WO2021164578A1 - 保护膜及其制备方法、贴合方法和终端 - Google Patents

保护膜及其制备方法、贴合方法和终端 Download PDF

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Publication number
WO2021164578A1
WO2021164578A1 PCT/CN2021/075534 CN2021075534W WO2021164578A1 WO 2021164578 A1 WO2021164578 A1 WO 2021164578A1 CN 2021075534 W CN2021075534 W CN 2021075534W WO 2021164578 A1 WO2021164578 A1 WO 2021164578A1
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WIPO (PCT)
Prior art keywords
layer
protective film
base film
polyurethane base
polyurethane
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PCT/CN2021/075534
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English (en)
French (fr)
Inventor
庞欢
胡成文
李鹏飞
周羽佳
黄义宏
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华为技术有限公司
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Application filed by 华为技术有限公司 filed Critical 华为技术有限公司
Priority to EP21757929.1A priority Critical patent/EP4094941A4/en
Priority to KR1020227031092A priority patent/KR20220140574A/ko
Publication of WO2021164578A1 publication Critical patent/WO2021164578A1/zh

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    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00—Presence of (meth)acrylic polymer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2475/00—Presence of polyurethane
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2475/00—Presence of polyurethane
    • C09J2475/006—Presence of polyurethane in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2483/00—Presence of polysiloxane

Definitions

  • This application relates to the technical field of display screen protective films, and in particular to a protective film, a preparation method thereof, a bonding method, and a terminal.
  • the use of curved display screens has become a major popular trend at present, and it is constantly developing toward greater bending angles.
  • the industry usually attaches a protective film to the surface of the curved display screen.
  • the currently commonly used PET (Polyethylene terephthalate) protective film 2 has poor adhesion performance due to its high hardness. It is easy to cause bonding bounce at the corners (area A in Figure 1) due to the mismatch of the arc.
  • the protective film needs to be expanded and contracted to avoid the curved area of the curved display, but this not only affects the appearance Exquisiteness, and most of the curved area is still exposed and unprotected.
  • the polyurethane protective film commonly used at present is soft and good for bonding, its hardness is low. Consumers are prone to nail marks and scratches during use, which seriously affects the user experience. Therefore, it is necessary to develop a protective film with high hardness, excellent scratch resistance and good bonding performance to adapt to the bonding of curved display screens.
  • the embodiment of the application discloses a protective film, which has high hardness and excellent scratch resistance, and can be formed into a shape matching the screen by hot pressing or UV irradiation when it is attached to the surface of the screen, thereby enabling protection
  • the film is more perfectly consistent with the curvature of the curved screen, and it is closely integrated with the curved screen, without warping and rebound.
  • the first aspect of the embodiments of the present application discloses a protective film for protecting a screen of an electronic device, the protective film including a polyurethane base film layer and a glue layer provided on one side of the polyurethane base film layer;
  • the Shore hardness of the polyurethane base film layer is in the range of 45D to 75D, the glass transition temperature Tg is in the range of 30°C to 70°C, the heat distortion temperature T is in the range of 50°C to 90°C, and Tg ⁇ T deformation ;
  • the adhesive layer is used for bonding with the screen of the electronic device.
  • the Young's modulus of the polyurethane base film layer is in the range of 500Mpa to 3Gpa.
  • the protective film has a planar structure.
  • the polyurethane base film layer is a polyurethane acrylate film layer or a thermoplastic polyurethane film layer.
  • the thickness of the polyurethane base film layer is 30 ⁇ m to 200 ⁇ m.
  • the glue layer is silica gel or acrylic glue.
  • the thickness of the adhesive layer is 10 ⁇ m-50 ⁇ m.
  • the peeling force of the adhesive layer is greater than 800gf/25mm.
  • the protective film further includes a dirt-resistant self-healing layer, and the dirt-resistant self-healing layer is disposed on a side of the polyurethane base film layer away from the glue layer.
  • the stain-resistant self-healing layer is a polyurethane coating doped with fluoroether and/or fluorocarbon additives, or a polyurethane acrylic resin coating doped with fluoroether and/or fluorocarbon additives.
  • Floor is a polyurethane coating doped with fluoroether and/or fluorocarbon additives, or a polyurethane acrylic resin coating doped with fluoroether and/or fluorocarbon additives.
  • the thickness of the stain-resistant self-healing layer is 5 ⁇ m-40 ⁇ m.
  • the pencil hardness of the stain-resistant self-healing layer is 500g, and the load is ⁇ 1H, and the water drop angle of the stain-resistant self-healing layer is ⁇ 90°.
  • the Young's modulus of the stain-resistant self-healing layer is less than the Young's modulus of the polyurethane base film layer.
  • the protective film further includes a primer layer disposed between the polyurethane base film layer and the adhesive layer, and the primer layer is a silane-modified polyurethane acrylic resin coating.
  • the protective film further includes a lower release layer, and the lower release layer is disposed on a side surface of the adhesive layer away from the polyurethane base film layer.
  • the protective film further includes an upper protective layer, and the upper protective layer is located on a side of the polyurethane base film layer away from the adhesive layer.
  • the second aspect of the embodiments of the present application provides a method for preparing a protective film, including:
  • the Shore hardness of the polyurethane base film is in the range of 45D to 75D
  • the glass transition temperature Tg is in the range of 30°C to 70°C
  • the heat distortion temperature T is in the range of 50°C to 90°C.
  • Tg ⁇ T deformation
  • a glue layer is prepared on the surface of one side of the polyurethane base film.
  • the preparation method further includes preparing a stain-resistant self-healing layer on the other side surface of the polyurethane base film.
  • the third aspect of the embodiments of the present application provides a method for attaching a protective film, including:
  • the protective film described in the first aspect of the embodiment of the present application is attached to the surface of the electronic device screen through the adhesive layer, and then the protective film is heated to soften the protective film, and the protective film is thermoformed by a heated soft rubber mold. A shape that matches the screen.
  • the hot press forming temperature is greater than the thermal deformation temperature of the protective film, and the hot press forming temperature is in the range of 50°C to 90°C.
  • the hot pressing holding time is greater than 20s.
  • the fourth aspect of the embodiments of the present application provides a protective film for protecting the screen of an electronic device.
  • the protective film includes a first polyurethane base film layer and an adhesive layer, and is disposed on the first polyurethane base film layer and the UV semi-cured layer between adhesive layers;
  • the protective film includes a first polyurethane base film layer and a glue layer, a UV semi-cured layer arranged between the first polyurethane base film layer and the glue layer, and a UV semi-cured layer arranged between the glue layer and the UV The second polyurethane base film layer between the semi-cured layers;
  • the Shore hardness of the first polyurethane base film layer and the second polyurethane base film layer is in the range of 45D to 75D, and the glass transition temperature Tg ⁇ 30°C;
  • the adhesive layer is used for bonding with the screen of the electronic device.
  • the Young's modulus of the first polyurethane base film layer and the second polyurethane base film layer is in the range of 500Mpa to 3Gpa.
  • the protective film has a planar structure.
  • the first polyurethane base film layer and the second polyurethane base film layer are polyurethane acrylate film layers or thermoplastic polyurethane film layers.
  • the thickness of the first polyurethane base film layer and the second polyurethane base film layer is 15 ⁇ m to 150 ⁇ m.
  • the UV semi-cured layer is a semi-cured urethane acrylate layer.
  • the semi-cured urethane acrylate layer includes a urethane acrylate containing double bonds.
  • the thickness of the UV semi-cured layer is in the range of 30 ⁇ m to 150 ⁇ m.
  • the glue layer is silica gel or acrylic glue.
  • the thickness of the adhesive layer is 10 ⁇ m-50 ⁇ m.
  • the peeling force of the adhesive layer is greater than 800gf/25mm.
  • the protective film further includes a dirt-resistant self-healing layer, and the dirt-resistant self-healing layer is disposed on a side of the first polyurethane base film layer away from the glue layer.
  • the stain-resistant self-healing layer is a polyurethane coating doped with fluoroether and/or fluorocarbon additives, or a polyurethane acrylic resin coating doped with fluoroether and/or fluorocarbon additives.
  • Floor is a polyurethane coating doped with fluoroether and/or fluorocarbon additives, or a polyurethane acrylic resin coating doped with fluoroether and/or fluorocarbon additives.
  • the thickness of the stain-resistant self-healing layer is 5 ⁇ m-40 ⁇ m.
  • the pencil hardness of the stain-resistant self-healing layer is 500g, and the load is ⁇ 1H, and the water drop angle of the stain-resistant self-healing layer is ⁇ 90°.
  • the Young's modulus of the stain-resistant self-healing layer is less than the Young's modulus of the polyurethane base film layer.
  • the protective film further includes a primer layer disposed between the UV semi-cured layer and the glue layer, or between the second polyurethane base film layer and the glue layer ,
  • the primer coating is a silane-modified polyurethane acrylic resin coating.
  • the protective film further includes a lower release layer, and the lower release layer is disposed on a side surface of the adhesive layer away from the first polyurethane base film layer.
  • the light transmittance of the lower release layer to the wavelength range of 10 nm to 400 nm is less than 10%.
  • the protective film further includes an upper protective layer, and the upper protective layer is located on a side of the first polyurethane base film layer away from the adhesive layer.
  • the light transmittance of the upper protective layer to the wavelength range of 10 nm to 400 nm is less than 10%.
  • the embodiments of the present application also provide a method for preparing a protective film, and the method for preparing includes:
  • a first polyurethane base film is prepared on a PET carrier film; the Shore hardness of the first polyurethane base film is in the range of 45D to 75D, and the glass transition temperature Tg is in the range of 30°C to 70°C;
  • a glue layer is prepared on the UV semi-cured layer.
  • the above preparation method further includes preparing a dirt-resistant self-healing layer on the surface of the first polyurethane base film away from the adhesive layer.
  • the embodiments of the present application also provide a method for preparing a protective film, and the method for preparing includes:
  • the first polyurethane base film layer is prepared on the PET carrier film; the Shore hardness of the first polyurethane base film layer is in the range of 45D to 75D, and the glass transition temperature Tg ⁇ 30°C;
  • a second polyurethane base film is prepared on the UV semi-cured layer; the Shore hardness of the second polyurethane base film layer is in the range of 45D to 75D, and the glass transition temperature Tg ⁇ 30°C;
  • a glue layer is prepared on the second polyurethane base film.
  • the above preparation method further includes preparing a dirt-resistant self-healing layer on the surface of the first polyurethane base film away from the adhesive layer.
  • the embodiment of the present application also provides a method for attaching a protective film, including:
  • the protective film provided by the fourth aspect of the embodiment of the present application is attached to the surface of the electronic device screen through the adhesive layer, and then the protective film is cured and molded by UV light irradiation.
  • the shape of the screen matches.
  • the UV light irradiation energy is in the range of 1000 mj/cm 2 to 3000 mj/cm 2 .
  • An embodiment of the present application further provides a terminal, the terminal including a display screen and a protective film attached to the display screen, the protective film being the protective film described in the first aspect of the embodiments of the application or
  • the protective film according to the fourth aspect of the embodiment the protective film is attached to the surface of the display screen through the adhesive layer.
  • the display screen of the terminal may be a curved display screen or a flat display screen.
  • the display screen includes cover glass, and the protective film is attached to the surface of the cover glass through an adhesive layer. If the display screen is a 3D large-angle curved display screen, the protective film is similar to the cover glass. match.
  • An embodiment of the present application also provides a terminal, the terminal including a display screen and a protective film attached to the display screen, the protective film including an adhesive layer and a polyurethane base film layer provided on the adhesive layer, The protective film is bonded to the display screen through the adhesive layer, the shore hardness of the polyurethane base film layer is in the range of 45D to 75D, the glass transition temperature Tg is in the range of 30°C to 70°C, and it is thermally deformed The temperature T deformation is in the range of 50°C to 90°C, and Tg ⁇ T deformation .
  • An embodiment of the present application also provides a terminal, the terminal includes a display screen and a protective film attached to the display screen, the protective film includes a glue layer bonded to the display screen, and is arranged on the glue layer
  • the Shore hardness of the first polyurethane base film layer is in the range of 45D to 75D, and the glass transition temperature Tg is greater than or equal to 30°C.
  • the protective film further includes a second polyurethane base film layer disposed between the adhesive layer and the fully cured UV semi-cured layer, and the Shore hardness of the second polyurethane base film layer is In the range of 45D ⁇ 75D, the glass transition temperature Tg ⁇ 30°C.
  • the protective film provided by the embodiments of the present application can adapt to the shape of the screen when it is attached to the surface of the screen, so it can fit perfectly on a 3D large-angle curved display screen, and form a close combination with the display screen without warping. Rebound; the protective film provided by the embodiments of the present application also has high hardness and excellent scratch resistance, which can improve user experience.
  • FIG. 1 is a schematic diagram of the bonding rebound when the existing PET protective film is bonded to the surface of the screen;
  • FIG. 2 is a schematic cross-sectional structure diagram of a protective film provided by an embodiment of the present application.
  • Fig. 3 is a schematic diagram of a post-hot-press bonding process provided by an embodiment of the present application.
  • FIG. 4 is a schematic diagram of a cross-sectional structure of a protective film provided by another embodiment of the present application.
  • Fig. 5 is a schematic diagram of a preparation process of a protective film provided by an embodiment of the present application.
  • FIG. 6 is a schematic diagram of a protective film bonding process provided by an embodiment of the present application.
  • FIG. 7 is a schematic diagram of a cross-sectional structure of a protective film provided by another embodiment of the present application.
  • FIG. 8 is a schematic diagram of a cross-sectional structure of a protective film provided by another embodiment of the present application.
  • FIG. 9 is a schematic cross-sectional structure diagram of a protective film provided by another embodiment of the present application.
  • FIG. 10 is a schematic cross-sectional structure diagram of a protective film provided by another embodiment of the present application.
  • FIG. 11 is a schematic diagram of a preparation process of a protective film provided by another embodiment of the present application.
  • FIG. 12 is a schematic diagram of a protective film bonding process provided by another embodiment of the present application.
  • FIG. 13 is a schematic structural diagram of a terminal provided by an embodiment of the present application.
  • FIG. 14 is a schematic diagram of the final bonding of the protective film provided by the embodiment of the present application on the surface of the curved display screen;
  • an embodiment of the present application provides a protective film 10 for attaching to a screen of an electronic device to protect the screen from external damage.
  • the screen of the electronic device may specifically be a display screen.
  • the protective film 10 can be applied to 2D, 2.5D, and 3D display screens, and can be applied to 3D large-angle display screens.
  • the protective film 10 includes a polyurethane base film layer 11 and a glue layer 12 provided on one side of the polyurethane base film layer 11.
  • the polyurethane base film layer 11 serves as the main material layer of the protective film, which can impart mechanical and optical properties to the protective film.
  • the polyurethane base film layer 11 has a relatively high hardness, a relatively high glass transition temperature Tg and a relatively low heat distortion temperature T deformation . Its Shore hardness is in the range of 45D ⁇ 75D, and the glass transition temperature Tg is in the range of 30°C ⁇ 70°C. , The thermal deformation temperature T deformation is in the range of 50°C ⁇ 90°C, and Tg ⁇ T deformation .
  • the polyurethane base film layer 11 has high hardness, which can provide high wear resistance and high scratch resistance for the protective film layer, and the polyurethane base film layer 11 has a higher glass transition temperature Tg It is beneficial to obtain a film with higher hardness and better scratch resistance, and a lower thermal deformation temperature T deformation can make the protective film suitable for the post-hot pressing laminating process, and solve the problem of the protective film due to the increase in hardness.
  • the rebound problem makes the protective film have both high hardness, excellent scratch resistance and good bonding performance.
  • the protective film 10 of the embodiment of the present application can be laminated to a 3D large-angle curved display screen without sacrificing the hardness and scratch resistance of the protective film, and is formed with a display screen CG (cover glass, cover glass) It is tightly combined, does not rebound and warp, so that the protective film can well protect the curved area of the display screen.
  • CG cover glass, cover glass
  • the post-hot pressing bonding process is specifically to first bond the protective film 10 to the surface of the screen 101, then heat the protective film 10 to soften it, and then soften it by profiling hot pressing.
  • the glue mold 102 is used as the "master mold”
  • the screen CG cover 101 is used as the "male mold” to heat and press the protective film 10 so that the protective film 10 is perfectly attached to the surface of the CG cover 101.
  • the post-hot press bonding process is to attach the protective film to the surface of the screen and then heat press it into a shape that matches the screen, it can be better matched and combined with the screen, effectively avoiding the prior hot press molding in the prior art
  • the bonding rebound due to the mismatch of the arc of the protective film and the screen can also reduce the distance between the protective film and the edge of the screen and improve the appearance refinement.
  • the protective film 10 has a planar structure, which is a planar protective film.
  • the adhesive layer 12 is bonded to the screen on the side away from the polyurethane base film layer 11.
  • the hardness of the polyurethane base film layer 11 can be obtained by a Shore hardness tester test, and the Shore hardness of the polyurethane base film layer 11 can also be in the range of 50D to 70D.
  • the glass transition temperature can be obtained by a differential scanning calorimetry (DSC) test, and the glass transition temperature Tg can also be in the range of 40°C to 60°C.
  • the heat deformation temperature T deformation can pass the ISO75-2 standard test, and the heat deformation temperature T deformation can also be in the range of 50°C to 80°C. Among them, the lower heat distortion temperature helps to ensure that the entire electronic equipment can withstand the post-hot pressing process.
  • the Young's modulus of the polyurethane base film layer 11 is in the range of 500Mpa to 3Gpa. In other embodiments of the present application, the Young's modulus of the polyurethane base film layer 11 may be in the range of 1Gpa to 2Gpa. . Controlling the Young's modulus within a suitable range can not only ensure that the protective film has a certain degree of elasticity, but also can effectively prevent the protective film from generating too much rebound stress due to the mismatch of the arc when the protective film is attached, resulting in a bonding rebound.
  • the polyurethane base film layer 11 may be a polyurethane acrylate (PUA, Polyurethane acrylate) film layer, or a thermoplastic polyurethane (TPU, Thermoplastic polyurethanes) film layer.
  • PVA polyurethane acrylate
  • TPU thermoplastic polyurethane
  • the polyurethane base film layer 11 is a polyurethane acrylate film layer
  • the polyurethane acrylate film layer can be formed by coating.
  • the raw materials for preparing the polyurethane acrylate film layer may include rigid isocyanate, tough isocyanate, polyol, hydroxy acrylate, photoinitiator, and coupling agent.
  • rigid isocyanate can increase the hardness and modulus of PUA
  • tough isocyanate can impart excellent toughness to the PUA base film.
  • Polyols can impart resilience and ductility to the PUA base film.
  • hydroxy acrylate can adjust the cross-linking density of PUA base film, and control the optical performance and thermal deformation temperature of PUA base film.
  • the rigid isocyanate may include isophorone diisocyanate (IPDI), xylylene diisocyanate (XDI), methylcyclohexyl diisocyanate (HTDI), norbornane diisocyanate (NBDI), 4,4- One or more of dicyclohexylmethane diisocyanate (H12MDI) and tetramethylm-xylylene diisocyanate (TMXDI).
  • the tough isocyanate may include one or more of hexamethylene diisocyanate (HDI), trimethyl hexamethylene diisocyanate (TMDI), and cyclohexane dimethylene diisocyanate (HXDI).
  • the polyol may include one or more of polyester polyol, polycaprolactone polyol, and polycarbonate diol.
  • the hydroxy acrylate may include one or more of hydroxyethyl acrylate, tripropylene glycol diacrylate, pentaerythritol diacrylate, trihydroxymethyl propane triacrylate, and pentaerythritol triacrylate.
  • the photoinitiator may include 2,4,6 (trimethylbenzoyl) diphenyl phosphine oxide, 2-methyl-1-[4-methylthiophenyl]-2-morpholin-1-acetone One or more of 1-hydroxy-cyclohexyl-phenyl ketone, 1-hydroxy-cyclohexyl-phenyl ketone, 4-chlorobenzophenone and methyl phthalate .
  • the coupling agent may include polymethylsiloxane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -aminopropyltrimethoxysilane, and ⁇ -glycidoxypropyltrimethoxysilane. One or more of.
  • the polyurethane base film layer 11 is a thermoplastic polyurethane film layer, and the thermoplastic polyurethane film layer may be cast molded.
  • the raw materials for preparing the thermoplastic polyurethane film layer include thermoplastic polyurethane particles, antioxidants, photoresist amine stabilizers and plasticizers.
  • the thermoplastic polyurethane particles can be synthesized from dicyclohexylmethane diisocyanate (H12MDI), diisocyanate (HDI), polycaprolactone polyol and chain extender.
  • the thickness of the polyurethane base film layer 11 may be 30 ⁇ m to 200 ⁇ m. In other embodiments of the present application, the thickness of the polyurethane base film layer 11 may also be 50 ⁇ m to 120 ⁇ m. In some other embodiments of the present application, the thickness of the polyurethane base film layer 11 may also be 80 ⁇ m to 100 ⁇ m.
  • the material of the adhesive layer 12 is pressure-sensitive adhesive, and specifically may be silica gel or acrylic adhesive.
  • the thickness of the adhesive layer 12 may be 10 ⁇ m to 50 ⁇ m. In some embodiments of the present application, the thickness of the adhesive layer 12 may be 20 ⁇ m to 30 ⁇ m. Wherein, under the condition of a peeling angle of 180°, the peeling force of the adhesive layer 12 is greater than 800gf/25mm.
  • the protective film 10 may also include a polyurethane base
  • the stain-resistant self-healing layer 13 on the side of the film layer 11 away from the adhesive layer 12.
  • the stain-resistant self-healing layer 13 may be a polyurethane (PU, polyurethane) coating doped with fluoroether and/or fluorocarbon additives, or a polyurethane acrylic resin doped with fluoroether and/or fluorocarbon additives (PUA) coating.
  • the stain-resistant self-healing layer 13 may be formed by light curing or thermal curing after coating.
  • the raw materials for preparing the polyurethane acrylic resin may include diisocyanate, polyol, hydroxy acrylate, photoinitiator and coupling agent.
  • fluoroether and fluorocarbon additives is not limited. It can be the commonly used anti-fingerprint and stain resistant materials. Specifically, it can be fluorosilane, perfluoropolyether silane, perfluoropolyether alcohol, fluorocarbon silane, and fluorocarbon. One or more of carbon alcohols.
  • the thickness of the stain-resistant self-healing layer 13 may be 5 ⁇ m-40 ⁇ m.
  • the thickness of the stain-resistant self-healing layer 13 may also be 10 ⁇ m-30 ⁇ m, or 15 ⁇ m-20 ⁇ m.
  • the 500g pencil hardness of the stain-resistant self-healing layer 13 may be ⁇ 1H, and the water drop angle may be ⁇ 90°. In some embodiments, the water drop angle of the stain-resistant self-healing layer 13 may be ⁇ 105°.
  • the Young's modulus of the stain-resistant self-healing layer 13 is lower than the Young's modulus of the polyurethane base film layer 11, and the resilience is good.
  • the Young's modulus of the stain-resistant self-healing layer 13 may be 50Mpa ⁇ 800Mpa, or 100Mpa ⁇ 600Mpa.
  • the stain-resistant self-healing layer may be made of hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, polycaprolactone polyol, fluorosilane, hydroxyethyl acrylate, 2,4,6 (three Methylbenzoyl) diphenyl phosphine oxide is formed by UV curing.
  • hexamethylene diisocyanate is a high-toughness hexamethylene diisocyanate
  • the polycaprolactone polyol is selected as a highly elastic polycaprolactone polyol.
  • a primer layer 14 can also be provided between the polyurethane base film layer 11 and the adhesive layer 12.
  • the primer layer 14 may be a silane-modified polyurethane acrylic resin coating with a thickness of 1 ⁇ m to 20 ⁇ m. Further, the thickness may be 1 ⁇ m to 5 ⁇ m.
  • the silane modifier can be, but is not limited to, methylsiloxane, methyltriacetylsilane. The silane modifier is chemically grafted on the polyurethane acrylate.
  • the protective film 10 further includes a lower release layer 15, and the lower release layer 15 is disposed on the side surface of the adhesive layer away from the polyurethane base film layer 11.
  • the material of the lower release layer 15 can be PET or PP (Polypropylene, polypropylene), the thickness can be in the range of 23 ⁇ m to 75 ⁇ m, and the thickness can also be 38 ⁇ m to 50 ⁇ m.
  • the lower release layer 15 is provided with an outwardly extending extension for tearing away from the adhesive layer.
  • the protective film 10 further includes an upper protective layer 16, which is located on the side of the polyurethane base film layer 11 away from the adhesive layer 12.
  • the upper protective layer 16 is disposed on one side surface of the stain-resistant self-healing layer 13.
  • the material of the upper protective layer 16 may be PET or PP, the thickness may be in the range of 23 ⁇ m to 75 ⁇ m, and the thickness may also be 38 ⁇ m to 50 ⁇ m.
  • the upper protective layer 16 is provided with an extension part extending outwards to facilitate tearing off.
  • the total thickness of the protective film 10 may be 70 ⁇ m to 300 ⁇ m.
  • the above-mentioned protective film 10 can be prepared in the following manner:
  • polyurethane base film (PU base film); the Shore hardness of the polyurethane base film is in the range of 45D ⁇ 75D, the glass transition temperature Tg is in the range of 30°C ⁇ 70°C, and the heat distortion temperature T is in the range of 50°C ⁇ 90. Within the range of °C, and Tg ⁇ T deformation ;
  • a glue layer is prepared on the surface of one side of the polyurethane base film.
  • the above-mentioned preparation method further includes preparing a stain-resistant self-healing layer on the other side surface of the polyurethane base film. In the embodiment of the present application, the above-mentioned preparation method may further include preparing other film layer structures as required. In some embodiments of the present application, the above-mentioned preparation method further includes providing an upper protective layer on the stain-resistant self-healing layer, preparing a primer layer between the adhesive layer and the polyurethane base film layer, and placing the adhesive layer away from the polyurethane base film layer. Set a lower release layer on the side.
  • the method for preparing the PU base film may be coating forming a PUA base film or casting a TPU base film.
  • the method for preparing the stain-resistant self-healing layer may be prepared by coating and curing the stain-resistant self-healing liquid.
  • the dirt-resistant self-repairing fluid includes fluoroether and/or fluorocarbon, and polyurethane or polyurethane acrylic resin raw materials.
  • the polyurethane acrylic resin raw material may include diisocyanate, polyol, hydroxy acrylate, photoinitiator and coupling agent.
  • the choice of fluoroether and fluorocarbon is not limited. It can be the commonly used anti-fingerprint and stain resistant materials, specifically fluorosilane, perfluoropolyether silane, perfluoropolyether alcohol, fluorocarbon silane, and fluorocarbon alcohol. One or more of.
  • the adhesive layer may be prepared by coating.
  • the method for preparing the primer layer may be to prepare the primer liquid by coating.
  • the primer liquid may include a silane modifier, a urethane acrylic resin oligomer, a chain extender, a leveling agent, an initiator, and a solvent.
  • the solvent may be a mixture of one or more of isopropanol, ethanol, ethyl acetate, butyl acetate, toluene, xylene, methyl ethyl ketone, and methyl isobutyl ketone.
  • the above-mentioned protective film 10 can be prepared in the following manner:
  • Step 1 Coating and molding PUA base film or casting TPU base film to obtain PU base film;
  • Step 2 Coat the dirt-resistant self-repairing liquid on the surface of the PU base film, and obtain the dirt-resistant self-repairing layer after curing;
  • Step 3 Coat the pressure-sensitive adhesive on the surface of the PU base film where the dirt-resistant self-healing layer is not provided, and form an adhesive layer after high-temperature curing;
  • Step 4 Cover the lower release film on the adhesive layer, and cover the protective film on the dirt-resistant self-healing layer to form an upper protective layer and a lower release layer, and wind up to obtain a protective film roll;
  • Step 5 Die-cut the protective film roll material to the corresponding electronic device screen protective film shape; after die-cutting, paste the hand-tear film on the upper protective layer and the lower release layer to obtain the protective film monomer finished product.
  • an embodiment of the present application also provides a method for attaching the above-mentioned protective film, including:
  • the protective film is attached to the surface of the screen of the electronic device through the adhesive layer, and then the protective film is softened by heating, and the protective film is thermoformed into a shape matching the screen through the heated soft rubber mold.
  • the hot press forming temperature is greater than the thermal deformation temperature of the protective film, wherein the hot press forming temperature is in the range of 50°C to 90°C, and the hot pressing holding time is >20s Specifically, for example, it may be 30s to 90s.
  • the protective film of the embodiment of the present application has a lower thermal deformation temperature, so the hot-press forming temperature can also be correspondingly controlled at a lower temperature, which can ensure that the entire electronic device can withstand the hot-pressing process.
  • the operation of attaching the protective film to the screen surface of the electronic device through the adhesive layer can be completed by using a film jig or device.
  • the soft rubber mold used in the hot press molding is a profiling soft rubber mold, and the side of the profiling soft rubber mold in contact with the protective film has a shape similar or consistent with the surface of the screen on which the protective film is to be attached.
  • the profiling soft rubber mold can specifically be a profiling silicone soft head.
  • the protective film is first attached to the flat area of the 3D large arc display screen, and then the protective film on the arc surface area of the display screen is fully heated and molded through the heated profiling silicone soft head. Activate the pressure-sensitive adhesive of the adhesive layer, so that the protective film is attached to the surface of the 3D large-angle display screen.
  • the protective film has a lower release layer and an upper protective layer
  • the lower release layer must be torn off first, and then the adhesive layer must be attached to the surface of the screen;
  • the upper protective layer is torn off.
  • the protective film provided in the embodiments of the present application is formed by attaching the protective film to the surface of the screen, and then forming the protective film by a hot pressing process, so that the protective film can better adapt to the curvature of the curved display screen, and the curved surface display
  • the arcs of the screen are completely consistent, so after the protective film of the present application is matched, the thermocompression molding can be applied to a larger-angle 3D curved display screen.
  • the protective film provided by the embodiments of the present application also has high hardness and excellent scratch resistance, which can improve user experience.
  • an embodiment of the present application also provides a protective film 20 for attaching to the screen of the electronic device to protect the screen from external damage.
  • the screen of the electronic device may specifically be a display screen.
  • the protective film 20 is suitable for 2D, 2.5D, and 3D display screens, and is suitable for 3D large-angle display screens.
  • the protective film 20 includes a first polyurethane base film layer 21 and an adhesive layer 201, and a UV semi-cured layer 23 disposed between the first polyurethane base film layer 21 and the adhesive layer 22.
  • the protective film 20 includes a first polyurethane base film layer 21 and an adhesive layer 201, and a UV semi-cured layer disposed between the first polyurethane base film layer 21 and the adhesive layer 22 23, and a second polyurethane base film layer 24 disposed between the adhesive layer 22 and the UV semi-cured layer 23.
  • the first polyurethane base film layer 21 and the second polyurethane base film layer 24 serve as the main material layer of the protective film, which can impart mechanical and optical properties to the protective film.
  • the first polyurethane base film layer 21 and the second polyurethane base film layer 24 have relatively high hardness and glass transition temperature Tg, the Shore hardness of which is in the range of 45D to 75D, and the glass transition temperature Tg ⁇ 30°C.
  • the first polyurethane base film layer 21 and the second polyurethane base film layer 24 have higher hardness and higher glass transition temperature Tg, which is beneficial to provide the protective film with high hardness and excellent wear resistance.
  • Anti-scratch performance, and the setting of a UV semi-cured layer can reduce the hardness of the protective film before it is attached to the screen surface.
  • it can apply the UV irradiation lamination process after the protective film is applied to improve the lamination performance of the protective film and effectively solve the problem.
  • the bonding rebound problem caused by the increased hardness of the protective film makes the protective film have high hardness, excellent scratch resistance and good bonding performance.
  • the protective film 20 of the embodiment of the present application can fit a 3D large-angle curved display screen without sacrificing the hardness and scratch resistance of the protective film. ) Form a tight bond without rebounding and warping, so that the protective film can well protect the arc area of the display screen.
  • the protective film 20 provided in the embodiments of the present application constructs a composite film system of "PU base film layer-UV semi-cured layer-adhesive layer” or "PU base film layer-UV semi-cured layer-PU base film layer-adhesive layer”. Since the UV semi-cured layer is in a semi-cured state that is not fully cured, it can reduce the hardness and modulus of the protective film before it is attached to the screen surface, and improve the adhesion of the protective film on the large-angle 3D screen surface.
  • the protective film By curing the UV semi-cured layer, the protective film can be cured and formed in situ, and the hardness and protective performance of the protective film can be improved after the protective film is attached to the screen surface, so that the protective film 20 can have both high hardness and excellent scratch resistance. And good fitting performance.
  • the post-UV irradiation bonding process specifically involves first bonding the protective film to the surface of the screen, and then curing the protective film by UV light irradiation, so that the protective film is perfectly bonded to the CG cover.
  • the surface of the board specifically involves first bonding the protective film to the surface of the screen, and then curing the protective film by UV light irradiation, so that the protective film is perfectly bonded to the CG cover. The surface of the board.
  • the post-UV irradiation bonding process is to bond the protective film to the surface of the screen and then solidify it into a shape that matches the screen, it can be better matched and combined with the screen, effectively avoiding pre-heating molding in the prior art
  • the bonding rebound caused by the mismatch of the arc of the protective film and the screen can make the protective film more secure when it is bonded to the curved display screen, and it can also reduce The shrinking distance of the protective film relative to the edge of the screen improves the vibrant appearance.
  • the protective film 20 has a planar structure, which is a planar protective film.
  • the side of the adhesive layer 22 away from the first polyurethane base film layer 21 is adhered to the screen of the electronic device.
  • the hardness of the first polyurethane base film layer 21 and the second polyurethane base film layer 24 can be obtained by a Shore durometer test.
  • the Shore hardness of the first polyurethane base film layer 21 and the second polyurethane base film layer 24 The hardness can be in the range of 50D to 70D.
  • the glass transition temperature can be obtained by a differential scanning calorimetry test, and the glass transition temperature Tg can be in the range of 30°C to 70°C.
  • the Young's modulus of the first polyurethane base film layer 21 and the second polyurethane base film layer 24 is controlled within the range of 500Mpa to 3Gpa. In other embodiments of the present application, the Young's modulus of the first polyurethane base film layer 21 and the second polyurethane base film layer 24 may be in the range of 1 Gpa to 2 Gpa. Controlling the Young's modulus within a suitable range can not only ensure that the protective film has a certain degree of elasticity, but also can effectively prevent the protective film from generating too much rebound stress due to the mismatch of the arc when the protective film is attached, resulting in a bonding rebound.
  • first polyurethane base film layer 21 and the second polyurethane base film layer 24 may be polyurethane acrylate (PUA) film layers, or may be thermoplastic polyurethane (TPU) film layers.
  • PUA polyurethane acrylate
  • TPU thermoplastic polyurethane
  • the first polyurethane base film layer 21 and the second polyurethane base film layer 24 are polyurethane acrylate film layers, and the polyurethane acrylate film layer can be formed by coating.
  • the raw materials for preparing the polyurethane acrylate film layer may include rigid isocyanate, tough isocyanate, polyol, hydroxy acrylate, photoinitiator, and coupling agent.
  • rigid isocyanate can increase the hardness and modulus of PUA
  • tough isocyanate can impart excellent toughness to the PUA base film.
  • Polyols can impart resilience and ductility to the PUA base film.
  • hydroxy acrylate can adjust the cross-linking density of PUA base film, and control the optical performance and thermal deformation temperature of PUA base film.
  • the rigid isocyanate may include isophorone diisocyanate (IPDI), xylylene diisocyanate (XDI), methylcyclohexyl diisocyanate (HTDI), norbornane diisocyanate (NBDI), 4,4- One or more of dicyclohexylmethane diisocyanate (H12MDI) and tetramethylm-xylylene diisocyanate (TMXDI).
  • the tough isocyanate may include one or more of hexamethylene diisocyanate (HDI), trimethyl hexamethylene diisocyanate (TMDI), and cyclohexane dimethylene diisocyanate (HXDI).
  • the polyol may include one or more of polyester polyol, polycaprolactone polyol, and polycarbonate diol.
  • the hydroxy acrylate may include one or more of hydroxyethyl acrylate, tripropylene glycol diacrylate, pentaerythritol diacrylate, trihydroxymethyl propane triacrylate, and pentaerythritol triacrylate.
  • the photoinitiator may include 2,4,6 (trimethylbenzoyl) diphenyl phosphine oxide, 2-methyl-1-[4-methylthiophenyl]-2-morpholin-1-acetone One or more of 1-hydroxy-cyclohexyl-phenyl ketone, 1-hydroxy-cyclohexyl-phenyl ketone, 4-chlorobenzophenone and methyl phthalate .
  • the coupling agent may include polymethylsiloxane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -aminopropyltrimethoxysilane, and ⁇ -glycidoxypropyltrimethoxysilane. One or more of.
  • the first polyurethane base film layer 21 and the second polyurethane base film layer 24 are thermoplastic polyurethane film layers, and the thermoplastic polyurethane film layers can be cast molded.
  • the raw materials for preparing the thermoplastic polyurethane film layer include thermoplastic polyurethane particles, antioxidants, photoresist amine stabilizers and plasticizers.
  • the thermoplastic polyurethane particles can be synthesized from dicyclohexylmethane diisocyanate (H12MDI), diisocyanate (HDI), polycaprolactone polyol and chain extender.
  • the thickness of the first polyurethane base film layer 21 and the second polyurethane base film layer 24 may be 15 ⁇ m to 150 ⁇ m. In other embodiments of the present application, the thickness of the first polyurethane base film layer 21 and the second polyurethane base film layer 24 may also be 20 ⁇ m to 120 ⁇ m. In some other embodiments of the present application, the thickness of the first polyurethane base film layer 21 and the second polyurethane base film layer 24 may also be 30 ⁇ m to 100 ⁇ m, or 40 ⁇ m to 80 ⁇ m.
  • the material and thickness of the first polyurethane base film layer 21 and the second polyurethane base film layer 24 may be the same or different.
  • the UV semi-cured layer 23 is a semi-cured urethane acrylate layer, that is, an incompletely cured urethane acrylate layer.
  • the UV semi-cured layer 23 includes a urethane acrylate containing a reactive functional group (such as a double bond).
  • the UV light irradiation pre-concentration energy of the UV semi-cured layer 23 is in the range of 10 mj/cm 2 to 500 mj/cm 2 .
  • the UV semi-cured layer has a low modulus before curing, which is conducive to improving the bonding performance, and a high modulus after fully curing is conducive to improving reliability and user experience.
  • the Shore hardness is in the range of 45D to 75D, and the glass transition temperature Tg is greater than or equal to 30°C.
  • the thickness of the UV semi-cured layer 23 is in the range of 30 ⁇ m to 150 ⁇ m. In some other embodiments of the present application, the thickness of the UV semi-cured layer 23 is in the range of 50 ⁇ m to 80 ⁇ m.
  • a third polyurethane base film layer and another UV semi-cured layer can be added to construct a PU base film layer-UV semi-cured layer-PU base film layer-UV semi-cured layer.
  • -PU base film layer-adhesive layer" composite film system -PU base film layer-adhesive layer
  • the material of the adhesive layer 22 is pressure-sensitive adhesive, and specifically may be silica gel or acrylic adhesive.
  • the thickness of the adhesive layer 22 may be 10 ⁇ m to 50 ⁇ m. In some embodiments of the present application, the thickness of the adhesive layer 22 may be 20 ⁇ m to 30 ⁇ m. Among them, under the condition of a peeling angle of 180°, the peeling force of the adhesive layer is greater than 800gf/25mm.
  • the protective film 20 may also include The dirt-resistant self-healing layer 25 on the side of the first polyurethane base film layer 21 away from the adhesive layer 22.
  • the stain-resistant self-healing layer 25 may be a polyurethane coating doped with fluoroether and/or fluorocarbon additives, or a polyurethane acrylic resin coating doped with fluoroether and/or fluorocarbon additives.
  • the raw materials of the polyurethane acrylic resin may include diisocyanate, polyol, hydroxy acrylate, photoinitiator and coupling agent.
  • the choice of fluoroether and fluorocarbon is not limited. It can be the commonly used anti-fingerprint and stain-resistant materials. Specifically, it can be fluorosilane, perfluoropolyether silane, perfluoropolyether alcohol, fluorocarbon silane, and fluorocarbon alcohol.
  • the thickness of the stain-resistant self-healing layer 25 may be 5 ⁇ m-40 ⁇ m.
  • the thickness of the stain-resistant self-healing layer 25 may also be 10 ⁇ m to 30 ⁇ m, or 15 ⁇ m to 20 ⁇ m.
  • the 500g pencil hardness of the stain-resistant self-healing layer 25 may be ⁇ 1H, and the water drop angle may be ⁇ 90°. In some embodiments, the water drop angle of the stain-resistant self-healing layer 25 may be ⁇ 105°.
  • the stain-resistant self-healing layer 25 may be made of hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, polycaprolactone polyol, fluorosilane, hydroxyethyl acrylate, 2,4,6 ( Trimethylbenzoyl)diphenylphosphine oxide is formed by UV curing.
  • hexamethylene diisocyanate is a high-toughness hexamethylene diisocyanate
  • the polycaprolactone polyol is selected as a highly elastic polycaprolactone polyol.
  • the Young's modulus of the stain-resistant self-healing layer 25 is smaller than the Young's modulus of the first polyurethane base film layer 21 and the second polyurethane base film layer 24, and the resilience is good.
  • the Young's modulus of the stain-resistant self-healing layer 25 may be 50Mpa ⁇ 800Mpa, or 100Mpa ⁇ 600Mpa.
  • a primer layer may be provided between the UV semi-cured layer 23 and the adhesive layer 22, or between the second polyurethane base film layer 24 and the adhesive layer 22.
  • the bottom coating is a silane-modified polyurethane acrylic resin coating, and the thickness can be 1 ⁇ m to 20 ⁇ m. Further, the thickness of the primer layer may be 1 ⁇ m to 5 ⁇ m.
  • the protective film 20 further includes a lower release layer 26, and the lower release layer 26 is disposed on the side surface of the adhesive layer 22 away from the first polyurethane base film layer 21.
  • the material of the lower release layer 26 may be PET or PP, and the thickness may be in the range of 23 ⁇ m to 75 ⁇ m, or 38 ⁇ m to 50 ⁇ m.
  • the lower release layer 26 has ultraviolet light shielding performance, and the light transmittance in the wavelength range of 10 nm to 400 nm is less than 10%.
  • the lower release layer 26 has ultraviolet light shielding properties, which can protect the protective film from ultraviolet light, and ensure that the UV semi-cured layer 23 is in a semi-cured state before being attached to the screen.
  • An extension part extending outward is provided on the lower release layer for tearing away from the adhesive layer.
  • the protective film 10 further includes an upper protective layer 27, which is located on the surface of the polyurethane base film layer away from the adhesive layer.
  • the material of the upper protective layer 27 may be PET or PP, and the thickness may be in the range of 23 ⁇ m to 75 ⁇ m, or 38 ⁇ m to 50 ⁇ m.
  • the upper protective layer 27 has ultraviolet light shielding performance, and the light transmittance in the wavelength range of 10 nm to 400 nm is less than 10%.
  • the upper protective layer 27 has ultraviolet light shielding properties, which can protect the protective film from ultraviolet light and ensure that the UV semi-cured layer 23 is in a semi-cured state before being attached to the screen.
  • An extension part extending outward is provided on the upper protective layer to facilitate tearing off.
  • the total thickness of the protective film 20 may be 70 ⁇ m to 300 ⁇ m.
  • An embodiment of the present application provides a method for preparing the protective film 20, including:
  • a first polyurethane base film is prepared on a PET carrier film; the Shore hardness of the first polyurethane base film is in the range of 45D to 75D, and the glass transition temperature Tg ⁇ 30°C;
  • a glue layer is prepared on the UV semi-cured layer.
  • Another embodiment of the present application provides a method for preparing the protective film 20, including:
  • the first polyurethane base film layer is prepared on the PET carrier film; the Shore hardness of the first polyurethane base film layer is in the range of 45D to 75D, and the glass transition temperature Tg ⁇ 30°C;
  • the Shore hardness of the second polyurethane base film layer is in the range of 45D to 75D, and the glass transition temperature Tg ⁇ 30°C;
  • a glue layer is prepared on the second polyurethane base film.
  • the preparation method further includes preparing a dirt-resistant self-repairing layer on the surface of the first polyurethane base film away from the adhesive layer.
  • the above-mentioned preparation method may further include preparing other film layer structures as required.
  • the above-mentioned preparation method further includes disposing an upper protective layer on the stain-resistant self-healing layer, and disposing a lower release layer on the side of the adhesive layer away from the first polyurethane base film layer.
  • the above preparation method further includes preparing a primer layer between the UV semi-cured layer and the adhesive layer, or between the second polyurethane base film layer and the adhesive layer.
  • the method for preparing the first PU base film and the second PU base film may be coating forming a PUA base film or casting a TPU base film.
  • the method for preparing the stain-resistant self-healing layer may be to prepare the stain-resistant self-healing liquid by coating.
  • the dirt-resistant self-repairing fluid may include fluoroether and/or fluorocarbon, and polyurethane or polyurethane acrylic resin raw materials.
  • the polyurethane acrylic resin raw material may include diisocyanate, polyol, hydroxy acrylate, photoinitiator and coupling agent.
  • the choice of fluoroether and fluorocarbon is not limited.
  • the adhesive layer may be prepared by coating.
  • the method for preparing the primer layer may be to prepare the primer liquid by coating.
  • the primer liquid may include a silane modifier, a urethane acrylic resin oligomer, a chain extender, a leveling agent, an initiator, and a solvent.
  • the solvent may be a mixture of one or more of isopropanol, ethanol, ethyl acetate, butyl acetate, toluene, xylene, methyl ethyl ketone, and methyl isobutyl ketone.
  • the above-mentioned protective film can be prepared in the following manner:
  • Step 1 Form the first PU base film layer on the surface of the PET carrier film, which can be specifically coated and UV-irradiated to form a PUA base film layer, or cast to form a TPU base film layer;
  • Step 2 Coat the dirt-resistant self-repairing liquid on the surface of the first PU base film layer, and form a dirt-resistant self-repairing layer after curing;
  • Step 3 Cover the PET carrier film on the side of the stain-resistant self-healing layer, tear off the PET carrier film on the side of the first PU base film layer, and coat the UV semi-cured layer material on the surface of the first PU base film layer. UV semi-cured layer is formed after UV radiation curing;
  • Step 4 Form a second PU base film layer on the surface of the UV semi-cured layer, which can be specifically coated and UV-irradiated to form a PUA base film layer, or cast to form a TPU base film layer;
  • Step 5 Coating pressure-sensitive adhesive on the surface of the second PU base film layer, and forming an adhesive layer after high-temperature curing;
  • Step 6 Cover the lower release film on the adhesive layer, tear off the PET carrier film on the side of the stain-resistant self-healing layer, and cover the stain-resistant self-healing layer with a protective film to form an upper protective layer and a lower release layer , Rewinding to obtain protective film rolls;
  • Step 7 Under the yellow light working environment, cut the protective film roll material through a knife die to cut out the shape of the corresponding electronic device screen protective film; after die cutting, paste the hand-tear film on the upper protective layer and the lower release layer to obtain protection Finished film monomer.
  • the UV semi-cured layer material is a polyurethane acrylate raw material, which may be the same or different from the raw material of the first PU base film layer.
  • the UV semi-cured layer is formed by radiation curing, low-power UV radiation is used.
  • the radiation energy of low-power UV radiation may be 10 mj/cm 2 to 500 mj/cm 2 .
  • step 4 in the above preparation method is omitted, and the adhesive layer can be directly prepared on the UV semi-cured layer.
  • an embodiment of the present application also provides a method for attaching the above-mentioned protective film, including:
  • the protective film 20 is attached to the surface of the screen of the electronic device through the adhesive layer 22, and then the protective film 20 is cured and formed into a shape matching the screen by UV light irradiation.
  • the UV light irradiation energy is in the range of 1000 mj/cm 2 to 3000 mj/cm 2 .
  • the operation of attaching the protective film to the screen surface of the electronic device through the adhesive layer can be completed by using a film jig or device.
  • the protective film has a lower release layer and an upper protective layer
  • the lower release layer needs to be removed first, and then the adhesive layer is attached to the surface of the screen; when the protective film is attached to the After the screen, the upper protective layer is torn off before the UV light is irradiated.
  • the operations of tearing off the release layer, attaching the protective film, and tearing up the protective layer are all performed in a yellow light working environment.
  • the protective film provided in the embodiments of the present application after the protective film is attached to the surface of the screen, the protective film is cured and molded by UV light irradiation, so that the protective film can better adapt to the curvature of the curved display screen, and The curved display screens are completely consistent. Therefore, after the protective film of the present application is combined, the UV irradiation molding can be adapted to a larger angle of the 3D curved display screen.
  • the protective film provided by the embodiments of the present application also has high hardness and excellent scratch resistance, which can improve user experience.
  • an embodiment of the present application also provides a terminal.
  • the terminal 200 may be a mobile phone, a tablet computer, a notebook computer, a portable computer, a smart wearable product, and the like.
  • the terminal 200 includes a display screen 201 and a protective film 202 attached to the surface of the display screen 201.
  • the display screen 201 includes a cover glass provided on the outermost layer, and the protective film 202 is tightly combined with the cover glass through an adhesive layer.
  • the display screen 201 may be a curved display screen or a flat display screen.
  • the curved display screen can be a 2.5D or 3D curved display screen.
  • the protective film 202 since the protective film 202 has good adhesion, when the display screen 201 is a 3D large-angle curved display screen, the protective film 202 can be attached closer to the edge of the display screen, reducing the relative relationship between the protective film and the display screen 201. The retracted distance. As shown in FIG. 14, when the protective film 202 is attached to the surface of the curved display screen 201, the shape of the protective film 202 matches the display screen, and the protective film 202 only has a retracted distance within the tolerance range.
  • the retracted distance of the protective film 202 may be less than or equal to 2 mm, and specifically, the retracted distance may be 0-1 mm, for example, 0.3 mm, 0.8 mm, or 1 mm.
  • the shape of the protective film 202 matches the display screen, which can not only better protect the display screen, but also improve theakiness of the appearance of the terminal.
  • the protective film 202 is formed by bonding the protective film 10. As shown in FIG. 15, the protective film 202 includes a glue layer 12 and a polyurethane base film layer 11 disposed on the glue layer 12. In some embodiments of the present application, the protective film 202 further includes a dirt-resistant self-healing layer 13 disposed on the polyurethane base film layer 11. In some embodiments of the present application, the protective film 202 further includes a primer layer 14 disposed between the polyurethane base film layer 11 and the adhesive layer 12.
  • the protective film 202 is formed by bonding the protective film 20.
  • the protective film 202 includes an adhesive layer 22, a fully cured UV semi-cured layer 23' and The first polyurethane base film layer 21 provided on the fully cured UV semi-cured layer 23'.
  • the protective film 202 further includes a stain-resistant self-healing layer 25 disposed on the first polyurethane base film layer 21.
  • the protective film 202 is formed by bonding the protective film 20.
  • the protective film 202 includes an adhesive layer 22, and a second polyurethane base film layer 24 disposed on the adhesive layer 22 is disposed on The fully cured UV semi-cured layer 23' on the second polyurethane base film layer 24 and the first polyurethane base film layer 21 provided on the fully cured UV semi-cured layer 23'.
  • the protective film 202 further includes a stain-resistant self-healing layer 25 disposed on the first polyurethane base film layer 21.
  • the UV semi-cured layer 23 is completely cured to form a fully cured UV semi-cured layer 23'.
  • the fully cured UV semi-cured layer 23' is a fully cured urethane acrylate layer.
  • the Shore hardness of the fully cured UV semi-cured layer 23' is in the range of 45D to 75D, and the glass transition temperature Tg is greater than or equal to 30°C.
  • the irradiation measurement is 2500mj/cm 2 , and a 18 ⁇ m thick dirt-resistant surface is formed on the surface of the high-hardness PUA film. Dirt self-healing layer to obtain dirt-resistant self-healing layer/high hardness PUA base film;
  • the mobile phone with the protective film laminated was placed at 55°C and 95% RH for 72 hours, and the protective film did not bounce and warp on the curved surface of the 3D large-angle curved display screen.
  • the protective film 500gf load pencil hardness ⁇ 2H, 500gf load copper brush friction (test conditions: Japanese OSAKA brand copper brush, brush head 4*6 bristles, stroke 20mm) after 50 times, no film falling and scratches; the surface of the protective film Water drop angle: 109 ⁇ 112°.
  • Example 2 Take the dirt-resistant self-healing liquid prepared in Example 1, and coat it on one side surface of the high-hardness TPU base film, and cure it by UV light irradiation with a mercury lamp source.
  • the irradiation measurement is 2800mj/cm 2 .
  • a stain-resistant self-healing layer with a thickness of 24 ⁇ m is formed on one side of the base film to obtain a stain-resistant self-healing layer/high-hardness TPU base film.
  • the mobile phone with the above-mentioned protective film was placed at 55°C and 95% RH for 72 hours.
  • the result showed that the protective film did not bounce and warp on the curved surface of the 3D large-angle curved display screen.
  • the protective film 500gf load pencil hardness ⁇ 1H, 500gf load copper brush friction (test conditions: Japanese OSAKA brand copper brush, brush head 4*6 bristles, stroke 20mm) after 50 times, no film falling and scratches; the surface of the protective film Water drop angle: 110 ⁇ 112°.
  • the mobile phone with the protective film laminated was placed at 55° C. and 95% RH for 72 hours. The result showed that the protective film did not rebound and warp on the curved surface of the 3D large-angle curved display screen.
  • the protective film 500gf load pencil hardness ⁇ 1H, 500gf load copper brush friction (test conditions: Japanese OSAKA brand copper brush, brush head 4*6 bristles, stroke 20mm) after 50 times, no film falling and scratches; the surface of the protective film Water drop angle: 108 ⁇ 111°.
  • the mobile phone with the protective film laminated was placed at 55° C. and 95% RH for 72 hours. The result showed that the protective film did not rebound and warp on the curved surface of the 3D large-angle curved display screen.
  • the protective film 500gf load pencil hardness ⁇ 1H, 500gf load copper brush friction (test conditions: Japanese OSAKA brand copper brush, brush head 4*6 bristles, stroke 20mm) after 50 times, no film falling and scratches; the surface of the protective film Water drop angle: 110 ⁇ 111°.
  • the test results of the above specific examples show that the protective film provided by the examples of the present application has good bonding performance on the surface of the 3D large-angle curved display screen, and has high hardness and excellent scratch resistance, and is suitable for large-angle 3D electronic devices.
  • the screen can be attached with a small indented protective film, and the protective film can be attached closer to the edge of the screen, thereby enhancing the protection capability and appearance refinement, and enhancing the user experience.

Abstract

一种保护膜，用于保护电子设备的屏幕，其包括聚氨酯基膜层（11）和胶层（12），聚氨酯基膜层（11）的邵氏硬度为45D～75D，玻璃化转变温度Tg为30℃～70℃，热变形温度T 变形为50℃～90℃，Tg＜T 变形；或包括第一聚氨酯基膜层（21）和胶层（22），及设在第一聚氨酯基膜层（21）和胶层（22）之间的UV半固化层（23）；第一聚氨酯基膜层（21）的邵氏硬度为45D～75D，玻璃化转变温度≥30℃。所述保护膜具有高硬度和优异耐划伤性能，且两种结构保护膜可在贴合至屏幕表面时分别经热压或UV辐照成型成与屏幕相匹配的形状，从而能完美地与曲面屏的弯曲弧度吻合形成紧密结合，不发生起翘反弹；此外，还提供了保护膜的制备方法和使用该保护膜的终端。

Description

保护膜及其制备方法、贴合方法和终端
本申请要求于2020年2月17日提交中国专利局、申请号为202010097709.3、申请名称为“一种保护膜，保护膜制备方法及电子设备”的中国专利申请的优先权，本申请要求于2020年3月20日提交中国专利局、申请号为202010206525.6、申请名称为“保护膜及其制备方法、贴合方法和终端”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本申请涉及显示屏保护膜技术领域，尤其涉及一种保护膜及其制备方法、贴合方法和终端。
背景技术
在电子产品中，曲面显示屏的使用成为目前一大流行趋势，并不断向更大弯曲角度发展。为保护曲面显示屏免受外界伤害，业界通常在曲面显示屏表面贴合保护膜。然而，如图1所示，目前常用的PET(Polyethylene terephthalate，聚对苯二甲酸乙二醇酯)保护膜2，由于硬度较大贴合性能不佳，在贴合至曲面显示屏1表面时容易因弧度不匹配在边角处(图1中A区域)产生贴合反弹，而为缓解贴合反弹，需要将保护膜扩大内缩，避让曲面显示屏的弧面区域，但这样不仅影响外观精致度，而且大部分弧面区域仍裸露在外，得不到保护。而目前常用的聚氨酯类保护膜，虽然质软有利于贴合，但其硬度低，消费者使用过程中容易出现指甲印与划痕，严重影响使用体验。因此，有必要开发一种兼具高硬度、优异耐划伤性能和良好贴合性能的保护膜，以适应曲面显示屏的贴合。
发明内容
本申请实施例公开了一种保护膜，具有高硬度和优异耐划伤性能，且能够在贴合至屏幕表面时经热压或UV辐照成型成与屏幕相匹配的形状，从而能够使保护膜更完美地与曲面屏的弯曲弧度吻合，与曲面屏形成紧密结合，不发生起翘反弹。
本申请实施例第一方面公开了一种保护膜，用于保护电子设备的屏幕，所述保护膜包括聚氨酯基膜层和设置在所述聚氨酯基膜层一侧的胶层；
所述聚氨酯基膜层的邵氏硬度在45D～75D范围内，玻璃化转变温度Tg在30℃～70℃范围内，热变形温度T 变形在50℃～90℃范围内，且Tg＜T 变形；
所述胶层用于与所述电子设备的屏幕粘合。
本申请实施方式中，所述聚氨酯基膜层的杨氏模量在500Mpa～3Gpa范围内。
本申请实施方式中，所述保护膜为平面结构。
本申请实施方式中，所述聚氨酯基膜层为聚氨酯丙烯酸酯膜层或热塑性聚氨酯膜层。
本申请实施方式中，所述聚氨酯基膜层的厚度为30μm～200μm。
本申请实施方式中，所述胶层为硅胶或丙烯酸胶。
本申请实施方式中，所述胶层的厚度为10μm～50μm。
本申请实施方式中，在剥离角度为180°条件下，所述胶层的剥离力大于800gf/25mm。
本申请实施方式中，所述保护膜还包括耐脏污自修复层，所述耐脏污自修复层设置在所述聚氨酯基膜层远离所述胶层的一侧。
本申请实施方式中，所述耐脏污自修复层为氟醚和/或氟碳类助剂掺杂的聚氨酯涂层，或氟醚和/或氟碳类助剂掺杂的聚氨酯丙烯酸树脂涂层。
本申请实施方式中，所述耐脏污自修复层的厚度为5μm～40μm。
本申请实施方式中，所述耐脏污自修复层的铅笔硬度500g载荷≥1H，所述耐脏污自修复层的水滴角≥90°。
本申请实施方式中，所述耐脏污自修复层的杨氏模量小于所述聚氨酯基膜层的杨氏模量。
本申请实施方式中，所述保护膜还包括设置在所述聚氨酯基膜层与所述胶层之间的底涂层，所述底涂层为硅烷改性的聚氨酯丙烯酸树脂涂层。
本申请实施方式中，所述保护膜还包括下离型层，所述下离型层设置在所述胶层远离所述聚氨酯基膜层的一侧表面。
本申请实施方式中，所述保护膜还包括上保护层，所述上保护层位于所述聚氨酯基膜层远离所述胶层的一侧。
本申请实施例第二方面提供一种保护膜的制备方法，包括：
提供或制备聚氨酯基膜；所述聚氨酯基膜的邵氏硬度在45D～75D范围内，玻璃化转变温度Tg在30℃～70℃范围内，热变形温度T 变形在50℃～90℃范围内，且Tg＜T 变形；
在所述聚氨酯基膜一侧表面制备胶层。
本申请实施方式中，所述的制备方法还包括在所述聚氨酯基膜的另一侧表面制备耐脏污自修复层。
本申请实施例第三方面提供一种保护膜贴合方法，包括：
将本申请实施例第一方面所述的保护膜通过所述胶层贴合在电子设备屏幕表面，然后加热软化所述保护膜，并通过加热的软胶模具使所述保护膜热压成型成与所述屏幕相匹配的形状。
本申请实施方式中，所述热压成型温度大于所述保护膜热变形温度，所述热压成型温度在50℃～90℃范围内。
本申请实施方式中，所述热压成型过程中，热压保压时间＞20s。
本申请实施例第四方面提供一种保护膜，用于保护电子设备的屏幕，所述保护膜包括第一聚氨酯基膜层和胶层，以及设置在所述第一聚氨酯基膜层和所述胶层之间的UV半固化层；
或者所述保护膜包括第一聚氨酯基膜层和胶层，设置在所述第一聚氨酯基膜层和所述胶层之间的UV半固化层，以及设置在所述胶层与所述UV半固化层之间的第二聚氨酯基膜层；
所述第一聚氨酯基膜层和所述第二聚氨酯基膜层的邵氏硬度在45D～75D范围内，玻璃化转变温度Tg≥30℃；
所述胶层用于与所述电子设备的屏幕粘合。
本申请实施方式中，所述第一聚氨酯基膜层和所述第二聚氨酯基膜层的杨氏模量在500Mpa～3Gpa范围内。
本申请实施方式中，所述保护膜为平面结构。
本申请实施方式中，所述第一聚氨酯基膜层和所述第二聚氨酯基膜层为聚氨酯丙烯酸酯膜层或热塑性聚氨酯膜层。
本申请实施方式中，所述第一聚氨酯基膜层和所述第二聚氨酯基膜层的厚度为15μm～150μm。
本申请实施方式中，所述UV半固化层为半固化聚氨酯丙烯酸酯层。
本申请实施方式中，所述半固化聚氨酯丙烯酸酯层包括含双键的聚氨酯丙烯酸酯。
本申请实施方式中，所述UV半固化层的厚度在30μm～150μm范围内。
本申请实施方式中，所述胶层为硅胶或丙烯酸胶。
本申请实施方式中，所述胶层的厚度为10μm～50μm。
本申请实施方式中，在剥离角度为180°条件下，所述胶层的剥离力大于800gf/25mm。
本申请实施方式中，所述保护膜还包括耐脏污自修复层，所述耐脏污自修复层设置在所述第一聚氨酯基膜层远离所述胶层的一侧。
本申请实施方式中，所述耐脏污自修复层为氟醚和/或氟碳类助剂掺杂的聚氨酯涂层，或氟醚和/或氟碳类助剂掺杂的聚氨酯丙烯酸树脂涂层。
本申请实施方式中，所述耐脏污自修复层的厚度为5μm～40μm。
本申请实施方式中，所述耐脏污自修复层的铅笔硬度500g载荷≥1H，所述耐脏污自修复层的水滴角≥90°。
本申请实施方式中，所述耐脏污自修复层的杨氏模量小于所述聚氨酯基膜层的杨氏模量。
本申请实施方式中，所述保护膜还包括设置在所述UV半固化层与所述胶层之间，或者设置在所述第二聚氨酯基膜层与所述胶层之间的底涂层，所述底涂层为硅烷改性的聚氨酯丙烯酸树脂涂层。
本申请实施方式中，所述保护膜还包括下离型层，所述下离型层设置在所述胶层远离所述第一聚氨酯基膜层的一侧表面。
本申请实施方式中，所述下离型层对10nm～400nm波长范围的光透过率＜10％。
本申请实施方式中，所述保护膜还包括上保护层，所述上保护层位于所述第一聚氨酯基膜层远离所述胶层的一侧。
本申请实施方式中，所述上保护层对10nm～400nm波长范围的光透过率＜10％。
本申请实施例还提供一种保护膜的制备方法，所述制备方法包括：
在PET载膜上制备第一聚氨酯基膜；所述第一聚氨酯基膜的邵氏硬度在45D～75D范围内，玻璃化转变温度Tg在30℃～70℃范围内；
在所述第一聚氨酯基膜一侧表面制备UV半固化层；
在UV半固化层上制备胶层。
本申请实施方式中，上述制备方法还包括在所述第一聚氨酯基膜远离所述胶层的一侧表面制备耐脏污自修复层。
本申请实施例还提供一种保护膜的制备方法，所述制备方法包括：
在PET载膜上制备第一聚氨酯基膜层；所述第一聚氨酯基膜层的邵氏硬度在45D～75D范围内，玻璃化转变温度Tg≥30℃；
在所述第一聚氨酯基膜层一侧表面制备UV半固化层；
在UV半固化层上制备第二聚氨酯基膜；所述第二聚氨酯基膜层的邵氏硬度在45D～75D范围内，玻璃化转变温度Tg≥30℃；
在所述第二聚氨酯基膜上制备胶层。
本申请实施方式中，上述制备方法还包括在所述第一聚氨酯基膜远离所述胶层的一侧表面制备耐脏污自修复层。
本申请实施例还提供一种保护膜贴合方法，包括：
在黄光作业环境下，将本申请实施例第四方面提供的所述的保护膜通过所述胶层贴合在电子设备屏幕表面，再采用UV光辐照使所述保护膜固化成型成与所述屏幕相匹配的形状。
本申请实施方式中，所述UV光辐照能量在1000mj/cm 2～3000mj/cm 2范围内。
本申请实施例还提供一种终端，所述终端包括显示屏和贴合在所述显示屏上的保护膜，所述保护膜为本申请实施例第一方面所述的保护膜或者为本申请实施例第四方面所述的保护膜，所述保护膜通过所述胶层贴合在所述显示屏的表面。其中，终端的显示屏可以为曲面显示屏，也可以为平面显示屏。本申请实施方式中，显示屏包括盖板玻璃，保护膜通过胶层贴合在盖板玻璃的表面，若显示屏为3D大角度的曲面显示屏，所述保护膜与所述盖板玻璃相匹配。
本申请实施例还提供一种终端，所述终端包括显示屏和贴合在所述显示屏上的保护膜，所述保护膜包括胶层和设置在所述胶层上的聚氨酯基膜层，所述保护膜通过所述胶层与所述显示屏粘合，所述聚氨酯基膜层的邵氏硬度在45D～75D范围内，玻璃化转变温度Tg在30℃～70℃范围内，热变形温度T 变形在50℃～90℃范围内，且Tg＜T 变形。
本申请实施例还提供一种终端，所述终端包括显示屏和贴合在所述显示屏上的保护膜，所述保护膜包括与所述显示屏粘合的胶层，设置在胶层上的完全固化的UV半固化层和设置在所述完全固化的UV半固化层上的第一聚氨酯基膜层，所述完全固化的UV半固化层为聚氨酯丙烯酸酯层，所述聚氨酯丙烯酸酯层和第一聚氨酯基膜层的邵氏硬度在45D～75D范围内，玻璃化转变温度Tg≥30℃。
本申请实施方式中，所述保护膜还包括设置在所述胶层与所述完全固化的UV半固化层之间的第二聚氨酯基膜层，所述第二聚氨酯基膜层的邵氏硬度在45D～75D范围内，玻璃化转变温度Tg≥30℃。
本申请实施例提供的保护膜，能够在贴合至屏幕表面时适应屏幕的形状成型，因此能够在3D大角度的曲面显示屏上完美地贴合，与显示屏形成紧密结合，不发生起翘反弹；本申请实施例提供的保护膜还具有高硬度和优异耐划伤性能，可以提升用户体验。
附图说明
图1是现有PET保护膜贴合至屏幕表面时产生贴合反弹的示意图；
图2是本申请一实施例提供的保护膜的截面结构示意图；
图3是本申请实施例提供的后热压贴合工艺制程示意图；
图4是本申请另一实施例提供的保护膜的截面结构示意图；
图5是本申请一实施例提供的保护膜的制备流程示意图；
图6是本申请一实施例提供的保护膜贴合流程示意图；
图7是本申请又一实施例提供的保护膜的截面结构示意图；
图8是本申请又一实施例提供的保护膜的截面结构示意图；
图9是本申请又一实施例提供的保护膜的截面结构示意图；
图10是本申请又一实施例提供的保护膜的截面结构示意图；
图11是本申请另一实施例提供的保护膜的制备流程示意图；
图12是本申请另一实施例提供的保护膜贴合流程示意图；
图13是本申请实施例提供的终端的结构示意图；
图14是本申请实施例提供的保护膜在曲面显示屏表面的贴合终示意图；
图15、图16和图17是本申请实施例提供的保护膜贴合在显示屏表面的截面示意图。
具体实施方式
下面结合本申请实施例中的附图对本申请实施例进行描述。
如图2所示，本申请实施例提供一种保护膜10，用于贴附在电子设备的屏幕上，以保护屏幕免受外界伤害，其中，电子设备的屏幕具体可以是显示屏。该保护膜10可适用于2D、2.5D、3D显示屏，而且可适用于3D大角度显示屏。保护膜10包括聚氨酯基膜层11和设置在聚氨酯基膜层11一侧的胶层12。
本申请实施方式中，聚氨酯基膜层11作为保护膜主体材料层，可赋予保护膜机械力学、光学性能。聚氨酯基膜层11具有较高硬度，较高玻璃化转变温度Tg和较低热变形温度T 变形，其邵氏硬度在45D～75D范围内，玻璃化转变温度Tg在30℃～70℃范围内，热变形温度T 变形在50℃～90℃范围内，且Tg＜T 变形。
本申请实施例提供的保护膜10，聚氨酯基膜层11具有较高硬度，可以为保护膜层提供高耐磨和高耐划伤性能，同时聚氨酯基膜层11具有较高玻璃化转变温度Tg有利于获得硬度较高和抗划伤性能较好的膜层，而具有较低热变形温度T 变形可使保护膜能够适用后热压贴合工艺，解决保护膜因硬度提高带来的贴合反弹问题，从而使得保护膜兼具高硬度、优异耐划伤性能和良好贴合性能。相比业界常规保护膜，本申请实施例保护膜10可以在不牺牲保护膜硬度与耐划伤体验下，贴合3D大角度曲面显示屏，与显示屏CG(cover glass，盖板玻璃)形成紧密结合，不发生反弹起翘，使保护膜很好地保护到显示屏的弧面区域。
具体地，本申请实施方式中，如图3所示，后热压贴合工艺具体是将保护膜10先贴合在屏幕101表面，然后将保护膜10加热软化，再通过仿形热压软胶模具102作为“母模”，屏幕CG盖板101作为“公模”，将保护膜10热压成型，使保护膜10完好贴合在CG盖板101表面。由于后热压贴合工艺是将保护膜贴合到屏幕表面之后再热压成型成与屏幕相匹配的形状，因此可以更好地与屏幕匹配结合，有效避免现有技术中将提前热压成型成与屏幕相匹配的形状的保护膜贴合到屏幕表面时，由于保护膜与屏幕弧度不匹配导致的贴合反 弹，同时还可以减少保护膜相对屏幕边缘的内缩距离，提高外观精致度。
本申请实施方式中，保护膜10为平面结构，是一种平面保护膜。
本申请实施方式中，当保护膜10贴合至屏幕表面时，胶层12远离聚氨酯基膜层11的一侧与屏幕粘合。
本申请实施方式中，聚氨酯基膜层11的硬度可通过邵氏硬度计测试获得，聚氨酯基膜层11的邵氏硬度还可以是在50D～70D范围内。玻璃化转变温度可以通过差示扫描量热法(Differential scanning calorimetry，DSC)测试获得，玻璃化转变温度Tg还可以是在40℃～60℃范围内。热变形温度T 变形可通过ISO75-2标准测试，热变形温度T 变形还可以是在50℃～80℃范围内。其中，较低热变形温度，有利于保证在后热压工艺过程中电子设备整机可耐受。
本申请一些实施方式中，聚氨酯基膜层11的杨氏模量在500Mpa～3Gpa范围内，本申请另一些实施方式中，聚氨酯基膜层11的杨氏模量可以是在1Gpa～2Gpa范围内。控制杨氏模量在适合范围，既能保证保护膜具有一定弹性，又能够有效避免保护膜在贴合时因弧度不匹配产生太大反弹应力，导致发生贴合反弹。
本申请实施方式中，聚氨酯基膜层11可以是聚氨酯丙烯酸酯(PUA，Polyurethane acrylate)膜层，也可以是热塑性聚氨酯(TPU，Thermoplastic polyurethanes)膜层。
本申请一些实施方式中，聚氨酯基膜层11为聚氨酯丙烯酸酯膜层，聚氨酯丙烯酸酯膜层可经涂布成型。具体地，制备聚氨酯丙烯酸酯膜层的原料可包括刚性异氰酸酯、韧性异氰酸酯、多元醇、丙烯酸羟基酯、光引发剂和偶联剂。其中，刚性异氰酸酯可提升PUA硬度与模量，韧性异氰酸酯可赋予PUA基膜优异韧性。多元醇可赋予PUA基膜回弹特性与延展性。丙烯酸羟基酯作为扩链剂，可调节PUA基膜交联密度，控制PUA基膜光学性能与热变形温度。
其中，刚性异氰酸酯可包括异佛尔酮二异氰酸酯(IPDI)、苯二亚甲基二异氰酸酯(XDI)、甲基环己基二异氰酸酯(HTDI)、降冰片烷二异氰酸酯(NBDI)、4，4‐二环己基甲烷二异氰酸酯(H12MDI)、四甲基间苯二亚甲基二异氰酸酯(TMXDI)中一种或多种。韧性异氰酸酯可包括己二异氰酸酯(HDI)、三甲基己二异氰酸酯(TMDI)、环己烷二亚甲基二异氰酸酯(HXDI)中的一种或多种。多元醇可包括聚酯多元醇、聚己内酯多元醇、聚碳酸酯二醇中的一种或多种。丙烯酸羟基酯可包括丙烯酸羟乙酯、三丙二醇二丙烯酸酯、季戊四醇二丙烯酸酯、三羟基甲基丙烷三丙烯酸酯、季戊四醇三丙烯酸酯中的一种或多种。光引发剂可包括2,4,6(三甲基苯甲酰基)二苯基氧化膦、2-甲基-1-[4-甲硫基苯基]-2-吗啉基-1-丙酮、1-羟基-环已基-苯基甲酮、1-羟基-环已基-苯基甲酮、4-氯二苯甲酮和邻苯甲酰苯甲酸甲酯中的一种或多种。偶联剂可包括聚甲基硅氧烷、γ-甲基丙烯酰氧基丙基三甲氧基硅烷、γ-氨丙基三甲氧基硅烷、γ-缩水甘油醚氧丙基三甲氧基硅烷中的一种或多种。
本申请另一些实施方式中，聚氨酯基膜层11为热塑性聚氨酯膜层，热塑性聚氨酯膜层可经流延成型。具体地，制备热塑性聚氨酯膜层的原料包括热塑性聚氨酯粒子、抗氧化剂、光阻胺稳定剂和增塑剂。其中，热塑性聚氨酯粒子可以是由二环己基甲烷二异氰酸酯(H12MDI)、二异氰酸酯(HDI)、聚己内酯多元醇以及扩链剂合成。
在本申请一些实施方式中，聚氨酯基膜层11的厚度可以是30μm～200μm。在本申请另一些实施方式中，聚氨酯基膜层11的厚度也可以是50μm～120μm。在本申请其他一些实施 方式中，聚氨酯基膜层11的厚度也可以是80μm～100μm。
在本申请实施方式中，胶层12的材质为压敏胶，具体可以是硅胶或丙烯酸胶。在本申请一些实施方式中，胶层12的厚度可以是10μm～50μm。在本申请一些实施方式中，胶层12的厚度可以是20μm～30μm。其中，在剥离角度为180°条件下，胶层12的剥离力大于800gf/25mm。
如图4所示，在本申请一些实施方式中，为了赋予保护膜耐脏污(低表面能和高水滴角)和自修复(高回弹性)性能，保护膜10还可以包括设置在聚氨酯基膜层11远离胶层12一侧的耐脏污自修复层13。耐脏污自修复层13可以是氟醚和/或氟碳类助剂掺杂的聚氨酯(PU,polyurethane)涂层，也可以是氟醚和/或氟碳类助剂掺杂的聚氨酯丙烯酸树脂(PUA)涂层。耐脏污自修复层13可以是涂布后经光固化或热固化形成。其中，制备聚氨酯丙烯酸树脂的原料可以是包括二异氰酸酯、多元醇、丙烯酸羟基酯、光引发剂和偶联剂。氟醚和氟碳类助剂的选择不限，可为现有常用的防指纹、耐脏污材料，具体可以是氟硅烷、全氟聚醚硅烷、全氟聚醚醇、氟碳硅烷、氟碳醇中的一种或多种。在本申请一些实施方式中，耐脏污自修复层13的厚度可以是5μm～40μm。在本申请另一些实施方式中，耐脏污自修复层13的厚度也可以是10μm～30μm，还可以是15μm～20μm。耐脏污自修复层13的铅笔硬度500g载荷可以是≥1H，水滴角可以是≥90°。在一些实施方式中，耐脏污自修复层13的水滴角可以是≥105°。
本申请实施方式中，耐脏污自修复层13的杨氏模量比聚氨酯基膜层11的杨氏模量低，回弹性好。具体地，耐脏污自修复层13的杨氏模量可以是50Mpa～800Mpa，还可以是100Mpa～600Mpa。
在本申请一具体实施方式中，耐脏污自修复层可以是由己二异氰酸酯、三甲基己二异氰酸酯、聚己内酯多元醇、氟硅烷、丙烯酸羟乙酯、2,4,6(三甲基苯甲酰基)二苯基氧化膦通过UV固化形成。其中，己二异氰酸酯为高韧性己二异氰酸酯，聚己内酯多元醇选择为高弹的聚己内酯多元醇。
如图4所示，本申请一些实施方式中，为增强保护膜在屏幕表面的附着力，还可以在聚氨酯基膜层11与胶层12之间设置底涂层14，底涂层14具有高交联度，底涂层14可以是硅烷改性的聚氨酯丙烯酸树脂涂层，厚度为1μm～20μm。进一步地，厚度可以是1μm～5μm。硅烷改性剂可以但不限于是甲基硅氧烷、甲基三乙酰基硅烷。硅烷改性剂化学接枝在聚氨酯丙烯酸酯上。
如图4所示，本申请一些实施方式中，保护膜10还包括下离型层15，下离型层15设置在胶层远离聚氨酯基膜层11的一侧表面。下离型层15的材质可以为PET或PP(Polypropylene，聚丙烯)，厚度可以是在23μm～75μm范围内，厚度还可以是38μm～50μm。下离型层15上设有向外延伸的延伸部，用于与胶层撕离。
如图4所示，本申请一些实施方式中，保护膜10还包括上保护层16，上保护层16位于聚氨酯基膜层11远离胶层12的一侧，当保护膜10包括耐脏污自修复层13时，上保护层16设置于耐脏污自修复层13的一侧表面上。上保护层16的材质可以为PET或PP，厚度可以是在23μm～75μm范围内，厚度还可以是38μm～50μm。上保护层16上设有向外延伸的延伸部，便于撕离。
本申请实施方式中，保护膜10的总厚度可以是70μm～300μm。
本申请实施方式中，上述保护膜10可通过如下方式制备得到：
提供或制备聚氨酯基膜(PU基膜)；聚氨酯基膜的邵氏硬度在45D～75D范围内，玻璃化转变温度Tg在30℃～70℃范围内，热变形温度T 变形在50℃～90℃范围内，且Tg＜T 变形；
在聚氨酯基膜一侧表面制备胶层。
本申请一些实施方式中，上述制备方法还包括在聚氨酯基膜的另一侧表面制备耐脏污自修复层。在本申请实施方式中，上述制备方法还可以根据需要进一步包括制备其他膜层结构。在本申请一些实施方式中，上述制备方法还包括在耐脏污自修复层上设置上保护层，在胶层与聚氨酯基膜层之间制备底涂层，在胶层远离聚氨酯基膜层一侧设置下离型层。
本申请实施方式中，制备PU基膜的方法可以是涂布成型PUA基膜或流延成型TPU基膜。本申请实施方式中，制备耐脏污自修复层的方法可以是将耐脏污自修复液经涂布固化制备。其中耐脏污自修复液包括氟醚和/或氟碳、以及聚氨酯或聚氨酯丙烯酸树脂原料。其中，聚氨酯丙烯酸树脂原料可以是包括二异氰酸酯、多元醇、丙烯酸羟基酯、光引发剂和偶联剂。氟醚和氟碳的选择不限，可为现有常用的防指纹、耐脏污材料，具体可以是氟硅烷、全氟聚醚硅烷、全氟聚醚醇、氟碳硅烷、氟碳醇中的一种或多种。
本申请实施方式中，胶层可以是涂布制备。本申请实施方式中，制备底涂层的方法可以是将底涂液经涂布制备。底涂液可包括硅烷改性剂，聚氨酯丙烯酸树脂齐聚物、扩链剂、流平剂、引发剂和溶剂。溶剂可以是异丙醇、乙醇、乙酸乙酯、乙酸丁酯、甲苯、二甲苯、丁酮、甲基异丁基酮中的一种或多种的混合。
如图5所示，在本申请一具体实施方式中，上述保护膜10可通过如下方式制备得到：
步骤一、涂布成型PUA基膜或流延成型TPU基膜，得到PU基膜；
步骤二、在PU基膜表面涂布耐脏污自修复液，固化后得到耐脏污自修复层；
步骤三、在PU基膜未设置耐脏污自修复层的一侧表面涂布压敏胶，高温熟化后形成胶层；
步骤四、在胶层上覆盖下离型膜，以及在耐脏污自修复层上覆盖上保护膜，形成上保护层和下离型层，收卷获得保护膜卷料；
步骤五、将保护膜卷料通过刀模模切出对应的电子设备屏幕保护膜外形；模切后，在上保护层与下离型层贴撕手膜，获得保护膜单体成品。
相应地，如图6所示，本申请实施例还提供了上述保护膜的贴合方法，包括：
将保护膜通过胶层贴合在电子设备屏幕表面，然后加热软化保护膜，并通过加热的软胶模具使保护膜热压成型成与屏幕相匹配的形状。
本申请实施方式中，上述贴合方法的热压成型过程中，热压成型温度大于保护膜热变形温度，其中，热压成型温度在50℃～90℃范围内，热压保压时间＞20s，具体例如可以是30s～90s。本申请实施例保护膜具有较低热变形温度，因此热压成型温度也可以相应控制在较低温度，这样可保证在热压工艺过程中电子设备整机可耐受。
其中，将保护膜通过胶层贴合在电子设备屏幕表面的操作可以使用贴膜治具或设备完成。热压成型采用的软胶模具为仿形软胶模具，仿形软胶模具与保护膜接触的一侧具有与待贴保护膜的屏幕表面相似或一致的形状。仿形软胶模具具体可以是仿形硅胶软头。
本申请一实施方式中，将保护膜首先贴合3D大弧度显示屏平面区域，再通过加热的仿形硅胶软头，对显示屏弧面区域的保护膜进行充分的加热成型，通过热压压力激活胶层的压敏胶，使保护膜贴合在3D大角度显示屏表面。
可以理解地，当保护膜具有下离型层和上保护层时，在贴合时，需先将下离型层撕除，然后将胶层贴合在屏幕表面；热压成型后，再将上保护层撕除。
本申请实施例提供的保护膜，通过将保护膜贴合至屏幕表面之后，再采用热压工艺使保护膜成型，从而可以使保护膜能更好地适应曲面显示屏的弯曲弧度，与曲面显示屏弧度完全吻合，因此本申请保护膜配合后热压成型可以适用更大角度的3D曲面显示屏贴合。本申请实施例提供的保护膜还具有高硬度和优异耐划伤性能，可以提升用户使用体验。
如图7所示，本申请实施例还提供一种保护膜20，用于贴附在电子设备的屏幕上，以保护屏幕免受外界伤害。其中，电子设备的屏幕具体可以是显示屏。该保护膜20适用于2D、2.5D、3D显示屏，而且可适用于3D大角度显示屏。在本申请一些实施方式中，保护膜20包括第一聚氨酯基膜层21和胶层201，以及设置在第一聚氨酯基膜层21和胶层22之间的UV半固化层23。
如图8所示，本申请另一些实施方式中，保护膜20包括第一聚氨酯基膜层21和胶层201，设置在第一聚氨酯基膜层21和胶层22之间的UV半固化层23，以及设置在胶层22与UV半固化层23之间的第二聚氨酯基膜层24。
本申请实施方式中，第一聚氨酯基膜层21和第二聚氨酯基膜层24作为保护膜主体材料层，可赋予保护膜机械力学、光学性能。第一聚氨酯基膜层21和第二聚氨酯基膜层24具有较高硬度和玻璃化转变温度Tg，其邵氏硬度在45D～75D范围内，玻璃化转变温度Tg≥30℃。
本申请实施例提供的保护膜20，第一聚氨酯基膜层21和第二聚氨酯基膜层24具有较高硬度和较高玻璃化转变温度Tg有利于为保护膜提供高硬度和优异耐磨、抗划伤性能，而设置UV半固化层，可以使保护膜在贴合至屏幕表面之前的硬度降低，同时可以使保护膜适用后UV辐照贴合工艺，提高保护膜贴合性能，有效解决保护膜因硬度提高带来的贴合反弹问题，从而使得保护膜兼具高硬度、优异耐划伤性能和良好贴合性能。因此，相比业界常规保护膜，本申请实施例保护膜20可以在不牺牲保护膜硬度与耐划伤体验下，贴合3D大角度曲面显示屏，与显示屏CG(cover glass，盖板玻璃)形成紧密结合，不发生反弹起翘，使保护膜很好地保护到显示屏的弧面区域。
本申请实施例提供的保护膜20，通过构建“PU基膜层-UV半固化层-胶层”或“PU基膜层-UV半固化层-PU基膜层-胶层”复合膜体系，由于UV半固化层为未完全固化的半固化状态，因此可以使保护膜在贴合至屏幕表面之前的硬度与模量降低，提高保护膜在大角度3D屏幕表面贴合性，而经UV辐照固化UV半固化层，使保护膜原位固化成型，又可在保护膜贴合至屏幕表面之后提高保护膜硬度与防护性能，因此可使得保护膜20兼具高硬度、优异耐划伤性能和良好贴合性能。
具体地，本申请实施方式中，后UV辐照贴合工艺具体是将保护膜先贴合在屏幕表面，然后采用UV光辐照使保护膜固化成型，从而使保护膜完好贴合在CG盖板表面。由于后UV辐照贴合工艺是将保护膜贴合到屏幕表面之后再固化成型成与屏幕相匹配的形状，因此 可以更好地与屏幕匹配结合，有效避免现有技术中将提前热压成型成与屏幕相匹配的形状的保护膜贴合到屏幕表面时，由于保护膜与屏幕弧度不匹配导致的贴合反弹，可使得保护膜在与曲面显示屏粘结时更加牢靠，同时还可以减少保护膜相对屏幕边缘的内缩距离，提高外观精致度。
本申请实施方式中，保护膜20为平面结构，是一种平面保护膜。
本申请实施方式中，当保护膜20贴合至屏幕表面时，胶层22远离第一聚氨酯基膜层21的一侧与电子设备的屏幕粘合。
本申请实施方式中，第一聚氨酯基膜层21和第二聚氨酯基膜层24的硬度可通过邵氏硬度计测试获得，第一聚氨酯基膜层21和第二聚氨酯基膜层24的邵氏硬度可以是在50D～70D范围内。玻璃化转变温度可以通过差示扫描量热法测试获得，玻璃化转变温度Tg可以是在30℃～70℃范围内。
本申请一些实施方式中，第一聚氨酯基膜层21和第二聚氨酯基膜层24的杨氏模量控制在500Mpa～3Gpa范围内。本申请另一些实施方式中，第一聚氨酯基膜层21和第二聚氨酯基膜层24的杨氏模量可以是在1Gpa～2Gpa范围内。控制杨氏模量在适合范围，既能保证保护膜具有一定弹性，又能够有效避免保护膜在贴合时因弧度不匹配产生太大反弹应力，导致发生贴合反弹。
本申请实施方式中，第一聚氨酯基膜层21和第二聚氨酯基膜层24可以是聚氨酯丙烯酸酯(PUA)膜层，也可以是热塑性聚氨酯(TPU)膜层。
本申请一些实施方式中，第一聚氨酯基膜层21和第二聚氨酯基膜层24为聚氨酯丙烯酸酯膜层，聚氨酯丙烯酸酯膜层可经涂布成型。具体地，制备聚氨酯丙烯酸酯膜层的原料可包括刚性异氰酸酯、韧性异氰酸酯、多元醇、丙烯酸羟基酯、光引发剂和偶联剂。其中，刚性异氰酸酯可提升PUA硬度与模量，韧性异氰酸酯可赋予PUA基膜优异韧性。多元醇可赋予PUA基膜回弹特性与延展性。丙烯酸羟基酯作为扩链剂，可调节PUA基膜交联密度，控制PUA基膜光学性能与热变形温度。
其中，刚性异氰酸酯可包括异佛尔酮二异氰酸酯(IPDI)、苯二亚甲基二异氰酸酯(XDI)、甲基环己基二异氰酸酯(HTDI)、降冰片烷二异氰酸酯(NBDI)、4，4‐二环己基甲烷二异氰酸酯(H12MDI)、四甲基间苯二亚甲基二异氰酸酯(TMXDI)中一种或多种。韧性异氰酸酯可包括己二异氰酸酯(HDI)、三甲基己二异氰酸酯(TMDI)、环己烷二亚甲基二异氰酸酯(HXDI)中的一种或多种。多元醇可包括聚酯多元醇、聚己内酯多元醇、聚碳酸酯二醇中的一种或多种。丙烯酸羟基酯可包括丙烯酸羟乙酯、三丙二醇二丙烯酸酯、季戊四醇二丙烯酸酯、三羟基甲基丙烷三丙烯酸酯、季戊四醇三丙烯酸酯中的一种或多种。光引发剂可包括2,4,6(三甲基苯甲酰基)二苯基氧化膦、2-甲基-1-[4-甲硫基苯基]-2-吗啉基-1-丙酮、1-羟基-环已基-苯基甲酮、1-羟基-环已基-苯基甲酮、4-氯二苯甲酮和邻苯甲酰苯甲酸甲酯中的一种或多种。偶联剂可包括聚甲基硅氧烷、γ-甲基丙烯酰氧基丙基三甲氧基硅烷、γ-氨丙基三甲氧基硅烷、γ-缩水甘油醚氧丙基三甲氧基硅烷中的一种或多种。
本申请另一些实施方式中，第一聚氨酯基膜层21和第二聚氨酯基膜层24为热塑性聚氨酯膜层，热塑性聚氨酯膜层可经流延成型。具体地，制备热塑性聚氨酯膜层的原料包括热塑性聚氨酯粒子、抗氧化剂、光阻胺稳定剂和增塑剂。其中，热塑性聚氨酯粒子可以是 由二环己基甲烷二异氰酸酯(H12MDI)、二异氰酸酯(HDI)、聚己内酯多元醇以及扩链剂合成。
在本申请一些实施方式中，第一聚氨酯基膜层21和第二聚氨酯基膜层24的厚度可以是15μm～150μm。在本申请另一些实施方式中，第一聚氨酯基膜层21和第二聚氨酯基膜层24的厚度也可以是20μm～120μm。在本申请其他一些实施方式中，第一聚氨酯基膜层21和第二聚氨酯基膜层24的厚度也可以是30μm～100μm，或40μm～80μm。
本申请实施方式中，第一聚氨酯基膜层21和第二聚氨酯基膜层24的材料和厚度可以是相同，也可以是不相同。
本申请实施方式中，UV半固化层23为半固化聚氨酯丙烯酸酯层，即未完全固化的聚氨酯丙烯酸酯层。UV半固化层23包括含活性官能团(如双键)的聚氨酯丙烯酸酯。UV半固化层23的UV光辐照预聚能量在10mj/cm 2～500mj/cm 2范围内。UV半固化层固化前模量低，有利于提升贴合性能，完全固化后模量高，有利于提升可靠性与用户体验。UV半固化层23完全固化后邵氏硬度在45D～75D范围内，玻璃化转变温度Tg≥30℃。
本申请一些实施方式中，UV半固化层23的厚度在30μm～150μm范围内。本申请另一些实施方式中，UV半固化层23的厚度在50μm～80μm范围内。
在本申请一些实施方式中，也可以再进一步增设第三聚氨酯基膜层、以及再增设一层UV半固化层，构建PU基膜层-UV半固化层-PU基膜层-UV半固化层-PU基膜层-胶层”复合膜体系。
在本申请实施方式中，胶层22的材质为压敏胶，具体可以是硅胶或丙烯酸胶。在本申请一些实施方式中，胶层22的厚度可以是10μm～50μm。在本申请一些实施方式中，胶层22的厚度可以是20μm～30μm。其中，在剥离角度为180°条件下，胶层的剥离力大于800gf/25mm。
如图9和图10所示，在本申请一些实施方式中，为了赋予保护膜耐脏污(低表面能和高水滴角)和自修复(高回弹性)性能，保护膜20还可以包括设置在第一聚氨酯基膜层21远离胶层22一侧的耐脏污自修复层25。耐脏污自修复层25可以是氟醚和/或氟碳类助剂掺杂的聚氨酯涂层，也可以是氟醚和/或氟碳类助剂掺杂的聚氨酯丙烯酸树脂涂层。其中，聚氨酯丙烯酸树脂的原料可以是包括二异氰酸酯、多元醇、丙烯酸羟基酯、光引发剂和偶联剂。氟醚、氟碳的选择不限，可为现有常用的防指纹、耐脏污材料，具体可以是氟硅烷、全氟聚醚硅烷、全氟聚醚醇、氟碳硅烷、氟碳醇中的一种或多种。在本申请一些实施方式中，耐脏污自修复层25的厚度可以是5μm～40μm。在本申请另一些实施方式中，耐脏污自修复层25的厚度也可以是10μm～30μm，还可以是15μm～20μm。耐脏污自修复层25的铅笔硬度500g载荷可以是≥1H，水滴角可以是≥90°。在一些实施方式中，耐脏污自修复层25的水滴角可以是≥105°。
在本申请一些具体实施方式中，耐脏污自修复层25可以是由己二异氰酸酯、三甲基己二异氰酸酯、聚己内酯多元醇、氟硅烷、丙烯酸羟乙酯、2,4,6(三甲基苯甲酰基)二苯基氧化膦通过UV固化形成。其中，己二异氰酸酯为高韧性己二异氰酸酯，聚己内酯多元醇选择为高弹的聚己内酯多元醇。
本申请实施方式中，耐脏污自修复层25的杨氏模量小于第一聚氨酯基膜层21和第二 聚氨酯基膜层24的杨氏模量，回弹性好。具体地，耐脏污自修复层25的杨氏模量可以是50Mpa～800Mpa，还可以是100Mpa～600Mpa。
本申请一些实施方式中，为增强保护膜在屏幕表面的附着力，UV半固化层23与胶层22之间，或者第二聚氨酯基膜层24与胶层22之间还可以设置有底涂层，底涂层为硅烷改性的聚氨酯丙烯酸树脂涂层，厚度可以是1μm～20μm。进一步地，底涂层厚度可以是1μm～5μm。
如图9和图10所示，本申请一些实施方式中，保护膜20还包括下离型层26，下离型层26设置在胶层22远离第一聚氨酯基膜层21的一侧表面。下离型层26的材质可以为PET或PP，厚度可以是在23μm～75μm范围内，也可以是38μm～50μm。下离型层26具有紫外光屏蔽性能，对10nm～400nm波长范围的光透过率＜10％。下离型层26具有紫外光屏蔽性能可以保护保护膜免受紫外光的影响，保证在贴合至屏幕之前UV半固化层23为半固化状态。下离型层上设有向外延伸的延伸部，用于与胶层撕离。
如图9和图10所示，本申请一些实施方式中，保护膜10还包括上保护层27，上保护层27位于聚氨酯基膜层远离胶层的一侧表面。上保护层27的材质可以为PET或PP，厚度可以是在23μm～75μm范围内，也可以是38μm～50μm。上保护层27具有紫外光屏蔽性能，对10nm～400nm波长范围的光透过率＜10％。上保护层27具有紫外光屏蔽性能可以保护保护膜免受紫外光的影响，保证在贴合至屏幕之前UV半固化层23为半固化状态。上保护层上设有向外延伸的延伸部，便于撕离。
本申请实施方式中，保护膜20的总厚度可以是70μm～300μm。
本申请一实施例提供了一种保护膜20的制备方法，包括：
在PET载膜上制备第一聚氨酯基膜；所述第一聚氨酯基膜的邵氏硬度在45D～75D范围内，玻璃化转变温度Tg≥30℃；
在第一聚氨酯基膜一侧表面制备UV半固化层；
在UV半固化层上制备胶层。
本申请另一实施例提供了一种保护膜20的制备方法，包括：
在PET载膜上制备第一聚氨酯基膜层；所述第一聚氨酯基膜层的邵氏硬度在45D～75D范围内，玻璃化转变温度Tg≥30℃；
在第一聚氨酯基膜层一侧表面制备UV半固化层；
在UV半固化层上制备第二聚氨酯基膜；第二聚氨酯基膜层的邵氏硬度在45D～75D范围内，玻璃化转变温度Tg≥30℃；
在第二聚氨酯基膜上制备胶层。
本申请上述实施方式中，其制备方法还包括在第一聚氨酯基膜远离胶层的一侧表面制备耐脏污自修复层。
在本申请实施方式中，上述制备方法还可以根据需要进一步包括制备其他膜层结构。在本申请一些实施方式中，上述制备方法还包括在耐脏污自修复层上设置上保护层，在胶层远离第一聚氨酯基膜层一侧设置下离型层。在本申请一些实施方式中，上述制备方法还包括在UV半固化层与胶层之间，或者在第二聚氨酯基膜层与胶层之间制备底涂层。
本申请实施方式中，制备第一PU基膜和第二PU基膜的方法可以是涂布成型PUA基 膜或流延成型TPU基膜。本申请实施方式中，制备耐脏污自修复层的方法可以是将耐脏污自修复液经涂布制备。其中耐脏污自修复液可包括氟醚和/或氟碳，以及聚氨酯或聚氨酯丙烯酸树脂原料。其中，聚氨酯丙烯酸树脂原料可以是包括二异氰酸酯、多元醇、丙烯酸羟基酯、光引发剂和偶联剂。氟醚、氟碳的选择不限，可为现有常用的防指纹、耐脏污材料，具体可以是氟硅烷、全氟聚醚硅烷、全氟聚醚醇、氟碳硅烷、氟碳醇中的一种或多种。本申请实施方式中，胶层可以是涂布制备。本申请实施方式中，制备底涂层的方法可以是将底涂液经涂布制备。底涂液可包括硅烷改性剂，聚氨酯丙烯酸树脂齐聚物、扩链剂、流平剂、引发剂和溶剂。溶剂可以是异丙醇、乙醇、乙酸乙酯、乙酸丁酯、甲苯、二甲苯、丁酮、甲基异丁基酮中的一种或多种的混合。
本申请一具体实施方式中，如图11所示，上述保护膜可通过如下方式制备得到：
步骤一、在PET载膜表面形成第一PU基膜层，具体可以是涂布并经UV辐照形成PUA基膜层，或者流延形成TPU基膜层；
步骤二、在第一PU基膜层表面涂布耐脏污自修复液，固化后形成耐脏污自修复层；
步骤三、在耐脏污自修复层一侧覆膜PET载膜，撕除第一PU基膜层一侧的PET载膜，在第一PU基膜层表面涂布UV半固化层材料，经UV辐照固化后形成UV半固化层；
步骤四、在UV半固化层表面形成第二PU基膜层，具体可以是涂布并经UV辐照形成PUA基膜层，或者流延形成TPU基膜层；
步骤五、在第二PU基膜层表面涂布压敏胶，高温熟化后形成胶层；
步骤六、在胶层上覆盖下离型膜，撕除耐脏污自修复层一侧PET载膜，并在耐脏污自修复层上覆盖上保护膜，形成上保护层和下离型层，收卷获得保护膜卷料；
步骤七、在黄光作业环境下，将保护膜卷料通过刀模模切出对应的电子设备屏幕保护膜外形；模切后，在上保护层与下离型层贴撕手膜，获得保护膜单体成品。
其中，UV半固化层材料为聚氨酯丙烯酸酯原料，可以是与第一PU基膜层原料相同或不同。辐照固化形成UV半固化层时，采用低功率UV辐照，具体地，低功率UV辐照的辐照能量可以是10mj/cm 2～500mj/cm 2。
可以理解地，当保护膜不包括第二PU基膜层时，省去上述制备方法中的步骤四，直接在UV半固化层上制备胶层即可。
相应地，如图12所示，本申请实施例还提供了上述保护膜的贴合方法，包括：
在黄光作业环境下，将保护膜20通过胶层22贴合在电子设备屏幕表面，再采用UV光辐照使保护膜20固化成型成与屏幕相匹配的形状。
本申请实施方式中，上述贴合方法中，UV光辐照能量在1000mj/cm 2～3000mj/cm 2范围内。
其中，将保护膜通过胶层贴合在电子设备屏幕表面的操作可以使用贴膜治具或设备完成。
可以理解地，当保护膜具有下离型层和上保护层时，在贴合时，需先将下离型层撕除，然后将胶层贴合在屏幕表面；在将保护膜贴合至屏幕后，UV光辐照之前，将上保护层撕除。其中，撕下离型层、贴合保护膜和撕上保护层的操作均在黄光作业环境下进行。
本申请实施例提供的保护膜，通过将保护膜贴合至屏幕表面之后，再采用UV光辐照 使保护膜固化成型，从而可以使保护膜能更好地适应曲面显示屏的弯曲弧度，与曲面显示屏完全吻合，因此本申请保护膜配合后UV辐照成型可以适应更大角度的3D曲面显示屏贴合。本申请实施例提供的保护膜还具有高硬度和优异耐划伤性能，可以提升用户使用体验。
如图13所示，本申请实施例还提供一种终端，该终端200可以是手机、也可以是平板电脑、笔记本电脑、便携机、智能穿戴产品等。终端200包括显示屏201、以及贴合在显示屏201表面的保护膜202，显示屏201包括设置在最外层的盖板玻璃，保护膜202通过胶层与盖板玻璃紧密结合在一起。
本申请实施方式中，显示屏201可以是曲面显示屏，也可以是平面显示屏。其中曲面显示屏可以是2.5D、3D曲面显示屏。
本申请实施方式中，由于保护膜202具有良好贴合性，当显示屏201为3D大角度曲面显示屏时，保护膜202可以更靠近显示屏的边缘贴合，减小保护膜相对显示屏201的内缩距离。如图14所示，保护膜202贴合在曲面显示屏201表面时，保护膜202的形状与显示屏相匹配，保护膜202仅存在公差范围内的内缩距离。具体地，保护膜202的内缩距离可以是小于或等于2mm，具体地内缩距离可以是0-1mm，例如0.3mm、0.8mm、1mm。保护膜202的形状与显示屏相匹配，不仅可以更好地实现对显示屏的保护，同时可以提高终端外观精致度。
本申请一实施方式中，保护膜202由保护膜10贴合形成，如图15所示，保护膜202包括胶层12和设置在胶层12上的聚氨酯基膜层11。本申请一些实施方式中，保护膜202还包括设置在聚氨酯基膜层11上的耐脏污自修复层13。本申请一些实施方式中，保护膜202还包括设置在聚氨酯基膜层11和胶层12之间的底涂层14。
本申请另一实施方式中，保护膜202由保护膜20贴合形成，如图16所示，保护膜202包括胶层22，设置在胶层22上的完全固化的UV半固化层23’和设置在完全固化的UV半固化层23’上的第一聚氨酯基膜层21。本申请一些实施方式中，保护膜202还包括设置在第一聚氨酯基膜层21上的耐脏污自修复层25。
本申请另一实施方式中，保护膜202由保护膜20贴合形成，如图17所示，保护膜202包括胶层22，设置在胶层22上的第二聚氨酯基膜层24，设置在第二聚氨酯基膜层24上的完全固化的UV半固化层23’和设置在完全固化的UV半固化层23’上的第一聚氨酯基膜层21。本申请一些实施方式中，保护膜202还包括设置在第一聚氨酯基膜层21上的耐脏污自修复层25。
其中，当保护膜20贴合至显示屏201表面时，经UV辐照后，UV半固化层23完全固化形成完全固化的UV半固化层23’。本申请实施方式中，完全固化的UV半固化层23’为完全固化的聚氨酯丙烯酸酯层。完全固化的UV半固化层23’的邵氏硬度在45D～75D范围内，玻璃化转变温度Tg≥30℃。
下面分多个具体实施例对本申请技术方案进行进一步阐述。
实施例一
保护膜制备方法及贴合方法：
(1)按重量份取异佛尔酮二异氰酸酯14份、己二异氰酸酯17份、聚己内酯多元醇 12份、聚酯多元醇16份、三羟基甲基丙烷三丙烯酸酯30份、丙烯酸羟乙酯25份、聚甲基硅氧烷4份、2,4,6(三甲基苯甲酰基)二苯基氧化膦1份、1-羟基-环已基-苯基甲酮1份制备PUA基膜涂布液，通过狭缝涂布UV辐照固化制备80μm厚度、65D硬度的高硬度PUA基膜。
(2)按重量份取苯二亚甲基二异氰酸酯12份、己二异氰酸酯25份、聚己内酯多元醇20份、聚酯多元醇10份、三羟基甲基丙烷三丙烯酸酯10份、丙烯酸羟乙酯15份、全氟聚醚硅烷0.5份、γ-甲基丙烯酰氧基丙基三甲氧基硅烷2份、2,4,6(三甲基苯甲酰基)二苯基氧化膦光引发剂1份、1-羟基-环已基-苯基甲酮0.5份制备耐脏污自修复液。在上述高硬度PUA基膜一侧涂布耐脏污自修复液，通过汞灯源UV光辐照固化，辐照计量2500mj/cm 2，在高硬度PUA膜一侧表面形成18μm厚度的耐脏污自修复层，获得耐脏污自修复层/高硬度PUA基膜；
(3)在耐脏污自修复层膜/高硬度PUA基膜的PUA层一侧涂布25μm厚度硅胶层，150℃熟化后覆50μm厚度的PET上保护膜与下离型膜，收卷获得保护膜卷料。
(4)将保护膜卷料通过刀模模切出对应的电子设备屏幕保护膜外形，内缩1.0mm，在上保护膜层与下离型层贴撕手膜，获得保护膜单体成品。
(5)将保护膜单体下离型层撕除，通过贴膜治具或设备，将保护膜贴合在手机3D大角度曲面显示屏表面，通过加热平台加热软化PU保护膜至膜面温度约60℃，通过加热软胶头热压成型30s，使保护膜紧密贴合在显示屏玻璃盖板上，最后撕除上保护膜层。
为了检测保护膜贴合效果，将上述保护膜贴合的手机放置在55℃、95％RH条件下72h，保护膜在3D大角度曲面显示屏的曲面位置未反弹起翘。
为了检测保护膜的表面性能，针对保护膜硬度、耐磨与耐脏污性能进行测试。具体地，保护膜500gf载荷铅笔硬度≥2H，500gf载荷铜刷摩擦(测试条件：日本OSAKA牌号铜刷，刷头4*6刷毛，行程20mm)50次后无掉膜与划伤；保护膜表面水滴角：109～112°。
实施例二
保护膜制备方法及贴合方法：
(1)按重量份取聚己内酯TPU粒子94份、抗氧化剂2份、光阻胺稳定剂1份、硅油增塑剂3份，在160℃～200℃温度下流延成型100μm厚度、64D硬度的高硬度TPU基膜。
(2)取实施例一制备的耐脏污自修复液，涂布在高硬度TPU基膜一侧表面，通过汞灯源UV光辐照固化，辐照计量2800mj/cm 2，在高硬度TPU基膜一侧表面形成24μm厚度耐脏污自修复层，获得耐脏污自修复层/高硬度TPU基膜。
(3)在耐脏污自修复层膜/高硬度TPU基膜的PU层一侧涂布20μm厚度的硅胶层，155℃熟化后覆50μm厚度的PET上保护膜与下离型膜，收卷获得保护膜卷料。
(4)将保护膜卷料通过刀模模切出对应的电子设备屏幕保护膜外形，内缩1.0mm，在上保护膜层与下离型层贴撕手膜，获得保护膜单体成品。
(5)将保护膜单体下离型层撕除，通过贴膜治具或设备，将保护膜贴合在手机3D大角度曲面显示屏表面，通过加热平台加热软化PU保护膜至膜面温度约55℃，通过加热软胶头热压成型40s，使保护膜紧密贴合在显示屏玻璃盖板上，最后撕除上保护膜层。
为了检测上述保护膜贴合效果，将上述保护膜贴合的手机放置在55℃、95％RH条件下72h，结果显示保护膜在3D大角度曲面显示屏的曲面位置未反弹起翘。
为了检测上述保护膜的表面性能，针对保护膜硬度、耐磨与耐脏污性能进行测试。具体地，保护膜500gf载荷铅笔硬度≥1H，500gf载荷铜刷摩擦(测试条件：日本OSAKA牌号铜刷，刷头4*6刷毛，行程20mm)50次后无掉膜与划伤；保护膜表面水滴角：110～112°。
实施例三
保护膜制备方法及贴合方法：
(1)按重量份取4，4-二环己基甲烷二异氰酸酯20份、己二异氰酸酯15份、聚己内酯多元醇20份、聚酯多元醇18份、季戊四醇二丙烯酸酯25份、丙烯酸羟乙酯25份、聚甲基硅氧烷4份、2,4,6(三甲基苯甲酰基)二苯基氧化膦光引发剂1份、1-羟基-环已基-苯基甲酮0.8份混合制备PUA基膜涂布液，在PET载膜上通过狭缝涂布UV辐照固化制备20μm厚度、68D硬度的高硬度PUA基膜。
(2)按重量份取4，4‐二环己基甲烷二异氰酸酯8份、己二异氰酸酯32份、聚己内酯多元醇35份、聚酯多元醇5份、三羟基甲基丙烷三丙烯酸酯15份、丙烯酸羟乙酯10份、全氟聚醚硅烷0.5份、γ-甲基丙烯酰氧基丙基三甲氧基硅烷2份、2,4,6(三甲基苯甲酰基)二苯基氧化膦光引发剂0.8份、1-羟基-环已基-苯基甲酮0.5份混合制备耐脏污自修复液。在上述高硬度PUA基膜一侧涂布耐脏污自修复液，通过汞灯源UV光辐照固化，辐照计量2500mj/cm 2，在高硬度PUA基膜一侧表面形成20μm厚度的耐脏污自修复层，再在耐脏污自修复层表面覆膜PET载膜，获得PET载膜/耐脏污自修复层/高硬度PUA基膜/PET载膜；
(3)撕除高硬度PUA基膜一侧的PET载膜，将4，4-二环己基甲烷二异氰酸酯20份、己二异氰酸酯15份、聚己内酯多元醇20份、聚酯多元醇18份、季戊四醇二丙烯酸酯25份、丙烯酸羟乙酯25份、聚甲基硅氧烷4份、2,4,6(三甲基苯甲酰基)二苯基氧化膦光引发剂1份、1-羟基-环已基-苯基甲酮0.8份混合制备UV半固化层涂布液，在高硬度PUA层一侧涂布UV半固化层涂布液，通过汞灯源UV光辐照固化，辐照计量500mj/cm 2，形成50μm厚度UV半固化层，最后在UV半固化层表面涂布25μm厚度硅胶层，150℃熟化后覆50μm厚度的PET上保护膜与下离型膜，收卷获得保护膜卷料。
(4)将保护膜卷料通过刀模模切出对应的电子设备屏幕保护膜外形，内缩1.0mm，在上保护膜层与下离型层贴撕手膜，获得保护膜单体成品。
(5)将保护膜单体下离型层撕除，通过贴膜治具或设备，将保护膜贴合在手机3D大角度曲面显示屏表面，然后撕除上保护膜层，再通过UV辐照对保护膜进行固化成型，辐照计量1800mj/cm 2。
为了检测上述得到的保护膜贴合质量，将上述保护膜贴合的手机放置在55℃、95％RH条件下72h，结果显示保护膜在3D大角度曲面显示屏的曲面位置未反弹起翘。
为了检测上述保护膜的表面性能，针对保护膜硬度、耐磨与耐脏污性能进行测试。具体地，保护膜500gf载荷铅笔硬度≥1H，500gf载荷铜刷摩擦(测试条件：日本OSAKA牌号铜刷，刷头4*6刷毛，行程20mm)50次后无掉膜与划伤；保护膜表面水滴角：108～111°。
实施例四：
保护膜制备方法及贴合方法：
(1)取实施例三制备的PUA基膜涂布液，在PET载膜上通过狭缝涂布UV辐照固化制备15μm厚度、70D硬度的高硬度PUA基膜。
(2)在高硬度PUA基膜一侧涂布实施例三制备的耐脏污自修复液，通过汞灯源UV光辐照固化，辐照计量2400mj/cm 2，在高硬度PUA膜一侧表面形成25μm厚度耐脏污自修复层，再在耐脏污自修复层表面覆膜PET载膜，获得PET载膜/耐脏污自修复层/高硬度PUA基膜/PET载膜。
(3)撕除高硬度PUA基膜一侧的PET载膜，在高硬度PUA基膜层一侧涂布实施例三制备的UV半固化层涂布液，通过汞灯源UV光辐照固化，辐照计量450mj/cm 2，形成60μm厚度的UV半固化层，最后在UV半固化层表面涂布20μm厚度硅胶层，150℃熟化后覆50μm厚度的PET上保护膜与下离型膜，收卷获得保护膜卷料。
(4)将保护膜卷料通过刀模模切出对应的电子设备屏幕保护膜外形，内缩0.8mm，在上保护膜层与下离型层贴撕手膜，获得保护膜单体成品。
(5)将保护膜单体下离型层撕除，通过贴膜治具或设备，将保护膜贴合在手机3D大角度曲面显示屏表面，然后撕除上保护膜层，再通过UV辐照对保护膜进行固化成型，辐照计量1500mj/cm 2。
为了检测上述得到的保护膜贴合质量，将上述保护膜贴合的手机放置在55℃、95％RH条件下72h，结果显示保护膜在3D大角度曲面显示屏的曲面位置未反弹起翘。
为了检测上述保护膜的表面性能，针对保护膜硬度、耐磨与耐脏污性能进行测试。具体地，保护膜500gf载荷铅笔硬度≥1H，500gf载荷铜刷摩擦(测试条件：日本OSAKA牌号铜刷，刷头4*6刷毛，行程20mm)50次后无掉膜与划伤；保护膜表面水滴角：110～111°。
以上具体实施例的测试结果表明，本申请实施例提供的保护膜，在3D大角度曲面显示屏表面贴合性能良好，且具有较高硬度与优异耐划伤性能，且针对大角度3D电子设备屏幕可实现小内缩保护膜贴合，保护膜贴合可以更靠近屏幕边缘，从而提升防护能力和外观精致度，提升用户体验。

Claims (54)

  1. 一种保护膜，用于保护电子设备的屏幕，其特征在于，所述保护膜包括聚氨酯基膜层和设置在所述聚氨酯基膜层一侧的胶层；
    所述聚氨酯基膜层的邵氏硬度在45D～75D范围内，玻璃化转变温度Tg在30℃～70℃范围内，热变形温度T 变形在50℃～90℃范围内，且Tg＜T 变形；
    所述胶层用于与所述电子设备的屏幕粘合。
  2. 如权利要求1所述的保护膜，其特征在于，所述聚氨酯基膜层的杨氏模量在500Mpa～3Gpa范围内。
  3. 如权利要求1或2所述的保护膜，其特征在于，所述保护膜为平面结构。
  4. 如权利要求1-3任一项所述的保护膜，其特征在于，所述聚氨酯基膜层为聚氨酯丙烯酸酯膜层或热塑性聚氨酯膜层。
  5. 如权利要求1-4任一项所述的保护膜，其特征在于，所述聚氨酯基膜层的厚度为30μm～200μm。
  6. 如权利要求1-5任一项所述的保护膜，其特征在于，所述胶层为硅胶或丙烯酸胶。
  7. 如权利要求1-6任一项所述的保护膜，其特征在于，所述胶层的厚度为10μm～50μm。
  8. 如权利要求1-7任一项所述的保护膜，其特征在于，在剥离角度为180°条件下，所述胶层的剥离力大于800gf/25mm。
  9. 如权利要求1-8任一项所述的保护膜，其特征在于，所述保护膜还包括耐脏污自修复层，所述耐脏污自修复层设置在所述聚氨酯基膜层远离所述胶层的一侧。
  10. 如权利要求9所述的保护膜，其特征在于，所述耐脏污自修复层为氟醚和/或氟碳类助剂掺杂的聚氨酯涂层，或氟醚和/或氟碳类助剂掺杂的聚氨酯丙烯酸树脂涂层。
  11. 如权利要求9或10所述的保护膜，其特征在于，所述耐脏污自修复层的厚度为5μm～40μm。
  12. 如权利要求9-11任一项所述的保护膜，其特征在于，所述耐脏污自修复层的铅笔硬度500g载荷≥1H，所述耐脏污自修复层的水滴角≥90°。
  13. 如权利要求9-12任一项所述的保护膜，其特征在于，所述耐脏污自修复层的杨氏模量小于所述聚氨酯基膜层的杨氏模量。
  14. 如权利要求1-13任一项所述的保护膜，其特征在于，所述保护膜还包括设置在所述聚氨酯基膜层与所述胶层之间的底涂层，所述底涂层为硅烷改性的聚氨酯丙烯酸树脂涂层。
  15. 如权利要求1-14任一项所述的保护膜，其特征在于，所述保护膜还包括下离型层，所述下离型层设置在所述胶层远离所述聚氨酯基膜层的一侧表面。
  16. 如权利要求1-15任一项所述的保护膜，其特征在于，所述保护膜还包括上保护层，所述上保护层位于所述聚氨酯基膜层远离所述胶层的一侧。
  17. 一种保护膜的制备方法，其特征在于，包括：
    提供或制备聚氨酯基膜；所述聚氨酯基膜的邵氏硬度在45D～75D范围内，玻璃化转变温度Tg在30℃～70℃范围内，热变形温度T 变形在50℃～90℃范围内，且Tg＜T 变形；
    在所述聚氨酯基膜一侧表面制备胶层。
  18. 如权利要求17所述的制备方法，其特征在于，还包括在所述聚氨酯基膜的另一侧表面制备耐脏污自修复层。
  19. 一种保护膜贴合方法，其特征在于，包括：
    将权利要求1-16任一项所述的保护膜通过所述胶层贴合在电子设备屏幕表面，然后加热软化所述保护膜，并通过加热的软胶模具使所述保护膜热压成型成与所述屏幕相匹配的形状。
  20. 如权利要求19所示的贴合方法，其特征在于，所述热压成型温度大于所述保护膜热变形温度，所述热压成型温度在50℃～90℃范围内。
  21. 如权利要求19所示的贴合方法，其特征在于，所述热压成型过程中，热压保压时间＞20s。
  22. 一种保护膜，用于保护电子设备的屏幕，其特征在于，所述保护膜包括第一聚氨酯基膜层和胶层，以及设置在所述第一聚氨酯基膜层和所述胶层之间的UV半固化层；
    或者所述保护膜包括第一聚氨酯基膜层和胶层，设置在所述第一聚氨酯基膜层和所述胶层之间的UV半固化层，以及设置在所述胶层与所述UV半固化层之间的第二聚氨酯基膜层；
    所述第一聚氨酯基膜层和所述第二聚氨酯基膜层的邵氏硬度在45D～75D范围内，玻璃化转变温度Tg≥30℃；
    所述胶层用于与所述电子设备的屏幕粘合。
  23. 如权利要求22所述的保护膜，其特征在于，所述第一聚氨酯基膜层和所述第二聚氨酯基膜层的杨氏模量在500Mpa～3Gpa范围内。
  24. 如权利要求22或23任一项所述的保护膜，其特征在于，所述保护膜为平面结构。
  25. 如权利要求22-24任一项所述的保护膜，其特征在于，所述第一聚氨酯基膜层和所述第二聚氨酯基膜层为聚氨酯丙烯酸酯膜层或热塑性聚氨酯膜层。
  26. 如权利要求22-25任一项所述的保护膜，其特征在于，所述第一聚氨酯基膜层和所述第二聚氨酯基膜层的厚度为15μm～150μm。
  27. 如权利要求22-26任一项所述的保护膜，其特征在于，所述UV半固化层为半固化聚氨酯丙烯酸酯层。
  28. 如权利要求27所述的保护膜，其特征在于，所述半固化聚氨酯丙烯酸酯层包括含双键的聚氨酯丙烯酸酯。
  29. 如权利要求22-28任一项所述的保护膜，其特征在于，所述UV半固化层的厚度在30μm～150μm范围内。
  30. 如权利要求22-29任一项所述的保护膜，其特征在于，所述胶层为硅胶或丙烯酸胶。
  31. 如权利要求22-30任一项所述的保护膜，其特征在于，所述胶层的厚度为10μm～50μm。
  32. 如权利要求22-31任一项所述的保护膜，其特征在于，在剥离角度为180°条件下，所述胶层的剥离力大于800gf/25mm。
  33. 如权利要求22-32任一项所述的保护膜，其特征在于，所述保护膜还包括耐脏污自修复层，所述耐脏污自修复层设置在所述第一聚氨酯基膜层远离所述胶层的一侧。
  34. 如权利要求33所述的保护膜，其特征在于，所述耐脏污自修复层为氟醚和/或氟碳类助剂掺杂的聚氨酯涂层，或氟醚和/或氟碳类助剂掺杂的聚氨酯丙烯酸树脂涂层。
  35. 如权利要求33或34所述的保护膜，其特征在于，所述耐脏污自修复层的厚度为5μm～40μm。
  36. 如权利要求33-35任一项所述的保护膜，其特征在于，所述耐脏污自修复层的铅笔硬度500g载荷≥1H，所述耐脏污自修复层的水滴角≥90°。
  37. 如权利要求33-36任一项所述的保护膜，其特征在于，所述耐脏污自修复层的杨氏模量小于所述第一聚氨酯基膜层的杨氏模量。
  38. 如权利要求22-37任一项所述的保护膜，其特征在于，所述保护膜还包括设置在所述UV半固化层与所述胶层之间，或者设置在所述第二聚氨酯基膜层与所述胶层之间的底涂层，所述底涂层为硅烷改性的聚氨酯丙烯酸树脂涂层。
  39. 如权利要求22-38任一项所述的保护膜，其特征在于，所述保护膜还包括下离型层，所述下离型层设置在所述胶层远离所述第一聚氨酯基膜层的一侧表面。
  40. 如权利要求39所述的保护膜，其特征在于，所述下离型层对10nm～400nm波长范围的光透过率＜10％。
  41. 如权利要求22-40任一项所述的保护膜，其特征在于，所述保护膜还包括上保护层，所述上保护层位于所述第一聚氨酯基膜层远离所述胶层的一侧。
  42. 如权利要求41所述的保护膜，其特征在于，所述上保护层对10nm～400nm波长范围的光透过率＜10％。
  43. 一种保护膜的制备方法，其特征在于，所述制备方法包括：
    在PET载膜上制备第一聚氨酯基膜；所述第一聚氨酯基膜的邵氏硬度在45D～75D范围内，玻璃化转变温度Tg≥30℃；
    在所述第一聚氨酯基膜一侧表面制备UV半固化层；
    在UV半固化层上制备胶层。
  44. 如权利要求43所述的制备方法，其特征在于，还包括在所述第一聚氨酯基膜远离所述胶层的一侧表面制备耐脏污自修复层。
  45. 一种保护膜的制备方法，其特征在于，所述制备方法包括：
    在PET载膜上制备第一聚氨酯基膜层；所述第一聚氨酯基膜层的邵氏硬度在45D～75D范围内，玻璃化转变温度Tg≥30℃；
    在所述第一聚氨酯基膜层一侧表面制备UV半固化层；
    在UV半固化层上制备第二聚氨酯基膜；所述第二聚氨酯基膜层的邵氏硬度在45D～75D范围内，玻璃化转变温度Tg≥30℃；
    在所述第二聚氨酯基膜上制备胶层。
  46. 如权利要求45所述的制备方法，其特征在于，还包括在所述第一聚氨酯基膜远离所述胶层的一侧表面制备耐脏污自修复层。
  47. 一种保护膜贴合方法，其特征在于，包括：
    在黄光作业环境下，将权利要求22-42任一项所述的保护膜通过所述胶层贴合在电子设备屏幕表面，再采用UV光辐照使所述保护膜固化成型成与所述屏幕相匹配的形状。
  48. 如权利要求47所述的贴合方法，其特征在于，所述UV光辐照能量在1000mj/cm 2～3000mj/cm 2范围内。
  49. 一种终端，其特征在于，所述终端包括显示屏和贴合在所述显示屏上的如权利要求1-16任一项所述的保护膜或者如权利要求22-42任一项所述的保护膜，所述保护膜通过所述胶层贴合在所述显示屏的表面。
  50. 如权利要求49所述的终端，其特征在于，所述显示屏为曲面显示屏或平面显示屏。
  51. 如权利要求49或50所述的终端，其特征在于，所述显示屏包括盖板玻璃，若显示屏为3D大角度的曲面显示屏，所述保护膜与所述盖板玻璃相匹配。
  52. 一种终端，其特征在于，所述终端包括显示屏和贴合在所述显示屏上的保护膜，所述保护膜包括胶层和设置在所述胶层上的聚氨酯基膜层，所述保护膜通过所述胶层与所述显示屏粘合，所述聚氨酯基膜层的邵氏硬度在45D～75D范围内，玻璃化转变温度Tg在30℃～70℃范围内，热变形温度T 变形在50℃～90℃范围内，且Tg＜T 变形。
  53. 一种终端，其特征在于，所述终端包括显示屏和贴合在所述显示屏上的保护膜，所述保护膜包括与所述显示屏粘合的胶层，设置在胶层上的完全固化的UV半固化层和设置在所述完全固化的UV半固化层上的第一聚氨酯基膜层，所述完全固化的UV半固化层为聚氨酯丙烯酸酯层，所述聚氨酯丙烯酸酯层和第一聚氨酯基膜层的邵氏硬度在45D～75D范围内，玻璃化转变温度Tg≥30℃。
  54. 如权利要求53所述的终端，其特征在于，所述保护膜还包括设置在所述胶层与所述完全固化的UV半固化层之间的第二聚氨酯基膜层，所述第二聚氨酯基膜层的邵氏硬度在45D～75D范围内，玻璃化转变温度Tg≥30℃。
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CN114133491A (zh) * 2021-12-02 2022-03-04 广东邦固化学科技有限公司 一种光学级疏水疏油型热修复树脂及其制备方法和自修复涂层
CN115404019A (zh) * 2022-08-30 2022-11-29 南通通易航天科技股份有限公司 高红外阻隔汽车天窗用tpu隔热防爆膜
CN115404019B (zh) * 2022-08-30 2023-09-29 南通通易航天科技股份有限公司 高红外阻隔汽车天窗用tpu隔热防爆膜

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