Claims

1. An acid-resistant protective film tape, characterized in that, It is composed of a substrate layer, a composite adhesive layer, and a nano-modified release layer, with the composite adhesive layer located between the substrate layer and the nano-modified release layer; the composite adhesive layer is made of the following raw materials in parts by weight: 40-50 parts of fluorosilicone polyurethane acrylic resin, 3-5 parts of N-(4-cyano-3-trifluoromethylphenyl)methacrylamide, 1-3 parts of (perfluoropropane-2,2-diyl)bis(4,1-phenylene)diacrylate, 2-4 parts of N-vinylcarbazole, 5-8 parts of nano silica, 1-3 parts of coupling agent, 0.8-1.2 parts of photoinitiator, and 30-40 parts of diluent.

2. The acid-resistant protective film tape according to claim 1, characterized in that, The total thickness of the substrate layer is 100μm-200μm; the thickness of the composite adhesive layer is 15μm-40μm; and the thickness of the nano-modified release layer is 25μm-75μm.

3. The acid-resistant protective film tape according to claim 1, characterized in that, The substrate layer is a multilayer co-extruded modified PBT base film, consisting of an inner layer, a middle layer, and an outer layer from the inside out. The inner layer is a blend of PBT and EVA, wherein the EVA content is 10wt%-20wt%, the compatibilizer content is 2wt%-4wt%, and the thickness is 30-50μm. The PBT is PBT 4012G RESIN, and the EVA is Hanwha Chemical EVA1828.

4. The acid-resistant protective film tape according to claim 3, characterized in that, The middle layer of PBT and nano-montmorillonite composite layer has a nano-montmorillonite content of 5wt%-10wt% and a thickness of 40-80μm; the average particle size of the nano-montmorillonite is 20-50nm.

5. The acid-resistant protective film tape according to claim 3, characterized in that, The outer layer is a composite layer of PBT and fluororesin, wherein the fluororesin content is 8wt%-15wt% and the compatibilizer is 2wt%-4wt%; the fluororesin is perfluoroethylene propylene copolymer FEP N3180; and the compatibilizer is Sumitomo BF-7M compatibilizer.

6. The acid-resistant protective film tape according to claim 1, characterized in that, The average particle size of the nano-silica is 10-80 nm; the coupling agent is at least one of silane coupling agent KH550, silane coupling agent KH560, and silane coupling agent KH570; the photoinitiator is benzoin ether; and the diluent is a mixture of isooctyl acrylate, methyl methacrylate, and 2-hydroxyethyl acrylate in a mass ratio of 1:(0.8-1.2):

1.

7. The acid-resistant protective film tape according to claim 1, characterized in that, The preparation method of the nano-modified release layer includes the following steps: uniformly dispersing nano-titanium dioxide and silane coupling agent KH560 in ethanol, then immersing the PET release film in it at an immersion speed of 2-3 m / min, and drying it at 120°C for 3-5 minutes after removal to obtain the nano-modified release layer.

8. The acid-resistant protective film tape according to claim 7, characterized in that, The mass ratio of nano-titanium dioxide, silane coupling agent KH560, and ethanol is (5-10):(0.5-0.8):100; the average particle size of the nano-titanium dioxide is 10-80 nm.

9. A method for preparing an acid-resistant protective film tape according to any one of claims 1-8, characterized in that, Includes the following steps: Step S1, Substrate layer preparation: The inner, middle and outer layer materials are melt-co-extruded using a three-layer co-extrusion equipment, and then shaped after biaxial stretching to obtain the substrate layer; Step S2, Preparation of composite adhesive: After mixing the raw materials of the composite adhesive layer evenly according to the weight parts, the composite adhesive is obtained; Step S3, Composite Molding: Coat the composite adhesive onto the nano-modified release layer at a coating speed of 2-4 m / min, pre-cur it under ultraviolet light with a wavelength of 220-260 nm for 10-15 min, then dry it at 60-70℃ for 3-5 min, and then bond it to the substrate layer by hot pressing. After winding, let it stand at 40℃ for 5 days to obtain the acid-resistant protective film tape.

10. The method for preparing the acid-resistant protective film tape according to claim 9, characterized in that, The hot pressing temperature is 60-80℃ and the pressure is 0.3-0.5MPa; the melt co-extrusion temperature is 230-260℃.