3D post-hot-pressing high-modulus TPU (thermoplastic polyurethane) protective film as well as preparation method and application thereof

Abstract

The invention discloses a 3D post-hot-pressing high-modulus TPU (thermoplastic polyurethane) protective film as well as a preparation method and application thereof. The protective film comprises a protective layer, a functional layer, a base material layer, a high-viscosity silica gel layer and a release layer which are sequentially stacked, the functional layer is obtained by coating the first surface of the base material layer with a functional layer coating liquid and then curing the functional layer coating liquid; the functional layer coating liquid comprises the following components in parts by weight: 100 parts of self-repairing resin; 10-30 parts of a curing agent; 10 to 30 parts of a leveling agent; and 1-20 parts of a first diluting solvent. The protective film disclosed by the invention has the functions of resisting smudginess, friction and fingernail marks while ensuring that no white edge or warping exists during fitting; the protective film product is subjected to initial lamination and then a post-hot-pressing lamination process, so that the 3D curved screen can be ensured to be free of a white edge warping phenomenon. The protective film provided by the invention is low in production cost, simple in production process and wide in application prospect.

Description

Technical Field

[0001] The present invention relates to the field of protective film materials, and in particular to a 3D post-hot pressing high modulus TPU protective film, a preparation method and application thereof. Background Art

[0002] With the rapid development of smart phones, people have higher and higher requirements for the screen ratio and hand-held feel of mobile phones. 3D curved screen mobile phones have high competitiveness in the mobile phone market due to their ultra-high screen ratio and comfortable hand-held feel. The existing TPU protective film for 3D curved screens cannot meet the requirements in terms of dirt resistance, friction resistance, nail mark resistance, no white edges, and no warping.

[0003] Patent CN113201158A discloses a TPU protective film and its TPU base film, and a preparation method thereof. A hardening liquid is coated on one side of the TPU base material, and a silicone is coated on the other side, thereby obtaining a TPU protective film with a hardened layer on one side and a sticky layer on the other side. This product has good anti-oil and anti-fingerprint functions, but its hardened layer is AF-HC, and the production cost is high.

[0004] Patent CN 108116020 A discloses a 3D curved screen TPU protective film and its preparation method. The protective film prepared includes a matte film layer, a first OCA adhesive layer, a self-repairing layer, a TPU film layer, a primer layer, a second OCA adhesive layer, a transparent PET layer, a high-viscosity low-peeling silicone layer and a fluorine film layer. The product structure is complex. Although the product can meet the requirements of laminating a 3D curved screen, the actual production process is complex and the production cost is high. Summary of the invention

[0005] The technical problem to be solved by the present invention is to provide a 3D post-heat-pressed high modulus TPU protective film, a preparation method and application thereof in view of the deficiencies in the above-mentioned prior art.

[0006] In order to solve the above technical problems, the technical solution adopted by the present invention is as follows: In a first aspect of the present invention, a 3D post-heat-pressed high modulus TPU protective film is provided, comprising a protective layer, a functional layer, a substrate layer, a high-viscosity silicone layer and a release layer stacked in sequence;

[0007] The functional layer is obtained by coating a functional layer coating liquid on the first surface of the substrate layer and then curing the coating liquid, wherein the functional layer coating liquid comprises the following components in parts by weight:

[0008]

[0009] Preferably, the self-healing resin is selected from at least one of polyurethane polyol, hydroxy acrylate, polyhydroxy polyurethane acrylate, and polyhydroxy polyether acrylate.

[0010] Preferably, the curing agent is selected from at least one of toluene diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate;

[0011] The leveling agent is selected from at least one of an organic silicon leveling agent, a fluorocarbon leveling agent, and an acrylic leveling agent;

[0012] Preferably, the first dilution solvent is selected from at least one of toluene, ethyl acetate, xylene, isopropanol, butanone, and cyclohexanone.

[0013] Preferably, the high-viscosity silicone layer is obtained by coating a high-viscosity silicone coating liquid on the second surface of the substrate layer and then curing the coating liquid, wherein the high-viscosity silicone coating liquid comprises the following components in parts by weight:

[0014]

[0015] Preferably, the crosslinking agent is selected from at least one of a deacidification type crosslinking agent, a deketoxime type crosslinking agent, and a dealcoholization type crosslinking agent; the anchoring agent is selected from at least one of a polyurethane anchoring agent, an epoxy resin anchoring agent, and a silicone anchoring agent; the catalyst is selected from at least one of an organic tin catalyst, an organic cobalt catalyst, and an organic amine catalyst;

[0016] The second dilution solvent is selected from at least one of toluene, ethyl acetate, xylene, isopropanol, butanone, and cyclohexanone.

[0017] Preferably, the substrate layer is selected from one of TPU with a modulus of 100-200 MPa, TPU with a modulus of 200-400 MPa, TPU with a modulus of 400-600 MPa, TPU with a modulus of 600-800 MPa, and TPU with a modulus of 800-1200 MPa, and the thickness of the substrate layer is 50-100 μm.

[0018] Preferably, the protective layer is selected from one of an acrylic protective film, a polyurethane protective film, and a silicone protective film.

[0019] The second aspect of the present invention provides a method for preparing the 3D post-hot pressing high modulus TPU protective film as described above, comprising the following steps:

[0020] S1. Mix the self-healing resin with the first dilution solvent, stir at a speed of 500-1500 r / min for 5-10 min; then add the leveling agent, stir at 500-1500 r / min for 30-60 min, add the curing agent, stir at 500-1500 r / min for 30-60 min, filter through 500 mesh gauze to obtain a functional layer coating liquid;

[0021] S2, coating the functional layer coating liquid on the first surface of the substrate layer, baking at 110-120° C. for 3-5 minutes to form a functional layer; and pasting a protective layer on the functional layer;

[0022] S3, mixing the silicone pressure-sensitive adhesive with the second solvent release agent, stirring at a speed of 500-1500 r / min for 10-30 min; then adding the cross-linking agent, stirring at 500-1500 r / min for 5-10 min, adding the anchoring agent, stirring at 500-1500 r / min for 5-10 min, adding the catalyst, stirring at 500-1500 r / min for 15-60 min, filtering through 500 mesh gauze to obtain a high-viscosity silicone coating;

[0023] S4, applying the high-viscosity silicone coating liquid to the second surface of the substrate layer, and baking at 140-160° C. for 1.5-6 minutes to form a high-viscosity silicone layer;

[0024] S5. A release layer is pasted on the high-viscosity silicone layer to obtain the 3D post-hot-pressed high-modulus TPU protective film.

[0025] The third aspect of the present invention provides an application of the 3D post-heat-pressed high modulus TPU protective film as described above in a 3D curved screen of a mobile phone.

[0026] The beneficial effects of the present invention are:

[0027] The present invention provides a 3D post-hot pressing high modulus TPU protective film, which not only ensures no white edge and warping during lamination, but also has the functions of dirt resistance, friction resistance and nail mark resistance. After the initial lamination, the protective film product is subjected to a post-hot pressing lamination process to ensure that the 3D curved screen has no white edge and warping. It can solve the problem of high production cost of traditional mobile phone 3D curved screen protective films when meeting the requirements of dirt resistance, friction resistance and nail mark resistance, and also solve the problem of complex product structure and cumbersome production process of traditional solutions. The present invention provides a protective film with low production cost and simple production process, and has broad application prospects. DETAILED DESCRIPTION

[0028] The present invention is further described in detail below in conjunction with embodiments so that those skilled in the art can implement the invention with reference to the description.

[0029] It should be understood that the terms such as “having”, “including” and “comprising” used herein do not exclude the existence or addition of one or more other elements or combinations thereof.

[0030] The test methods used in the following examples are conventional methods unless otherwise specified. The materials and reagents used in the following examples are all commercially available unless otherwise specified. In the following examples, if no specific conditions are specified, the experiments were carried out under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used, if the manufacturer is not specified, are all conventional products that can be purchased commercially.

[0031] The present invention provides a 3D post-hot pressing high modulus TPU protective film, comprising a protective layer, a functional layer, a substrate layer, a high-viscosity silicone layer and a release layer which are stacked in sequence.

[0032] In a preferred embodiment, the protective layer is selected from one of an acrylic protective film, a polyurethane protective film, and a silicone protective film, and is more preferably an acrylic protective film.

[0033] In a preferred embodiment, the functional layer is obtained by coating a functional layer coating liquid on the first surface of the substrate layer and then curing the coating liquid, wherein the functional layer coating liquid comprises the following components in parts by weight:

[0034]

[0035] In a preferred embodiment, the self-healing resin is selected from at least one of polyurethane polyol, hydroxy acrylate, polyhydroxy polyurethane acrylate, and polyhydroxy polyether acrylate, and more preferably polyhydroxy polyurethane acrylate.

[0036] In a preferred embodiment, the curing agent is selected from at least one of toluene diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate, and more preferably hexamethylene diisocyanate.

[0037] In a preferred embodiment, the leveling agent is selected from at least one of an organic silicon leveling agent, a fluorocarbon leveling agent, and an acrylic leveling agent, and is more preferably an organic silicon leveling agent.

[0038] In a preferred embodiment, the first dilution solvent is selected from at least one of toluene, ethyl acetate, xylene, isopropanol, butanone, and cyclohexanone, more preferably ethyl acetate.

[0039] In a preferred embodiment, the high-viscosity silicone layer is obtained by coating a high-viscosity silicone coating liquid on the second surface of the substrate layer and then curing the coating liquid. The high-viscosity silicone coating liquid includes the following components in parts by weight:

[0040]

[0041] In a preferred embodiment, the crosslinking agent is selected from at least one of a deacidification type crosslinking agent, a deketoxime type crosslinking agent, and a dealcoholization type crosslinking agent; the anchoring agent is selected from at least one of a polyurethane anchoring agent, an epoxy resin anchoring agent, and a silicone anchoring agent; and the catalyst is selected from at least one of an organic tin catalyst, an organic cobalt catalyst, and an organic amine catalyst.

[0042] In a preferred embodiment, the second dilution solvent is selected from at least one of toluene, ethyl acetate, xylene, isopropanol, butanone, and cyclohexanone, more preferably toluene.

[0043] In a preferred embodiment, the substrate layer is selected from one of TPU with a modulus of 100-200 MPa, TPU with a modulus of 200-400 MPa, TPU with a modulus of 400-600 MPa, TPU with a modulus of 600-800 MPa, and TPU with a modulus of 800-1200 MPa, and the thickness of the substrate layer is 50-100 μm.

[0044] The present invention also provides a method for preparing the above 3D post-heat-pressing high modulus TPU protective film, comprising the following steps:

[0045] S1. Mix the self-healing resin with the first dilution solvent, stir at a speed of 500-1500 r / min for 5-10 min; then add the leveling agent, stir at 500-1500 r / min for 30-60 min, add the curing agent, stir at 500-1500 r / min for 30-60 min, filter through 500 mesh gauze to obtain a functional layer coating liquid;

[0046] S2, coating the functional layer coating liquid on the first surface of the substrate layer by an anilox roller, a doctor blade, micro-dimples or slit extrusion, baking at 110-120° C. for 3-5 minutes to form a functional layer; and pasting a protective layer on the functional layer;

[0047] S3, mixing the silicone pressure-sensitive adhesive with the second solvent release agent, stirring at a speed of 500-1500 r / min for 10-30 min; then adding the cross-linking agent, stirring at 500-1500 r / min for 5-10 min, adding the anchoring agent, stirring at 500-1500 r / min for 5-10 min, adding the catalyst, stirring at 500-1500 r / min for 15-60 min, filtering through 500 mesh gauze to obtain a high-viscosity silicone coating;

[0048] S4, applying the high-viscosity silicone coating liquid to the second surface of the substrate layer by means of anilox roller, scraper, micro-concave or slit extrusion, and baking at 140-160° C. for 1.5-6 minutes to form a high-viscosity silicone layer;

[0049] S5. A release layer is pasted on the high-viscosity silicone layer to obtain a 3D post-hot-pressed high-modulus TPU protective film.

[0050] In a preferred embodiment, the prepared functional layer has a water drop angle of more than 100°, is resistant to copper brushing 200 times, has a transmittance of >92%, and a haze of less than 1%. The prepared high-viscosity silicone layer has a transmittance of greater than 92%, a haze of less than 1%, and an AF screen adhesion of >40g / 25mm. The final finished product has a light transmittance of greater than 91%, a haze of less than 1%, a water drop angle of more than 100°, is resistant to copper brushing 200 times, a surface hardness of 500g, 1H, and an AF screen adhesion of >40g / 25mm. The 3D post-hot pressing high-modulus TPU protective film provided by the present invention has the functions of being resistant to dirt and friction while ensuring the lamination without white edges and warping.

[0051] The present invention also provides an application of the above 3D post-heat-pressed high modulus TPU protective film in a 3D curved screen of a mobile phone.

[0052] The 3D post-hot-pressing high modulus TPU protective film product prepared by the present invention has a simple use process, and only needs to tear off the release film and stick it on the 3D mobile phone screen, and then hot-press to shape it. Hot-pressing for 10 seconds can complete the shaping of the factory protective film.

[0053] The above is the overall concept of the present invention, and detailed embodiments and comparative examples are provided below on the basis of the overall concept of the present invention to further illustrate the present invention.

[0054] Example 1

[0055] S1. By weight, 100 parts of self-repairing resin (Hangzhi New Material ZPU-206A) were mixed with 10 parts of ethyl acetate, stirred at 500 r / min for 5 min, 10 parts of leveling agent (Hangzhi New Material ZPU-206C) were added, stirred at 500 r / min for 30 min, 10 parts of curing agent (Hangzhi New Material ZPU-206B) were added, stirred at 500 r / min for 30 min, and filtered through 500 mesh gauze to obtain a functional layer coating liquid;

[0056] S2, applying the functional layer coating liquid to the first surface of the TPU substrate layer having a thickness of 80 μm and a modulus of 600 MPa by slit extrusion, and baking at 120° C. for 3 minutes to form a functional layer; and applying a protective layer (acrylic protective film) on the functional layer;

[0057] S3. By weight, 100 parts of organic silicone pressure-sensitive adhesive (DS-9860B) and 100 parts of toluene were mixed and stirred at a speed of 500 r / min for 10 min, 1 part of cross-linking agent (DS-008W) was added, and stirred at a speed of 500 r / min for 5 min, 1 part of anchoring agent (DS-300) was added, and stirred at a speed of 500 r / min for 5 min, 1 part of catalyst (DS-1500) was added, and stirred at a speed of 500 r / min for 30 min, and then filtered with 500 mesh gauze to obtain a high-viscosity silicone coating liquid;

[0058] S4, applying the high-viscosity silicone coating liquid to the second surface of the substrate layer by a doctor blade coating method, and baking at 150° C. for 3 minutes to form a high-viscosity silicone layer;

[0059] S5. Paste a release film with a release force of 3g on the high-viscosity silicone layer to form a release layer to obtain a 3D post-heat-pressed high-modulus TPU protective film

[0060] S6. Die-cut the finished protective film into the size of the 3D screen. When using it, tear off the release layer, first use a laminating machine to stick it on the 3D mobile phone screen, and then use a hot press to heat and fix it into shape.

[0061] Example 2

[0062] S1. By weight, 100 parts of self-repairing resin (Hangzhi New Material ZPU-206A) were mixed with 10 parts of ethyl acetate, stirred at 500 r / min for 5 min, 15 parts of leveling agent (Hangzhi New Material ZPU-206C) were added, stirred at 500 r / min for 30 min, 10 parts of curing agent (Hangzhi New Material ZPU-206B) were added, stirred at 500 r / min for 30 min, and filtered through 500 mesh gauze to obtain a functional layer coating liquid;

[0063] S2, applying the functional layer coating liquid to the first surface of the TPU substrate layer having a thickness of 80 μm and a modulus of 400 MPa by slit extrusion, and baking at 120° C. for 3 minutes to form a functional layer; and applying a protective layer (acrylic protective film) on the functional layer;

[0064] S3. By weight, 100 parts of organic silicone pressure-sensitive adhesive (DS-9860B) and 100 parts of toluene were mixed and stirred at a speed of 500 r / min for 10 min, 1.5 parts of cross-linking agent (DS-008W) were added, and stirred at a speed of 500 r / min for 5 min, 1 part of anchoring agent (DS-300) was added, and stirred at a speed of 500 r / min for 5 min, 1 part of catalyst (DS-1500) was added, and stirred at a speed of 500 r / min for 30 min, and then filtered with 500 mesh gauze to obtain a high-viscosity silicone coating liquid;

[0065] S4, applying the high-viscosity silicone coating liquid to the second surface of the substrate layer by a doctor blade coating method, and baking at 150° C. for 3 minutes to form a high-viscosity silicone layer;

[0066] S5. Paste a release film with a release force of 3g on the high-viscosity silicone layer to form a release layer to obtain a 3D post-heat-pressed high-modulus TPU protective film

[0067] S6. Die-cut the finished protective film into the size of the 3D screen. When using it, tear off the release layer, first use a laminating machine to stick it on the 3D mobile phone screen, and then use a hot press to heat and fix it into shape.

[0068] Example 3

[0069] S1. By weight, 100 parts of self-repairing resin (Hangzhi New Material ZPU-206A) were mixed with 10 parts of ethyl acetate, stirred at 500 r / min for 5 min, 10 parts of leveling agent (Hangzhi New Material ZPU-206C) were added, stirred at 500 r / min for 30 min, 12 parts of curing agent (Hangzhi New Material ZPU-206B) were added, stirred at 500 r / min for 30 min, and filtered through 500 mesh gauze to obtain a functional layer coating liquid;

[0070] S2, applying the functional layer coating liquid to the first surface of the TPU substrate layer having a thickness of 80 μm and a modulus of 800 MPa by micro-concave coating, and baking at 120° C. for 3 minutes to form a functional layer; and applying a protective layer (acrylic protective film) on the functional layer;

[0071] S3. By weight, 100 parts of organic silicone pressure-sensitive adhesive (DS-9860B) and 100 parts of toluene were mixed and stirred at a speed of 500 r / min for 10 min, 1 part of cross-linking agent (DS-008W) was added, and stirred at a speed of 500 r / min for 5 min, 1 part of anchoring agent (DS-300) was added, and stirred at a speed of 500 r / min for 5 min, 1.5 parts of catalyst (DS-1500) was added, and stirred at a speed of 500 r / min for 30 min, and then filtered with 500 mesh gauze to obtain a high-viscosity silicone coating liquid;

[0072] S4, applying a high-viscosity silicone coating liquid to the second surface of the substrate layer by slit extrusion, and baking at 150° C. for 3 minutes to form a high-viscosity silicone layer;

[0073] S5. Paste a release film with a release force of 3g on the high-viscosity silicone layer to form a release layer to obtain a 3D post-heat-pressed high-modulus TPU protective film

[0074] S6. Die-cut the finished protective film into the size of the 3D screen. When using it, tear off the release layer, first use a laminating machine to stick it on the 3D mobile phone screen, and then use a hot press to heat and fix it into shape.

[0075] Comparative Example 1

[0076] S1. By weight, 100 parts of self-repairing resin (Hangzhi New Material ZPU-206A) were mixed with 10 parts of ethyl acetate, stirred at 500 r / min for 5 min, 10 parts of leveling agent (Hangzhi New Material ZPU-206C) were added, stirred at 500 r / min for 30 min, 10 parts of curing agent (Hangzhi New Material ZPU-206B) were added, stirred at 500 r / min for 30 min, and filtered through 500 mesh gauze to obtain a functional layer coating liquid;

[0077] S2, applying the functional layer coating liquid to the first surface of the TPU substrate layer having a thickness of 80 μm and a modulus of 50 MPa by slit extrusion, and baking at 120° C. for 3 minutes to form a functional layer; and applying a protective layer (acrylic protective film) on the functional layer;

[0078] S3. By weight, 100 parts of organic silicone pressure-sensitive adhesive (DS-9860B) and 100 parts of toluene were mixed and stirred at a speed of 500 r / min for 10 min, 1 part of cross-linking agent (DS-008W) was added, and stirred at a speed of 500 r / min for 5 min, 1 part of anchoring agent (DS-300) was added, and stirred at a speed of 500 r / min for 5 min, 1 part of catalyst (DS-1500) was added, and stirred at a speed of 500 r / min for 30 min, and then filtered with 500 mesh gauze to obtain a high-viscosity silicone coating liquid;

[0079] S4, applying the high-viscosity silicone coating liquid to the second surface of the substrate layer by a doctor blade coating method, and baking at 150° C. for 3 minutes to form a high-viscosity silicone layer;

[0080] S5. Paste a release film with a release force of 3g on the high-viscosity silicone layer to form a release layer to obtain a 3D post-heat-pressed high-modulus TPU protective film

[0081] S6. Die-cut the finished protective film into the size of the 3D screen. When using it, tear off the release layer, first use a laminating machine to stick it on the 3D mobile phone screen, and then use a hot press to heat and fix it into shape.

[0082] Comparative Example 2

[0083] S1. By weight, 100 parts of self-repairing resin (Hangzhi New Material ZPU-206A) were mixed with 10 parts of ethyl acetate, stirred at 500 r / min for 5 min, 10 parts of leveling agent (Hangzhi New Material ZPU-206C) were added, stirred at 500 r / min for 30 min, 10 parts of curing agent (Hangzhi New Material ZPU-206B) were added, stirred at 500 r / min for 30 min, and filtered through 500 mesh gauze to obtain a functional layer coating liquid;

[0084] S2, applying the functional layer coating liquid to the first surface of the TPU substrate layer having a thickness of 80 μm and a modulus of 1400 MPa by slit extrusion, and baking at 120° C. for 3 minutes to form a functional layer; and applying a protective layer (acrylic protective film) on the functional layer;

[0085] S3. By weight, 100 parts of organic silicone pressure-sensitive adhesive (DS-9860B) and 100 parts of toluene were mixed and stirred at a speed of 500 r / min for 10 min, 1 part of cross-linking agent (DS-008W) was added, and stirred at a speed of 500 r / min for 5 min, 1 part of anchoring agent (DS-300) was added, and stirred at a speed of 500 r / min for 5 min, 1 part of catalyst (DS-1500) was added, and stirred at a speed of 500 r / min for 30 min, and then filtered with 500 mesh gauze to obtain a high-viscosity silicone coating liquid;

[0086] S4, applying the high-viscosity silicone coating liquid to the second surface of the substrate layer by a doctor blade coating method, and baking at 150° C. for 3 minutes to form a high-viscosity silicone layer;

[0087] S5. Paste a release film with a release force of 3g on the high-viscosity silicone layer to form a release layer to obtain a 3D post-heat-pressed high-modulus TPU protective film

[0088] S6. Die-cut the finished protective film into the size of the 3D screen. When using it, tear off the release layer, first use a laminating machine to stick it on the 3D mobile phone screen, and then use a hot press to heat and fix it into shape.

[0089] Comparative Example 3

[0090] S1. By weight, 100 parts of self-repairing resin (Hangzhi New Material ZPU-206A) were mixed with 10 parts of ethyl acetate, stirred at 500 r / min for 5 min, 5 parts of leveling agent (Hangzhi New Material ZPU-206C) were added, stirred at 500 r / min for 30 min, 10 parts of curing agent (Hangzhi New Material ZPU-206B) were added, stirred at 500 r / min for 30 min, and filtered through 500 mesh gauze to obtain a functional layer coating liquid;

[0091] S2, applying the functional layer coating liquid to the first surface of the TPU substrate layer having a thickness of 80 μm and a modulus of 600 MPa by slit extrusion, and baking at 120° C. for 3 minutes to form a functional layer; and applying a protective layer (acrylic protective film) on the functional layer;

[0092] S3. By weight, 100 parts of organic silicone pressure-sensitive adhesive (DS-9860B) and 100 parts of toluene were mixed and stirred at a speed of 500 r / min for 10 min, 1 part of cross-linking agent (DS-008W) was added, and stirred at a speed of 500 r / min for 5 min, 1 part of anchoring agent (DS-300) was added, and stirred at a speed of 500 r / min for 5 min, 1 part of catalyst (DS-1500) was added, and stirred at a speed of 500 r / min for 30 min, and then filtered with 500 mesh gauze to obtain a high-viscosity silicone coating liquid;

[0093] S4, applying the high-viscosity silicone coating liquid to the second surface of the substrate layer by a doctor blade coating method, and baking at 150° C. for 3 minutes to form a high-viscosity silicone layer;

[0094] S5. Paste a release film with a release force of 3g on the high-viscosity silicone layer to form a release layer to obtain a 3D post-heat-pressed high-modulus TPU protective film

[0095] S6. Die-cut the finished protective film into the size of the 3D screen. When using it, tear off the release layer, first use a laminating machine to stick it on the 3D mobile phone screen, and then use a hot press to heat and fix it into shape.

[0096] Comparative Example 4

[0097] S1. By weight, 100 parts of self-healing resin (Hangzhi New Material ZPU-206A) were mixed with 10 parts of ethyl acetate, stirred at 500 r / min for 5 min, 10 parts of leveling agent (Hangzhi New Material ZPU-206C) were added, stirred at 500 r / min for 30 min, 5 parts of curing agent (Hangzhi New Material ZPU-206B) were added, stirred at 500 r / min for 30 min, and filtered through 500 mesh gauze to obtain a functional layer coating liquid;

[0098] S2, applying the functional layer coating liquid to the first surface of the TPU substrate layer having a thickness of 80 μm and a modulus of 600 MPa by slit extrusion, and baking at 120° C. for 3 minutes to form a functional layer; and applying a protective layer (acrylic protective film) on the functional layer;

[0099] S3. By weight, 100 parts of organic silicone pressure-sensitive adhesive (DS-9860B) and 100 parts of toluene were mixed and stirred at a speed of 500 r / min for 10 min, 1 part of cross-linking agent (DS-008W) was added, and stirred at a speed of 500 r / min for 5 min, 1 part of anchoring agent (DS-300) was added, and stirred at a speed of 500 r / min for 5 min, 1 part of catalyst (DS-1500) was added, and stirred at a speed of 500 r / min for 30 min, and then filtered with 500 mesh gauze to obtain a high-viscosity silicone coating liquid;

[0100] S4, applying the high-viscosity silicone coating liquid to the second surface of the substrate layer by a doctor blade coating method, and baking at 150° C. for 3 minutes to form a high-viscosity silicone layer;

[0101] S5. Paste a release film with a release force of 3g on the high-viscosity silicone layer to form a release layer to obtain a 3D post-heat-pressed high-modulus TPU protective film

[0102] S6. Die-cut the finished protective film into the size of the 3D screen. When using it, tear off the release layer, first use a laminating machine to stick it on the 3D mobile phone screen, and then use a hot press to heat and fix it into shape.

[0103] Comparative Example 5

[0104] S1. By weight, 100 parts of self-repairing resin (Hangzhi New Material ZPU-206A) were mixed with 10 parts of ethyl acetate, stirred at 500 r / min for 5 min, 10 parts of leveling agent (Hangzhi New Material ZPU-206C) were added, stirred at 500 r / min for 30 min, 10 parts of curing agent (Hangzhi New Material ZPU-206B) were added, stirred at 500 r / min for 30 min, and filtered through 500 mesh gauze to obtain a functional layer coating liquid;

[0105] S2, applying the functional layer coating liquid to the first surface of the TPU substrate layer having a thickness of 80 μm and a modulus of 600 MPa by slit extrusion, and baking at 120° C. for 3 minutes to form a functional layer; and applying a protective layer (acrylic protective film) on the functional layer;

[0106] S3. By weight, 100 parts of organic silicone pressure-sensitive adhesive (DS-9860B) and 100 parts of toluene were mixed and stirred at a speed of 500 r / min for 10 min, 1 part of anchoring agent (DS-300) was added, and stirred at a speed of 500 r / min for 5 min, 1 part of catalyst (DS-1500) was added, and stirred at a speed of 500 r / min for 30 min, and then filtered with 500 mesh gauze to obtain a high-viscosity silicone coating liquid;

[0107] S4, applying the high-viscosity silicone coating liquid to the second surface of the substrate layer by a doctor blade coating method, and baking at 150° C. for 3 minutes to form a high-viscosity silicone layer;

[0108] S5. Paste a release film with a release force of 3g on the high-viscosity silicone layer to form a release layer to obtain a 3D post-heat-pressed high-modulus TPU protective film

[0109] S6. Die-cut the finished protective film into the size of the 3D screen. When using it, tear off the release layer, first use a laminating machine to stick it on the 3D mobile phone screen, and then use a hot press to heat and fix it into shape.

[0110] Comparative Example 6

[0111] S1. By weight, 100 parts of self-repairing resin (Hangzhi New Material ZPU-206A) were mixed with 10 parts of ethyl acetate, stirred at 500 r / min for 5 min, 10 parts of leveling agent (Hangzhi New Material ZPU-206C) were added, stirred at 500 r / min for 30 min, 10 parts of curing agent (Hangzhi New Material ZPU-206B) were added, stirred at 500 r / min for 30 min, and filtered through 500 mesh gauze to obtain a functional layer coating liquid;

[0112] S2, applying the functional layer coating liquid to the first surface of the TPU substrate layer having a thickness of 80 μm and a modulus of 600 MPa by slit extrusion, and baking at 120° C. for 3 minutes to form a functional layer; and applying a protective layer (acrylic protective film) on the functional layer;

[0113] S3. By weight, 100 parts of organic silicone pressure-sensitive adhesive (DS-9860B) and 100 parts of toluene were mixed and stirred at a speed of 500 r / min for 10 min, 1 part of cross-linking agent (DS-008W) was added, and stirred at a speed of 500 r / min for 5 min, 1 part of catalyst (DS-1500) was added, and stirred at a speed of 500 r / min for 30 min, and then filtered with 500 mesh gauze to obtain a high-viscosity silicone coating liquid;

[0114] S4, applying the high-viscosity silicone coating liquid to the second surface of the substrate layer by a doctor blade coating method, and baking at 150° C. for 3 minutes to form a high-viscosity silicone layer;

[0115] S5. Paste a release film with a release force of 3g on the high-viscosity silicone layer to form a release layer to obtain a 3D post-heat-pressed high-modulus TPU protective film

[0116] S6. Die-cut the finished protective film into the size of the 3D screen. When using it, tear off the release layer, first use a laminating machine to stick it on the 3D mobile phone screen, and then use a hot press to heat and fix it into shape.

[0117] Comparative Example 7

[0118] S1. By weight, 100 parts of self-repairing resin (Hangzhi New Material ZPU-206A) were mixed with 10 parts of ethyl acetate, stirred at 500 r / min for 5 min, 10 parts of leveling agent (Hangzhi New Material ZPU-206C) were added, stirred at 500 r / min for 30 min, 10 parts of curing agent (Hangzhi New Material ZPU-206B) were added, stirred at 500 r / min for 30 min, and filtered through 500 mesh gauze to obtain a functional layer coating liquid;

[0119] S2, applying the functional layer coating liquid to the first surface of the TPU substrate layer having a thickness of 80 μm and a modulus of 600 MPa by slit extrusion, and baking at 120° C. for 3 minutes to form a functional layer; and applying a protective layer (acrylic protective film) on the functional layer;

[0120] S3. By weight, 100 parts of organic silicone pressure-sensitive adhesive (DS-9860B) and 100 parts of toluene were mixed and stirred at a speed of 500 r / min for 10 min, 1 part of cross-linking agent (DS-008W) was added, and stirred at a speed of 500 r / min for 5 min, 1 part of anchoring agent (DS-300) was added, and stirred at a speed of 500 r / min for 30 min, and then filtered with 500 mesh gauze to obtain a high-viscosity silicone coating liquid;

[0121] S4, applying the high-viscosity silicone coating liquid to the second surface of the substrate layer by a doctor blade coating method, and baking at 150° C. for 3 minutes to form a high-viscosity silicone layer;

[0122] S5. Paste a release film with a release force of 3g on the high-viscosity silicone layer to form a release layer to obtain a 3D post-heat-pressed high-modulus TPU protective film

[0123] S6. Die-cut the finished protective film into the size of the 3D screen. When using it, tear off the release layer, first use a laminating machine to stick it on the 3D mobile phone screen, and then use a hot press to heat and fix it into shape.

[0124] In the above embodiments and comparative examples, the thicknesses of the protective layer, functional layer, high-viscosity silicone layer and release layer are the same, specifically as follows: the protective layer is 60 μm thick, the functional layer is 20 μm thick, the high-viscosity silicone layer is 50 μm thick, and the release layer is 50 μm thick.

[0125] The 3D post-heat-pressed high modulus TPU protective films prepared in the examples and comparative examples were subjected to the following performance tests:

[0126] 1. Transmittance, tested according to GB 2410-2008 test method;

[0127] 2. Haze: tested according to GB 2410-2008 test method;

[0128] 3. AF peel strength, tested according to ASTM D-3330 test method;

[0129] The test results are shown in Table 1 below:

[0130] Table 1

[0131]

[0132] According to the test results in Table 1, compared with the example, comparative example 1 has poor copper brush resistance test and offset printing test; compared with the example, white edges will appear in the sample after aging and poor fitting will occur in comparative example 2; compared with the example, the water drop angle is low, the oil resistance is unqualified, and the copper brush resistance is poor; compared with the example, the functional layer of comparative example 4 is not fully cured, and the offset printing and copper brush resistance tests are NG; compared with the example, the high viscosity silicone layer has no cross-linking, low AF force, and poor fitting in comparative example 5; compared with the example, the high viscosity silicone AF force adhesion is too low in comparative example 6; compared with the example, the high viscosity silicone does not react sufficiently and the AF force is too low.

[0133] Although the embodiments of the present invention have been disclosed as above, they are not limited to the applications listed in the specification and the implementation modes. They can be fully applied to various fields suitable for the present invention. For those familiar with the art, additional modifications can be easily implemented. Therefore, without departing from the general concept defined by the claims and the scope of equivalents, the present invention is not limited to specific details.

Claims

1. A 3D post-heat-pressed high modulus TPU protective film, characterized in that: It includes a protective layer, a functional layer, a substrate layer, a high-viscosity silicone layer and a release layer which are stacked in sequence; The functional layer is obtained by coating a functional layer coating liquid on the first surface of the substrate layer and then curing the coating liquid, wherein the functional layer coating liquid comprises the following components in parts by weight:

2. The 3D post-heat-pressed high modulus TPU protective film according to claim 1, characterized in that: The self-repairing resin is selected from at least one of polyurethane polyol, hydroxy acrylate, polyhydroxy polyurethane acrylate and polyhydroxy polyether acrylate.

3. The 3D post-heat-pressed high modulus TPU protective film according to claim 1, characterized in that: The curing agent is selected from at least one of toluene diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate. The leveling agent is selected from at least one of an organic silicon leveling agent, a fluorocarbon leveling agent, and an acrylic leveling agent.

4. The 3D post-heat-pressed high modulus TPU protective film according to claim 1, characterized in that: The first dilution solvent is selected from at least one of toluene, ethyl acetate, xylene, isopropanol, butanone, and cyclohexanone.

5. The 3D post-heat-pressed high modulus TPU protective film according to claim 1, characterized in that: The high-viscosity silicone layer is obtained by coating a high-viscosity silicone coating liquid on the second surface of the substrate layer and then curing the coating liquid. The high-viscosity silicone coating liquid includes the following components in parts by weight:

6. The 3D post-heat-pressed high modulus TPU protective film according to claim 5, characterized in that: The crosslinking agent is selected from at least one of a deacidification type crosslinking agent, a deketoxime type crosslinking agent, and a dealcoholization type crosslinking agent; the anchoring agent is selected from at least one of a polyurethane anchoring agent, an epoxy resin anchoring agent, and a silicone anchoring agent; the catalyst is selected from at least one of an organic tin catalyst, an organic cobalt catalyst, and an organic amine catalyst; The second dilution solvent is selected from at least one of toluene, ethyl acetate, xylene, isopropanol, butanone, and cyclohexanone.

7. The 3D post-heat-pressed high modulus TPU protective film according to claim 1, characterized in that: The substrate layer is selected from one of TPU with a modulus of 100-200 MPa, TPU with a modulus of 200-400 MPa, TPU with a modulus of 400-600 MPa, TPU with a modulus of 600-800 MPa, and TPU with a modulus of 800-1200 MPa, and the thickness of the substrate layer is 50-100 μm.

8. The 3D post-heat-pressed high modulus TPU protective film according to claim 1, characterized in that: The protective layer is selected from one of an acrylic protective film, a polyurethane protective film, and a silicone protective film.

9. A method for preparing a 3D post-hot pressing high modulus TPU protective film according to any one of claims 1 to 8, characterized in that: The following steps are involved: S1. Mix the self-healing resin with the first dilution solvent, stir at a speed of 500-1500 r / min for 5-10 min; then add the leveling agent, stir at 500-1500 r / min for 30-60 min, add the curing agent, stir at 500-1500 r / min for 30-60 min, filter through 500 mesh gauze to obtain a functional layer coating liquid; S2, coating the functional layer coating liquid on the first surface of the substrate layer, baking at 110-120° C. for 3-5 minutes to form a functional layer; and pasting a protective layer on the functional layer; S3, mixing the silicone pressure-sensitive adhesive with the second solvent release agent, stirring at a speed of 500-1500 r / min for 10-30 min; then adding the cross-linking agent, stirring at 500-1500 r / min for 5-10 min, adding the anchoring agent, stirring at 500-1500 r / min for 5-10 min, adding the catalyst, stirring at 500-1500 r / min for 15-60 min, filtering through 500 mesh gauze to obtain a high-viscosity silicone coating; S4, applying the high-viscosity silicone coating liquid to the second surface of the substrate layer, and baking at 140-160° C. for 1.5-6 minutes to form a high-viscosity silicone layer; S5. A release layer is pasted on the high-viscosity silicone layer to obtain the 3D post-hot-pressed high-modulus TPU protective film.

10. Application of the 3D post-heat-pressed high modulus TPU protective film as claimed in any one of claims 1 to 8 in a 3D curved screen of a mobile phone.

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