High-transmittance superhard mobile phone protection film and preparation method thereof

Abstract

The invention discloses a high-transmittance superhard mobile phone protective film and a preparation method thereof. The protective film comprises a protective film layer, an externally coated AF layer, a substrate hardened layer 1, a base material layer, a substrate hardened layer 2, an organic silica gel layer and a release layer which are sequentially stacked. The protective film provided by the invention has very high transmittance and hardness and excellent wear resistance, and in addition, the fitting effect is excellent; the outer coated AF coating and the two substrate hardened layers provide sufficient hardness and wear resistance for the mobile phone film, the flexible fitness of the organic silica gel layer enables the fitting effect of a mobile phone to be improved, and the protective film can be tightly fitted with a mobile phone screen, so that the problems of white edges, warping and the like of the fitting and annular thickness measurement protective film are avoided; the protective film provided by the invention has the advantages that the cost is reduced, the hardness and light transmittance are very high, the wear resistance is excellent, and the extremely low dynamic friction coefficient can bring excellent smooth hand feeling.

Description

Technical Field

[0001] This invention relates to the field of protective film materials, and in particular to a high-transmittance ultra-hard mobile phone protective film and its preparation method. Background Technology

[0002] With mobile phones playing an increasingly important role in people's lives and work, and as people's demands for visual appeal and user experience evolve, the performance of mobile phone screens also needs to be upgraded. In response to this demand, screen protectors that do not hinder the user experience, while protecting fragile and expensive screens, have emerged. Common tempered glass screen protectors, while hard enough, lack impact resistance, are easily broken and shattered under stress, and are also expensive. Ordinary PET screen protectors have poor smoothness, defective optical properties, and, more importantly, insufficient hardness, making it difficult to effectively protect the screen.

[0003] Some manufacturers can produce PET protective films with a hardness as high as 9H. However, while the hardness is very high, there are obvious defects that prevent mass production and widespread application: (1) High warpage leads to poor adhesion between the protective film and the phone screen, resulting in a large amount of gray edges; (2) Poor optical performance, such as transmittance and haze; (3) The laminated structure uses two substrates, resulting in a thicker finished product, which reduces the fingerprint fading rate, and the cost of two optical PET substrates is also high. Therefore, the market urgently needs a high-hardness, high-transmittance, and low-cost ultra-hard protective film to solve the defects of existing PET protective films, such as fragility, high warpage, and low transmittance. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to provide a protective film with high hardness, high transparency and high smoothness, in order to overcome the shortcomings of the prior art.

[0005] To solve the above-mentioned technical problems, the technical solution adopted by the present invention is: a high transmittance ultra-hard mobile phone protective film, comprising a protective film layer, an outer coating AF layer, a substrate hardening layer 1, a substrate layer, a substrate hardening layer 2, an organic silicone layer and a release layer stacked sequentially. The substrate hardening layer 1 is obtained by coating a substrate hardening liquid 1 and then curing it. The substrate hardening liquid 1 includes the following raw material components by weight: 100 parts of photocurable resin A, 30-70 parts of photocurable resin B, 40-60 parts of ethyl acetate, and 3-5 parts of photoinitiator.

[0006] Preferably, the substrate hardening layer 2 is obtained by coating the substrate hardening liquid 2 and then curing it. The substrate hardening liquid 1 includes the following raw material components by weight: 100 parts of photocurable resin A, 40-80 parts of photocurable resin B, 40-60 parts of ethyl acetate, and 3-5 parts of photoinitiator.

[0007] Preferably, the light-curing resin A is U-CURE 9345 from Kunshan Castel Polymer Materials Co., Ltd.

[0008] Preferably, the light-curing resin B is BEBECRYL® 1290 from ZIN Resins (China) Co., Ltd.

[0009] Preferably, the silicone layer is obtained by coating with silicone adhesive and then curing it. The silicone adhesive comprises the following raw material components by weight: 100 parts silicone A, 30-40 parts silicone B, 100-200 parts solvent, 1.0-2.4 parts curing agent, 0.5-1.2 parts anchoring agent, and 1.0-2.4 parts platinum complexing catalyst.

[0010] Preferably, the solvent is a mixture of toluene and ethyl acetate.

[0011] Preferably, silicone A is FC-618 from Sichuan Fucai Technology Co., Ltd., silicone B is FC-619 from Sichuan Fucai Technology Co., Ltd., curing agent is FC-203 from Sichuan Fucai Technology Co., Ltd., anchoring agent is 297 from Dow Chemical Company, and platinum complexing catalyst is PT-4000 from Dow Chemical Company.

[0012] Preferably, the external AF coating layer is obtained by applying an AF slip agent and then curing it. The AF slip agent is AF-3304 from Trifluorochemicals.

[0013] Preferably, the thickness of the protective film layer is 50-150 μm, the thickness of the outer AF coating layer is 30-50 nm, the thickness of the substrate hardening layer 1 is 20-40 μm, the thickness of the substrate layer is 50-150 μm, the thickness of the substrate hardening layer 2 is 30-50 μm, and the thickness of the release layer is 25-100 μm.

[0014] The present invention also provides a method for preparing the high transmittance ultra-hard mobile phone protective film as described above, comprising the following steps: S1. The substrate hardening liquid 2 is uniformly coated on the first surface of the substrate layer, dried and then photocured to form the substrate hardening layer 2, and a semi-finished product 1 is obtained. S2. The substrate hardening liquid 1 is uniformly coated on the second surface of the substrate layer of the semi-finished product 1, dried and then photocured to form the substrate hardening layer 1, thus obtaining the semi-finished product 2. S3. AF slip agent is uniformly coated on the surface of the substrate hardening layer 1 of semi-finished product 2, dried and then photocured to form an outer coating AF layer, thus obtaining semi-finished product 3. S4. Apply silicone adhesive evenly to the surface of the substrate hardening layer 2 of the semi-finished product 3, and after drying and curing, form a silicone layer to obtain the semi-finished product 4. S5. Finally, the protective film layer and release layer are respectively attached to the surface of the outer coating AF layer and the silicone layer of the semi-finished product 4 to obtain the high transmittance ultra-hard mobile phone protective film.

[0015] The beneficial effects of this invention are: This invention provides a high-transmittance, ultra-hard mobile phone screen protector, comprising a protective film layer, an outer AF coating layer, a substrate hardening layer 1, a substrate layer, a substrate hardening layer 2, an organic silicone layer, and a release layer, stacked sequentially. This protective film exhibits high transmittance, hardness, and excellent wear resistance, along with excellent adhesion. The outer AF coating and two substrate hardening layers provide sufficient hardness and wear resistance, while the softness and conformability of the organic silicone layer enhances the fit, ensuring a tight bond between the protective film and the phone screen. This avoids issues such as white edges and warping associated with traditional screen protectors. The protective film provided by this invention reduces costs while possessing very high hardness, light transmittance, and excellent wear resistance. Its extremely low coefficient of dynamic friction also provides an excellent smooth feel. Detailed Implementation

[0016] The present invention will be further described in detail below with reference to embodiments, so that those skilled in the art can implement it based on the description.

[0017] It should be understood that terms such as “having,” “comprising,” and “including” as used herein do not exclude the presence or addition of one or more other elements or combinations thereof.

[0018] Unless otherwise specified, the experimental methods used in the following examples are conventional methods. Unless otherwise specified, the materials and reagents used in the following examples are commercially available. For examples where specific conditions are not specified, conventional conditions or conditions recommended by the manufacturer are followed. For reagents or instruments whose manufacturers are not specified, they are all commercially available products.

[0019] The present invention provides a high transmittance ultra-hard mobile phone protective film, comprising a protective film layer, an outer coating AF layer, a substrate hardening layer 1, a substrate layer, a substrate hardening layer 2, an organic silicone layer and a release layer stacked sequentially. The substrate hardening layer 1 is obtained by coating the substrate hardening liquid 1 and then curing it. The substrate hardening liquid 1 includes the following raw material components by weight: 100 parts of photocurable resin A, 30-70 parts of photocurable resin B, 40-60 parts of ethyl acetate, and 3-5 parts of photoinitiator.

[0020] In a preferred embodiment, the substrate hardening layer 2 is obtained by coating a substrate hardening liquid 1 and then curing it. The substrate hardening liquid 1 comprises the following raw material components by weight: 100 parts of photocurable resin A, 40-80 parts of photocurable resin B, 40-60 parts of ethyl acetate, and 3-5 parts of photoinitiator. The photoinitiator is preferably photoinitiator 184.

[0021] In a preferred embodiment, the photocurable resin A is U-CURE9345 from Kunshan Castel Polymer Materials Co., Ltd. In a preferred embodiment, the light-curing resin B is BEBECRYL® 1290 from ZIN Resins (China) Co., Ltd.

[0022] In a preferred embodiment, the silicone layer is obtained by coating with silicone adhesive and then curing it. The silicone adhesive includes the following raw material components by weight: 100 parts silicone A, 30-40 parts silicone B, 100-200 parts solvent, 1.0-2.4 parts curing agent, 0.5-1.2 parts anchoring agent, and 1.0-2.4 parts platinum complexing catalyst.

[0023] In a preferred embodiment, the solvent is a mixture of toluene and ethyl acetate.

[0024] In a preferred embodiment, silicone A is FC-618 from Sichuan Fucai Technology Co., Ltd., silicone B is FC-619 from Sichuan Fucai Technology Co., Ltd., curing agent is FC-203 from Sichuan Fucai Technology Co., Ltd., anchoring agent is 297 from Dow Chemical Co., Ltd., and platinum complexing catalyst is PT-4000 from Dow Chemical Co., Ltd.

[0025] In a preferred embodiment, the external AF layer is obtained by applying an AF slip agent and then curing it. The AF slip agent is AF-3304 from Trifluorochemicals.

[0026] In a preferred embodiment, the protective film layer is selected from conventional high-temperature resistant silicone protective film or polyurethane protective film; the thickness of the protective film layer is 50-150 μm. The solid content is approximately 0.5 wt%.

[0027] In a preferred embodiment, the thickness of the external AF layer is 30-50 nm.

[0028] In a preferred embodiment, the thickness of the substrate hardening layer 1 is 20-40 μm.

[0029] In a preferred embodiment, the substrate layer is selected from optical-grade PET film, and the thickness of the substrate layer is 50-150 μm, more preferably about 100-125 μm, but not limited thereto. The surface of the substrate layer is often subjected to conventional treatments, such as corona treatment, plasma treatment, and coating, in order to increase the adhesion between the adhesive and the substrate layer.

[0030] In a preferred embodiment, the thickness of the substrate hardening layer 2 is 30-50 μm.

[0031] In a preferred embodiment, the release layer is an isolation layer on the silicone surface, and a fluorinated release film with PET as the substrate is generally selected. The selected thickness is usually below 100μm, preferably 25-100μm, and more preferably 50μm.

[0032] This invention also provides a method for preparing the above-mentioned high-transmittance ultra-hard mobile phone protective film, comprising the following steps: S1. The substrate hardening liquid 2 is uniformly coated on the first surface of the substrate layer, dried and then photocured to form the substrate hardening layer 2, and a semi-finished product 1 is obtained. S2. The substrate hardening liquid 1 is uniformly coated on the second surface of the substrate layer of the semi-finished product 1, dried and then photocured to form the substrate hardening layer 1, thus obtaining the semi-finished product 2. S3. AF slip agent is uniformly coated on the surface of the substrate hardening layer 1 of semi-finished product 2, dried and then photocured to form an outer coating AF layer, thus obtaining semi-finished product 3. S4. Apply silicone adhesive evenly to the surface of the substrate hardening layer 2 of the semi-finished product 3, and after drying and curing, form a silicone layer to obtain the semi-finished product 4. S5. Finally, the protective film layer and release layer are respectively attached to the surface of the outer coating AF layer and the silicone layer of the semi-finished product 4 to obtain a high-transmittance ultra-hard mobile phone protective film.

[0033] The ultra-hard protective film proposed in this invention employs a combination of an outer AF layer, a substrate hardening layer 1, a substrate layer, a substrate hardening layer 2, and an organic silicone layer. This reduces the need for a single PET layer. During the bonding process with the mobile phone screen, substrate hardening layers 1 and 2 provide the required hardness and abrasion resistance; the organic silicone layer provides excellent adhesion, bonding tightly to the screen and exhibiting excellent performance in a series of environmental tests, possessing the properties of soft tempered glass. The protective film provided by this invention reduces costs while also possessing very high hardness, light transmittance, and excellent abrasion resistance. Its extremely low coefficient of dynamic friction also provides an excellent smooth feel.

[0034] In the present invention, the selection, combination, and dosage of the formulation components in the external AF layer, substrate hardening layers 1 and 2, and silicone layer all significantly affect the performance of the protective film. In this invention: The selection of photocurable resins is determined by the reaction mechanism of photoinitiators, which break the chemical bonds between carbonyl carbon atoms and α-carbon atoms under light irradiation, and the resulting free radicals react with multifunctional acrylic molecules and polyurethane acrylate copolymers. Adjust the type of silicone by selecting the appropriate viscosity; A substrate hardening layer with suitable hardness was prepared by adjusting the content of two photocurable resins, A and B. After further experimental design and verification, the appropriate dosage and formula were finally determined, and a protective film product with qualified hardness, adhesion, optical properties and wear resistance was prepared.

[0035] The above is the general concept of the present invention. Based on this, detailed embodiments and comparative examples are provided below to further illustrate the present invention.

[0036] Example 1 A high-transmittance, ultra-hard mobile phone protective film includes a protective film layer, an outer coating AF layer, a substrate hardening layer 1, a substrate layer, a substrate hardening layer 2, an organosilicon layer, and a release layer, which are sequentially stacked. The preparation method includes the following steps: S0. An 85μm high-temperature resistant silicone protective film (3g / 25mm adhesion) is selected as the protective film layer, an optical grade PET film with a thickness of 100μm is selected as the substrate layer, and a PET release film with a thickness of 50μm is selected as the release layer.

[0037] S1. Preparation of substrate hardening layer 2: S1-1, Preparation of substrate hardening solution 2 The substrate curing solution 2 comprises the following raw material components by weight: 100 parts of photocurable resin A (U-CURE 9345 purchased from Kunshan Castel Polymer Materials Co., Ltd.), 50 parts of photocurable resin B (BEBECRYL® 1290 purchased from Zhanxin Resin (China) Co., Ltd.), 60 parts of ethyl acetate, and 5 parts of photoinitiator (184).

[0038] According to the above formula, take photocurable resin A and photocurable resin B, add ethyl acetate and photoinitiator, stir and mix evenly, and then let stand to degas to obtain substrate hardening liquid 2. S1-2. Apply substrate curing liquid 2 evenly to the first surface of the substrate layer, bake in an oven at 90℃ for 3 minutes, and then cure online with a mercury lamp (the light curing energy is about 800mJ) to form a substrate curing layer 2 with a thickness of 30μm, and obtain semi-finished product 1; note that this product should be coated with yellow light throughout the process and packaged with black film.

[0039] S2, Preparation of substrate hardening layer 1: S2-1, Preparation of substrate hardening solution 1 The substrate curing solution 1 comprises the following raw material components by weight: 100 parts of photocurable resin A (U-CURE 9345 purchased from Kunshan Castel Polymer Materials Co., Ltd.), 50 parts of photocurable resin B (BEBECRYL® 1290 purchased from Zhanxin Resin (China) Co., Ltd.), 60 parts of ethyl acetate, and 5 parts of photoinitiator (184).

[0040] According to the above formula, take photocurable resin A and photocurable resin B, add ethyl acetate and photoinitiator, stir and mix evenly, and then let stand to degas to obtain substrate hardening liquid 1. S2-2. Apply substrate curing liquid 1 evenly to the second surface of the substrate layer, bake in an oven at 90°C for 3 minutes, and then cure online with a mercury lamp (the light curing energy is about 800mJ) to form a substrate curing layer 2 with a thickness of 20μm, thus obtaining semi-finished product 2. Note that this product should be coated with yellow light throughout the process and packaged with black film.

[0041] S3. Preparation of the external coating AF layer AF slip agent is uniformly coated on the surface of the substrate hardening layer 1 of semi-finished product 2. After baking in an oven at 90°C for 1 minute, it is cured online with a mercury lamp (curing energy of about 800mJ) to form an outer AF coating layer with a thickness of 50nm. The coating is then rolled up to obtain semi-finished product 3. Note that this product should be coated with yellow light throughout the process and packaged with black film. The outer AF curing liquid is AF-3304 purchased from Sanfluoro Chemicals, with a solid content of about 0.5wt%.

[0042] S4. Preparation of silicone layer S4-1. Preparation of silicone adhesive solution The silicone adhesive comprises, by weight, 100 parts silicone A (FC-618 purchased from Sichuan Fucai Technology Co., Ltd.), 40 parts silicone B (FC-619 purchased from Sichuan Fucai Technology Co., Ltd.), 70 parts toluene, 70 parts ethyl acetate, 1.8 parts curing agent (FC-203 purchased from Sichuan Fucai Technology Co., Ltd.), 0.8 parts anchoring agent (297 purchased from Dow Chemical Co., Ltd.), and 1.8 parts platinum complexing catalyst (PT-4000 purchased from Dow Chemical Co., Ltd.).

[0043] According to the above formula, take silicone A and B, add toluene, ethyl acetate, curing agent and anchoring agent in sequence, stir evenly, and finally add platinum catalyst and continue stirring. Let stand to remove bubbles to obtain silicone adhesive solution. S4-2. Apply silicone adhesive evenly to the surface of the substrate hardening layer 2 of the semi-finished product 3, bake in an oven at 160°C for 2 minutes to cure, and form a silicone layer with a thickness of 35μm to obtain the semi-finished product 4. S5. Finally, the protective film layer and release layer are respectively attached to the surface of the outer coating AF layer and the silicone layer of the semi-finished product 4, and then rolled up to obtain a high-transmittance ultra-hard mobile phone protective film.

[0044] Example 2 A high-transmittance, ultra-hard mobile phone protective film includes a protective film layer, an outer coating AF layer, a substrate hardening layer 1, a substrate layer, a substrate hardening layer 2, an organosilicon layer, and a release layer, which are sequentially stacked. The preparation method includes the following steps: S0. An 85μm high-temperature resistant silicone protective film (3g / 25mm adhesion) is selected as the protective film layer, an optical grade PET film with a thickness of 100μm is selected as the substrate layer, and a PET release film with a thickness of 50μm is selected as the release layer.

[0045] S1. Preparation of substrate hardening layer 2: S1-1, Preparation of substrate hardening solution 2 The substrate curing solution 2 comprises the following raw material components by weight: 100 parts of photocurable resin A (U-CURE 9345 purchased from Kunshan Castel Polymer Materials Co., Ltd.), 50 parts of photocurable resin B (BEBECRYL® 1290 purchased from Zhanxin Resin (China) Co., Ltd.), 60 parts of ethyl acetate, and 5 parts of photoinitiator (commonly 184).

[0046] According to the above formula, take photocurable resin A and photocurable resin B, add ethyl acetate and photoinitiator, stir and mix evenly, and then let stand to degas to obtain substrate hardening liquid 2. S1-2. Apply substrate curing liquid 2 evenly to the first surface of the substrate layer, bake in an oven at 90℃ for 3 minutes, and then cure online with a mercury lamp (the light curing energy is about 800mJ) to form a substrate curing layer 2 with a thickness of 40μm, and obtain semi-finished product 1; note that this product should be coated with yellow light throughout the process and packaged with black film.

[0047] S2, Preparation of substrate hardening layer 1: S2-1, Preparation of substrate hardening solution 1 The substrate curing solution comprises the following raw material components by weight: 75 parts of UV-curable resin A (U-CURE 9345 purchased from Kunshan Castel Polymer Materials Co., Ltd.), 25 parts of UV-curable resin B (BEBECRYL® 1290 purchased from Zhanxin Resin (China) Co., Ltd.), 60 parts of ethyl acetate, and 5 parts of photoinitiator (commonly 184).

[0048] According to the above formula, take photocurable resin A and photocurable resin B, add ethyl acetate and photoinitiator, stir and mix evenly, and then let stand to degas to obtain substrate hardening liquid 1. S2-2. Apply substrate curing liquid 1 evenly to the second surface of the substrate layer, bake in an oven at 90°C for 3 minutes, and then cure online with a mercury lamp (the light curing energy is about 800mJ) to form a substrate curing layer 2 with a thickness of 20μm, thus obtaining semi-finished product 2. Note that this product should be coated with yellow light throughout the process and packaged with black film.

[0049] S3. Preparation of the external AF coating layer: AF slip agent is uniformly coated on the surface of the substrate hardening layer 1 of semi-finished product 2. After baking in an oven at 90°C for 1 minute, it is cured online with a mercury lamp (curing energy of about 800mJ) to form an outer AF coating layer with a thickness of 50nm. The coating is then rolled up to obtain semi-finished product 3. Note that this product should be coated with yellow light throughout the process and packaged with black film. The outer AF curing liquid is AF-3304 purchased from Sanfluoro Chemicals, with a solid content of about 0.5wt%.

[0050] S4. Preparation of silicone layer S4-1. Preparation of silicone adhesive solution The silicone adhesive comprises, by weight, 100 parts silicone A (FC-618 purchased from Sichuan Fucai Technology Co., Ltd.), 35 parts silicone B (FC-619 purchased from Sichuan Fucai Technology Co., Ltd.), 70 parts toluene, 70 parts ethyl acetate, 1.8 parts curing agent (FC-203 purchased from Sichuan Fucai Technology Co., Ltd.), 1 part anchoring agent (297 purchased from Dow Chemical Co., Ltd.), and 1.6 parts platinum complexing catalyst (PT-4000 purchased from Dow Chemical Co., Ltd.).

[0051] According to the above formula, take silicone A and B, add toluene, ethyl acetate, curing agent and anchoring agent in sequence, stir evenly, and finally add platinum catalyst and continue stirring. Let stand to remove bubbles to obtain silicone adhesive solution. S4-2. Apply silicone adhesive evenly to the surface of the substrate hardening layer 2 of the semi-finished product 3, bake in an oven at 160°C for 2 minutes to cure, and form a silicone layer with a thickness of 35μm to obtain the semi-finished product 4. S5. Finally, the protective film layer and release layer are respectively attached to the surface of the outer coating AF layer and the silicone layer of the semi-finished product 4, and then rolled up to obtain a high-transmittance ultra-hard mobile phone protective film.

[0052] Example 3 A high-transmittance, ultra-hard mobile phone protective film includes a protective film layer, an outer coating AF layer, a substrate hardening layer 1, a substrate layer, a substrate hardening layer 2, an organosilicon layer, and a release layer, which are sequentially stacked. The preparation method includes the following steps: S0. An 85μm high-temperature resistant silicone protective film (3g / 25mm adhesion) is selected as the protective film layer, an optical grade PET film with a thickness of 100μm is selected as the substrate layer, and a PET release film with a thickness of 50μm is selected as the release layer.

[0053] S1. Preparation of substrate hardening layer 2: S1-1, Preparation of substrate hardening solution 2 The substrate curing solution 2 comprises the following raw material components by weight: 100 parts of photocurable resin A (U-CURE 9345 purchased from Kunshan Castel Polymer Materials Co., Ltd.), 50 parts of photocurable resin B (BEBECRYL® 1290 purchased from Zhanxin Resin (China) Co., Ltd.), 60 parts of ethyl acetate, and 5 parts of photoinitiator (184).

[0054] According to the above formula, take photocurable resin A and photocurable resin B, add ethyl acetate and photoinitiator, stir and mix evenly, and then let stand to degas to obtain substrate hardening liquid 2. S1-2. Apply substrate curing liquid 2 evenly to the first surface of the substrate layer, bake in an oven at 90℃ for 3 minutes, and then cure online with a mercury lamp (the light curing energy is about 800mJ) to form a substrate curing layer 2 with a thickness of 30μm, and obtain semi-finished product 1; note that this product should be coated with yellow light throughout the process and packaged with black film.

[0055] S2, Preparation of substrate hardening layer 1: S2-1, Preparation of substrate hardening solution 1 The substrate curing solution 1 comprises the following raw material components by weight: 50 parts of photocurable resin A (U-CURE 9345 purchased from Kunshan Castel Polymer Materials Co., Ltd.), 50 parts of photocurable resin B (BEBECRYL® 1290 purchased from Zhanxin Resin (China) Co., Ltd.), 60 parts of ethyl acetate, and 5 parts of photoinitiator (184).

[0056] According to the above formula, take photocurable resin A and photocurable resin B, add ethyl acetate and photoinitiator, stir and mix evenly, and then let stand to degas to obtain substrate hardening liquid 1. S2-2. Apply substrate curing liquid 1 evenly to the second surface of the substrate layer, bake in an oven at 90°C for 3 minutes, and then cure online with a mercury lamp (the light curing energy is about 800mJ) to form a substrate curing layer 2 with a thickness of 20μm, thus obtaining semi-finished product 2. Note that this product should be coated with yellow light throughout the process and packaged with black film.

[0057] S3. Preparation of the external coating AF layer AF slip agent is uniformly coated on the surface of the substrate hardening layer 1 of semi-finished product 2. After baking in an oven at 90°C for 1 minute, it is cured online with a mercury lamp (curing energy of about 800mJ) to form an outer AF coating layer with a thickness of 50nm. The coating is then rolled up to obtain semi-finished product 3. Note that this product should be coated with yellow light throughout the process and packaged with black film. The outer AF curing liquid is AF-3304 purchased from Sanfluoro Chemicals, with a solid content of about 0.5wt%.

[0058] S4. Preparation of silicone layer S4-1. Preparation of silicone adhesive solution The silicone adhesive comprises, by weight, 100 parts silicone A (FC-618 purchased from Sichuan Fucai Technology Co., Ltd.), 30-40 parts silicone B (FC-619 purchased from Sichuan Fucai Technology Co., Ltd.), 70 parts toluene, 70 parts ethyl acetate, 1.5 parts curing agent (FC-203 purchased from Sichuan Fucai Technology Co., Ltd.), 0.7 parts anchoring agent (297 purchased from Dow Chemical Company), and 1.6 parts platinum complexing catalyst (PT-4000 purchased from Dow Chemical Company).

[0059] According to the above formula, take silicone A and B, add toluene, ethyl acetate, curing agent and anchoring agent in sequence, stir evenly, and finally add platinum catalyst and continue stirring. Let stand to remove bubbles to obtain silicone adhesive solution. S4-2. Apply silicone adhesive evenly to the surface of the substrate hardening layer 2 of the semi-finished product 3, bake in an oven at 160°C for 2 minutes to cure, and form a silicone layer with a thickness of 35μm to obtain the semi-finished product 4. S5. Finally, the protective film layer and release layer are respectively attached to the surface of the outer coating AF layer and the silicone layer of the semi-finished product 4, and then rolled up to obtain a high-transmittance ultra-hard mobile phone protective film.

[0060] Comparative Example 1 The only difference between this example and Example 1 is: Different substrate hardening coating thicknesses: The thickness of the outer AF layer is reduced from 50nm to 20nm.

[0061] Comparative Example 2 The only difference between this example and Example 2 is the raw material composition of substrate hardening solution 1 and substrate hardening solution 2. The specific details of this example are as follows: The substrate curing solution 2 comprises the following raw material components by weight: 80 parts of photocurable resin A (U-CURE 9345 purchased from Kunshan Castel Polymer Materials Co., Ltd.), 20 parts of photocurable resin B (BEBECRYL® 1290 purchased from Zhanxin Resin (China) Co., Ltd.), 60 parts of ethyl acetate, and 5 parts of photoinitiator (184).

[0062] The substrate curing solution 1 comprises the following raw material components by weight: 80 parts of photocurable resin A (U-CURE 9345 purchased from Kunshan Castel Polymer Materials Co., Ltd.), 20 parts of photocurable resin B (BEBECRYL® 1290 purchased from Zhanxin Resin (China) Co., Ltd.), 60 parts of ethyl acetate, and 5 parts of photoinitiator (184).

[0063] Comparative Example 3 The only difference between this example and Example 3 is the raw material composition of the substrate hardening solution 2: The specifics of this example are as follows: The substrate curing solution 2 comprises the following raw material components by weight: 50 parts of photocurable resin A (U-CURE 9345 purchased from Kunshan Castel Polymer Materials Co., Ltd.), 50 parts of photocurable resin B (BEBECRYL® 1290 purchased from Zhanxin Resin (China) Co., Ltd.), 60 parts of ethyl acetate, and 5 parts of photoinitiator (184).

[0064] The following performance tests were conducted on Examples 1-3 and Comparative Examples 1-3: 1. Transmittance / Haze: Before testing, the sample is cured with a UV lamp. 1) Turn on the Murakami color haze meter and wait for the self-test to complete before preheating the light source for 15 minutes; 2) After preheating, press the OK button to open the sample chamber, and then test the blank total light transmittance and haze. The blank should have a transmittance of 100% and a haze of 0%; 3) Close the sample chamber, cut the sample to completely cover the light aperture, start the measurement, and record the data; 4) Measure each sample at least at two different locations.

[0065] 2. Water droplet angle: The water contact angle is tested using a contact angle tester with a water volume of 2-3 μL.

[0066] 3. Adhesion effect: Remove the base film and apply the working layer (with the face film) to the surface of the 2D phone. The water droplet angle on the surface should be >115°. Store at 50°C for 24 hours. Check for defects such as peeling edges and bubbles.

[0067] 4. Pencil Hardness: 1) First, cure the sample with a UV lamp and attach the protective film to the glass cover of the mobile phone. 2) Use a Mitsubishi pencil (UNI series) at a 45-degree angle and a load of 500gf to draw 3-5 lines of 3-5cm length on the sample surface from different directions.

[0068] 5. Universal tensile testing machine (sensor 5kg and below), mobile phone glass cover (surface water droplet angle > 110°), tensile testing machine speed 300mm / min.

[0069] 6. Coefficient of dynamic friction: Before testing, cure the sample with a UV lamp and test it using a coefficient of dynamic friction meter. Remove the protective film from the sample, place it on the test stage, and fix it. Load: 200±20g (weights, 2cm*2cm coverslip, 2cm*2cm double-sided tape, 2cm*2cm test paper hakuai 2022); Test instrument: MXD-02 (or equivalent); Fix the test sample and move the load by 50mm (test speed: 100mm / min); Test 3 samples.

[0070] 7. Steel wool friction: Before testing, cure the sample with a UV lamp, attach the protective film to the glass cover, and rub the surface of the protective film with 20mm*20mm steel wool with a line 30-40mm long; steel wool model is #0000; pressure is 1000g; test frequency: 35-50 times / minute, number of rubbing times: 1000 / 2500 times.

[0071] The test results are shown in Table 1 below: Table 1 Performance test results for each example and comparison example Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Haze ＞0.2 ＞0.2 ＞0.2 ＞0.2 ＞0.2 ＞0.2 Light transmittance ＞92.0 ＞92.0 ＞92.0 ＞92.0 ＞92.0 ＞92.0 Adhesion at 55℃ / 24h No white edges, no cracking No white edges, no cracking No white edges, no cracking No white edges, no cracking It has white edges and is cracked. No white edges, no cracking Surface pencil hard / 500g 9H OK 9H OK 8H OK 7H OK 9H OK 6H OK Surface water droplet angle (°) ＞115 ＞115 ＞115 ＞110 ＞115 ＞110 Steel wool abrasion resistant ＞10000 ＞12000 ＞9000 ＞8000 ＞12000 ＞6000 Water droplet angle after grinding (°) ＞100 ＞100 ＞100 ＞85 ＞103 ＞80 coefficient of kinetic friction ≤0.05 ≤0.05 ≤0.05 ≤0.08 ≤0.05 ≤0.08 AF screen peel force ＞60 ＞60 ＞60 ＞60 ＞60 ＞60 Warp (mm) ＜5 ＜5 ＜5 ＜3 ＞10 ＜3 The test results from the above examples and comparative examples show that the wear resistance and hardness of Example 1 are higher than those of Comparative Example 1. This is because, compared to Example 1, Comparative Example 1 reduced the thickness of the external AF coating layer in the sample structure, thus reducing the pencil hardness and wear resistance, while the haze and transmittance remained largely unchanged. Compared to Example 2, Comparative Example 2 changed the formulation of the substrate hardening layer, increasing the proportion of the hard component, which significantly improved the hardness of the Comparative Example 2 sample, achieving a pencil hardness of 9H. This is because the content and functionality of the multifunctional acrylic polymer in the formulation were increased. The multifunctional structure of the multifunctional acrylic polymer, after crosslinking, imparts excellent wear resistance and surface hardness to the sample, thus increasing the polymer content in the formulation is crucial. The increased functionality and crosslinking density improve the performance of the sample in Comparative Example 2. However, excessive hardness leads to insufficient flexibility, reduced adhesion, and increased warpage. This results in white edges during screen application, severe breakage during film removal, and makes the sample unsuitable for use. Compared to Example 3, Comparative Example 3 altered the substrate hardening layer formulation, reducing the content of hard components and decreasing hardness. The pencil hardness dropped to 6H, significantly impacting abrasion resistance. Even after 8000 cycles, the water droplet angle remained at 80°. This is because the formulation reduced the content and functionality of multifunctional acrylic polymers, resulting in a significant decrease in crosslinking. However, it improved the sample's flexibility and conformability, leading to excellent ring testing performance and warpage resistance after screen application. The present invention provides a high-transparency and ultra-hard 2D protective film with excellent optical performance: haze <0.2%, light transmittance >92%; high hardness, >9H / 500g; excellent wear resistance, using #0000 steel wool, with a load of 1000g, the wear resistance is >10000 times, and the water droplet angle after wear is still >100°, with outstanding smoothness and a dynamic friction coefficient ≤0.05. The product of the present invention can provide sufficient smoothness for mobile phone screen protectors, with good adhesion, and no whitening or warping.

[0072] Although the embodiments of the present invention have been disclosed above, they are not limited to the applications listed in the specification and embodiments. They can be applied to various fields suitable for the present invention. For those skilled in the art, other modifications can be easily made. Therefore, without departing from the general concept defined by the claims and their equivalents, the present invention is not limited to the specific details.

Claims

1. A high-transmittance, ultra-hard mobile phone protective film, characterized in that, It includes a protective film layer, an outer coating AF layer, a substrate hardening layer 1, a substrate layer, a substrate hardening layer 2, an organosilicon layer, and a release layer, which are stacked sequentially. The substrate hardening layer 1 is obtained by coating a substrate hardening liquid 1 and then curing it. The substrate hardening liquid 1 includes the following raw material components by weight: 100 parts of photocurable resin A, 30-70 parts of photocurable resin B, 40-60 parts of ethyl acetate, and 3-5 parts of photoinitiator.

2. The high transmittance ultra-hard mobile phone protective film according to claim 1, characterized in that, The substrate hardening layer 2 is obtained by coating the substrate hardening liquid 2 and then curing it. The substrate hardening liquid 1 includes the following raw material components by weight: 100 parts of photocurable resin A, 40-80 parts of photocurable resin B, 40-60 parts of ethyl acetate, and 3-5 parts of photoinitiator.

3. The high transmittance ultra-hard mobile phone protective film according to claim 2, characterized in that, The light-curing resin A is U-CURE 9345 from Kunshan Castel Polymer Materials Co., Ltd.

4. The high transmittance ultra-hard mobile phone protective film according to claim 2, characterized in that, The light-curing resin B is BEBECRYL® 1290 from ZIN Resins (China) Co., Ltd.

5. The high transmittance ultra-hard mobile phone protective film according to claim 1, characterized in that, The silicone layer is obtained by coating with silicone adhesive and then curing it. The silicone adhesive comprises the following raw material components by weight: 100 parts silicone A, 30-40 parts silicone B, 100-200 parts solvent, 1.0-2.4 parts curing agent, 0.5-1.2 parts anchoring agent, and 1.0-2.4 parts platinum complexing catalyst.

6. The high transmittance ultra-hard mobile phone protective film according to claim 5, characterized in that, The solvent is a mixture of toluene and ethyl acetate.

7. The high transmittance ultra-hard mobile phone protective film according to claim 5, characterized in that, Silicone A is FC-618 from Sichuan Fucai Technology Co., Ltd., silicone B is FC-619 from Sichuan Fucai Technology Co., Ltd., curing agent is FC-203 from Sichuan Fucai Technology Co., Ltd., anchoring agent is 297 from Dow Chemical Company, and platinum complexing catalyst is PT-4000 from Dow Chemical Company.

8. The high transmittance ultra-hard mobile phone protective film according to claim 1, characterized in that, The external AF coating layer is obtained by applying AF slip agent and then curing it. The AF slip agent is AF-3304 from Trifluorochemicals.

9. The high transmittance ultra-hard mobile phone protective film according to claim 1, characterized in that, The thickness of the protective film layer is 50-150 μm, the thickness of the outer AF coating layer is 30-50 nm, the thickness of the substrate hardening layer 1 is 20-40 μm, the thickness of the substrate layer is 50-150 μm, the thickness of the substrate hardening layer 2 is 30-50 μm, and the thickness of the release layer is 25-100 μm.

10. A method for preparing a high-transmittance, ultra-hard mobile phone protective film as described in any one of claims 1-9, characterized in that, Includes the following steps: S1. The substrate hardening liquid 2 is uniformly coated on the first surface of the substrate layer, dried and then photocured to form the substrate hardening layer 2, and a semi-finished product 1 is obtained. S2. The substrate hardening liquid 1 is uniformly coated on the second surface of the substrate layer of the semi-finished product 1, dried and then photocured to form the substrate hardening layer 1, thus obtaining the semi-finished product 2. S3. AF slip agent is uniformly coated on the surface of the substrate hardening layer 1 of semi-finished product 2, dried and then photocured to form an outer coating AF layer, thus obtaining semi-finished product 3. S4. Apply silicone adhesive evenly to the surface of the substrate hardening layer 2 of the semi-finished product 3, and after drying and curing, form a silicone layer to obtain the semi-finished product 4. S5. Finally, the protective film layer and release layer are respectively attached to the surface of the outer coating AF layer and the silicone layer of the semi-finished product 4 to obtain the high transmittance ultra-hard mobile phone protective film.