Optical-grade PET release film as well as preparation method and application thereof

Abstract

The invention discloses an optical-grade PET release film and a preparation method and application thereof, and belongs to the technical field of PET release liners.The preparation method comprises the steps that organic silicon resin, polyacrylate and functional silicone oil serve as raw materials, hexadecafluorophthalocyanine copper serves as a catalyst, sodium hydroxide provides hydroxyl anions, and hydroxyl-containing fluorinated hydroxyaniline is obtained; amino groups on the surface of fluorinated hydroxyaniline react with carboxyl groups of graphene oxide and are grafted on the surface of graphene oxide, then hydroxyl groups in the fluorinated hydroxyaniline and carboxyl groups of acrylic acid are subjected to esterification reaction under the action of a catalyst, so that acrylic acid is grafted on fluorinated modified graphene oxide, and the fluorinated modified graphene oxide is obtained. Therefore, hydroxyl and epoxy functional groups on the surface of the graphene oxide are consumed, hindering of electron transmission is reduced, the conductivity of the release film is improved, and the antistatic requirement of the release film is met.

Description

Technical Field

[0001] The present invention belongs to the technical field of PET release films, and specifically relates to an optical-grade PET release film, a preparation method thereof, and an application thereof. Background Art

[0002] A release film, also known as an isolation film, a stripping film, a separation film, etc. A PET release film is a surface treatment of a PET substrate, including coating a silicone release coating, a fluorine-based release coating, or performing plasma treatment, so that it has a very light and stable release force for different organic pressure-sensitive adhesives, and is one of the most common release film products.

[0003] Polyethylene terephthalate has excellent light transmittance, heat resistance, toughness, and insulation properties. However, PET is flammable, has low surface hardness, is not wear-resistant and scratch-resistant, and at the same time, due to its high resistivity, it is extremely easy to generate static electricity, restricting its application fields. Coating a release coating on the surface of the PET film is an effective method to improve its performance. Among them, silicone resin has a low surface energy, a small elastic modulus, and a low price, and has become the main raw material of the release coating. However, it still has low wear resistance, low surface energy, and easy accumulation of static electricity, resulting in the release film adsorbing dust or causing spark discharge during high-speed peeling. Although it can be improved by adding an antistatic agent, such additives may migrate to the surface, sacrificing the transparency and long-term stability of the coating.

[0004] Chinese Patent Publication No. CN118406354B discloses an easily peelable PET release film and a preparation process thereof. In this solution, glycidyl methacrylate is used to modify graphene oxide. Among them, graphene oxide can improve the conductivity, antistatic property, wear resistance and other properties of the material, making the release film have excellent mechanical properties. However, in this solution, the carboxyl group of graphene oxide reacts with the epoxy group in glycidyl methacrylate, leaving a large number of hydroxyl groups on the surface. Due to the residual hydroxyl functional groups, the conjugated structure is damaged, the electron migration is blocked, and the conductivity drops significantly, unable to meet the antistatic requirement of the release film. Summary of the Invention

[0005] The purpose of the present invention is to provide an optical-grade PET release film, a preparation method thereof, and an application thereof. By using the amino group of fluorinated hydroxyaniline to consume the hydroxyl and epoxy functional groups on the surface of graphene oxide, the hindrance of electron transmission is reduced, the conductivity of the release film is improved, and the antistatic requirement of the release film is met.

[0006] The purpose of the present invention can be achieved by the following technical solutions:

[0007] A preparation method of an optical-grade PET release film includes the following steps:

[0008] Step 1: Mix acrylic acid modified graphene oxide, toluene, hydrogen-containing silicone oil, and a 1% chloroplatinic acid - isopropanol solution, and stir under a nitrogen atmosphere at 90 - 100 °C and 400 - 500 r / min for 7 - 8 h, then perform vacuum distillation to obtain functionalized silicone oil.

[0009] Step 2: Mix organosilicon resin, polyacrylate, functionalized silicone oil, 1 - hydroxy - cyclohexyl phenyl ketone as a photoinitiator, fatty alcohol polyoxyethylene ether as an antifoaming agent, and sodium polyacrylate as a leveling agent uniformly, and let it stand to defoam to obtain a release coating; corona - treat one side of an optical - grade PET film, coat the release coating on the corona - treated side of the optical - grade PET film, and then cure to obtain a release layer, thus obtaining an optical - grade PET release film.

[0010] Further, in Step 1, the dosage ratio of acrylic acid modified graphene oxide, toluene, hydrogen - containing silicone oil, and chloroplatinic acid - isopropanol solution is 70 - 80 g: 4 - 5 L: 20 - 30 g: 100 - 120 mL.

[0011] Further, in Step 2, the dosage ratio of organosilicon resin, polyacrylate, functionalized silicone oil, 1 - hydroxy - cyclohexyl phenyl ketone, fatty alcohol polyoxyethylene ether, and sodium polyacrylate is 300 - 400 g: 170 - 180 g: 15 - 20 g: 2 - 3 g: 0.5 - 0.7 g: 0.3 - 0.5 g.

[0012] Further, the acrylic acid modified graphene oxide in Step 1 is prepared through the following steps:

[0013] Mix fluorinated modified graphene oxide, acrylic acid solution, and hydroquinone as a polymerization inhibitor, and stir at 20 - 25 °C and 400 - 500 r / min for 30 - 40 min, then add a 98% sulfuric acid solution, heat to 80 - 90 °C, and continue to react for 1 - 2 h. Naturally cool to room temperature, filter, wash the filter cake with deionized water 2 - 3 times, and vacuum - dry at 60 - 80 °C for 1 - 2 h to obtain acrylic acid modified graphene oxide.

[0014] Further, the dosage ratio of fluorinated modified graphene oxide, acrylic acid solution, hydroquinone, and sulfuric acid solution is 70 - 80 g: 50 - 60 mL: 0.5 - 0.8 g: 3 - 4 mL.

[0015] Further, the fluorinated modified graphene oxide is prepared through the following steps:

[0016] Add graphene oxide powder, fluorinated hydroxyaniline, absolute ethanol and deionized water into a reaction kettle, stir at 100 - 120 °C and 400 - 500 r / min for 12 - 14 h, naturally cool to room temperature, filter, wash the filter cake with absolute ethanol and deionized water for 2 - 3 times to obtain fluorinated modified graphene oxide.

[0017] Furthermore, the dosage ratio of graphene oxide powder, fluorinated hydroxyaniline, absolute ethanol and deionized water is 80 - 90 g : 30 - 40 g : 100 - 120 mL : 400 - 500 mL.

[0018] Furthermore, fluorinated hydroxyaniline is prepared through the following steps:

[0019] Add copper hexadecafluorophthalocyanine as a catalyst, sodium hydroxide, dimethyl sulfoxide and deionized water into a reaction kettle, stir at 20 - 25 °C and 400 - 500 r / min for 30 - 40 min under an argon atmosphere, then add fluorinated chloroaniline powder, heat to 130 - 140 °C, continue to react for 4 - 6 h, naturally cool to room temperature, add hydrochloric acid with a concentration of 1 mol / L to adjust the pH value to 6 - 7, then extract with ethyl acetate and wash with saturated brine for 2 - 3 times, combine the organic phases, dry with anhydrous sodium sulfate and concentrate under vacuum. Use petroleum ether / ethyl acetate with a volume ratio of 40 - 45 : 1 - 2 as the mobile phase and purify by flash column chromatography to obtain fluorinated hydroxyaniline.

[0020] Furthermore, the dosage ratio of copper hexadecafluorophthalocyanine, sodium hydroxide, dimethyl sulfoxide, deionized water and fluorinated chloroaniline powder is 0.1 - 0.2 g : 3 - 4 g : 100 - 120 mL : 100 - 120 mL : 80 - 90 g.

[0021] Furthermore, fluorinated chloroaniline powder is prepared through the following steps:

[0022] Add perfluorooctyl iodide, 2 - chloro - 4 - iodoaniline and dimethyl sulfoxide into a reaction kettle, stir at 20 - 25 °C and 400 - 500 r / min for 30 - 40 min, then add copper powder, heat to 120 - 130 °C, continue to react for 12 - 14 h, filter by suction, wash the filter cake with ether and deionized water for 2 - 3 times respectively, and dry in vacuum at 60 - 80 °C for 1 - 2 h to obtain fluorinated chloroaniline powder.

[0023] Furthermore, the dosage ratio of perfluorooctyl iodide, 2 - chloro - 4 - iodoaniline, dimethyl sulfoxide and copper powder is 80 - 90 g : 40 - 50 g : 2 - 3 L : 30 - 40 g.

[0024] The present invention also provides an application of an optical - grade PET release film in a flexible OLED manufacturing module.

[0025] Advantages of the present invention:

[0026] 1. The optical-grade PET release film prepared by the present invention has remarkable antistatic performance, stable peel strength, excellent light transmittance and stability in the flexible OLED manufacturing module. It has a high residual adhesion rate of the release layer, has no performance impact on the bonding material, and has good wear resistance and waterproofness, meeting the daily use of the release film and being able to be used under harsh environmental conditions.

[0027] 2. The fluorinated modified graphene oxide of the present invention uses copper hexadecafluorophthalocyanine as a catalyst and sodium hydroxide to provide hydroxyl anions to obtain fluorinated hydroxyaniline containing hydroxyl groups. The amino group on the surface of the fluorinated hydroxyaniline reacts with the carboxyl group of graphene oxide to graft the fluorinated hydroxyaniline onto the surface of graphene oxide. The hydroxyl group in the fluorinated hydroxyaniline, under the action of the catalyst, reacts with the carboxyl group of acrylic acid through an esterification reaction to graft acrylic acid onto the fluorinated modified graphene oxide, and the carboxyl group of acrylic acid can also react with the remaining hydroxyl groups on graphene oxide to form an ester group. The polarity of the ester group is lower than that of the hydroxyl group, and the degree of damage to the π electron cloud is smaller, further improving the conductive performance of the overall material; the amino functional group of the fluorinated hydroxyaniline can attack the epoxy group on GO to form a hydroxyl group accompanied by a proton transfer. The hydroxyl group on the surface of graphene oxide is very easy to first form a transition state of the epoxy group, and then the obtained epoxy group is attacked by the amino functional group, thereby reducing the number of oxygen-containing functional groups on the surface of graphene oxide and improving the conductive ability of graphene oxide.

[0028] 3. The acrylic acid modified graphene oxide of the present invention grafts acrylic acid onto the surface of graphene oxide through an esterification reaction. The grafting process of acrylic acid will further consume the hydroxyl groups remaining on the fluorinated modified graphene oxide, reducing the number of oxygen-containing functional groups of the acrylic acid modified graphene oxide. The reduction of oxygen-containing functional groups will further weaken the polar interaction between the functionalized silicone oil and the optical-grade PET film, thereby reducing the peel force. Detailed implementation manners

[0029] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0030] Example 1: A preparation method of an optical-grade PET release film, comprising the following steps:

[0031] S1: Add 80 g of perfluorooctyl iodide, 40 g of 2-chloro-4-iodoaniline, and 2 L of dimethyl sulfoxide into a reaction kettle. Stir for 30 min at 20 °C and 400 r / min, then add 30 g of copper powder, heat to 120 °C, and continue the reaction for 12 h. Perform suction filtration, wash the filter cake twice with ether and deionized water respectively, and dry in vacuum at 60 °C for 1 h to obtain fluorinated chloroaniline powder.

[0032] Perfluorooctyl iodide provides a long-chain perfluoroalkyl structure, which can significantly enhance the hydrophobicity and anti-oil pollution ability of materials.

[0033] S2: Add 0.1 g of copper(II) hexadecafluorophthalocyanine as a catalyst, 3 g of sodium hydroxide, 100 mL of dimethyl sulfoxide, and 100 mL of deionized water into a reaction kettle. Stir for 30 min at 20 °C and 400 r / min under an argon atmosphere, then add 80 g of fluorinated chloroaniline powder, heat to 130 °C, and continue the reaction for 4 h. Naturally cool to room temperature, add hydrochloric acid with a concentration of 1 mol / L to adjust the pH value to 6, then extract with ethyl acetate and wash twice with saturated brine. Combine the organic phases, dry with anhydrous sodium sulfate and concentrate in vacuum. Use petroleum ether / ethyl acetate with a volume ratio of 40:1 as the mobile phase and purify by flash column chromatography to obtain fluorinated hydroxyaniline.

[0034] Copper(II) hexadecafluorophthalocyanine acts as a catalyst. Its core copper ions activate the C-Cl bond in the fluorinated chloroaniline powder through coordination. Sodium hydroxide provides hydroxyl anions as nucleophiles, which attack the activated C-Cl bond through aromatic nucleophilic substitution reaction to obtain fluorinated hydroxyaniline containing hydroxyl groups.

[0035] S3: Add 80 g of graphene oxide powder, 30 g of fluorinated hydroxyaniline, 100 mL of absolute ethanol, and 400 mL of deionized water into a reaction kettle. Stir for 12 h at 100 °C and 400 r / min, naturally cool to room temperature, filter, and wash the filter cake twice with absolute ethanol and deionized water to obtain fluorinated modified graphene oxide.

[0036] The nucleophilicity of amino groups is stronger than that of hydroxyl groups. The reaction between amino groups and carboxyl groups belongs to nucleophilic substitution reaction, while the esterification reaction between hydroxyl groups and carboxyl groups usually requires a catalyst. Therefore, the amino groups in fluorinated hydroxyaniline react preferentially with the carboxyl groups on the surface of graphene oxide.

[0037] The amino functional group of fluorinated hydroxyaniline can attack the epoxy group on GO to form a hydroxyl group accompanied by a proton transfer. The hydroxyl group on the surface of graphene oxide is easily converted into the transition state of the epoxy group first, and then the obtained epoxy group is attacked by the amino functional group, thereby reducing the number of oxygen-containing functional groups on the surface of graphene oxide and improving the electrical conductivity of graphene oxide.

[0038] S4: Stir 70 g of fluorinated modified graphene oxide, 50 mL of acrylic acid solution, and 0.5 g of hydroquinone as a polymerization inhibitor at 20 °C and 400 r / min for 30 min. Then add 3 mL of concentrated sulfuric acid solution with a mass fraction of 98%, heat to 80 °C, and continue to react for 1 h. Naturally cool to room temperature, filter, wash the filter cake twice with deionized water, and dry it in vacuum at 60 °C for 1 h to obtain acrylic acid modified graphene oxide.

[0039] By grafting fluorinated hydroxyaniline on the surface of graphene oxide, fluorinated modified graphene oxide is obtained. The hydroxyl group in fluorinated hydroxyaniline, under the action of a catalyst, reacts with the carboxyl group of acrylic acid through an esterification reaction to graft acrylic acid on the fluorinated modified graphene oxide. Moreover, the carboxyl group of acrylic acid can also react with the residual hydroxyl groups on graphene oxide to form ester groups. The polarity of the ester group is lower than that of the hydroxyl group, and the degree of damage to the π electron cloud is smaller, further improving the electrical conductivity of the overall material.

[0040] S5: Stir 70 - 80 g of acrylic acid modified graphene oxide, 4 - 5 L of toluene, 20 - 30 g of hydrogen-containing silicone oil, and 100 - 120 mL of a 1% chloroplatinic acid - isopropanol solution under a nitrogen atmosphere at 90 - 100 °C and 400 - 500 r / min for 7 - 8 h, and then perform vacuum distillation to obtain functionalized silicone oil.

[0041] The reduction of oxygen-containing functional groups on the surface of acrylic acid modified graphene oxide will further weaken the polar interaction between the functionalized silicone oil and the optical grade PET film, thereby reducing the peel force.

[0042] S6: Mix 300 - 400 g of silicone resin, 170 - 180 g of polyacrylate, 15 - 20 g of functionalized silicone oil, 2 - 3 g of 1 - hydroxy - cyclohexyl phenyl ketone as a photoinitiator, 0.5 - 0.7 g of fatty alcohol polyoxyethylene ether as an antifoaming agent, and 0.3 - 0.5 g of sodium polyacrylate as a leveling agent evenly, and let it stand to defoam to obtain a release coating; corona-treat one side of the optical grade PET film, coat the release coating on the corona-treated side of the optical grade PET film, and then cure to obtain a release layer, thus obtaining an optical grade PET release film.

[0043] Example 2: A method for preparing an optical grade PET release film, comprising the following steps:

[0044] S1: Add 85 g of perfluorooctyl iodide, 45 g of 2 - chloro - 4 - iodoaniline, and 2.5 L of dimethyl sulfoxide to a reaction kettle, stir at 22.5 °C and 450 r / min for 35 min, then add 35 g of copper powder, heat to 125 °C, and continue to react for 13 h. Perform suction filtration, wash the filter cake twice with ether and deionized water respectively, and dry it in vacuum at 70 °C for 1.5 h to obtain fluorinated chloroaniline powder.

[0045] S2: Add 0.15 g of copper hexadecafluorophthalocyanine as a catalyst, 3.5 g of sodium hydroxide, 110 mL of dimethyl sulfoxide, and 110 mL of deionized water into a reaction kettle. Stir for 35 min under the conditions of an argon atmosphere, 22.5 °C, and 450 r / min. Then add 85 g of fluorochloroaniline powder, heat to 135 °C, and continue the reaction for 5 h. Naturally cool to room temperature, adjust the pH value to 6.5 with 1 mol / L hydrochloric acid, then extract with ethyl acetate and wash twice with saturated brine. Combine the organic phases, dry with anhydrous sodium sulfate, and concentrate under vacuum. Use petroleum ether / ethyl acetate with a volume ratio of 42.5:1.5 as the mobile phase and purify by flash column chromatography to obtain fluorinated hydroxyaniline.

[0046] S3: Add 85 g of graphene oxide powder, 35 g of fluorinated hydroxyaniline, 110 mL of absolute ethanol, and 450 mL of deionized water into a reaction kettle. Stir for 13 h under the conditions of 110 °C and 450 r / min. Naturally cool to room temperature, filter, and wash the filter cake twice with absolute ethanol and deionized water to obtain fluorinated modified graphene oxide.

[0047] S4: Add 75 g of fluorinated modified graphene oxide, 55 mL of acrylic acid solution, and 0.65 g of hydroquinone as an inhibitor. Stir for 35 min under the conditions of 22.5 °C and 450 r / min. Then add 3.5 mL of 98% sulfuric acid solution, heat to 85 °C, and continue the reaction for 1.5 h. Naturally cool to room temperature, filter, wash the filter cake twice with deionized water, and dry in vacuum at 70 °C for 1.5 h to obtain acrylic acid modified graphene oxide.

[0048] S5: Add 70 g of acrylic acid modified graphene oxide, 4 L of toluene, 20 g of hydrogen-containing silicone oil, and 100 mL of 1% chloroplatinic acid-isopropanol solution. Stir for 7 h under a nitrogen atmosphere, at 90 °C and 400 r / min, and then perform vacuum distillation to obtain functionalized silicone oil.

[0049] S6: Mix 300 g of silicone resin, 170 g of polyacrylate, 15 g of functionalized silicone oil, 2 g of 1-hydroxy-cyclohexyl phenyl ketone as a photoinitiator, 0.5 g of fatty alcohol polyoxyethylene ether as an antifoaming agent, and 0.3 g of sodium polyacrylate as a leveling agent evenly, and let it stand to defoam to obtain a release coating; corona-treat one side of an optical grade PET film, coat the release coating on the corona-treated side of the optical grade PET film, and then cure to obtain a release layer, thus obtaining an optical grade PET release film.

[0050] Example 3: A method for preparing an optical grade PET release film, comprising the following steps:

[0051] S1: Add 90 g of perfluorooctyl iodide, 50 g of 2-chloro-4-iodoaniline, and 3 L of dimethyl sulfoxide into a reaction kettle. Stir at 25 °C and 500 r / min for 40 min, then add 40 g of copper powder, heat to 130 °C, and continue the reaction for 14 h. Perform suction filtration, wash the filter cake 3 times with ether and deionized water respectively, and dry in vacuum at 80 °C for 2 h to obtain fluorinated chloroaniline powder.

[0052] S2: Add 0.2 g of copper hexadecafluorophthalocyanine as a catalyst, 4 g of sodium hydroxide, 120 mL of dimethyl sulfoxide, and 120 mL of deionized water into a reaction kettle. Stir at 25 °C and 500 r / min for 40 min under an argon atmosphere, then add 90 g of fluorinated chloroaniline powder, heat to 140 °C, and continue the reaction for 6 h. Naturally cool to room temperature, add hydrochloric acid with a concentration of 1 mol / L to adjust the pH value to 7, then extract with ethyl acetate and wash 3 times with saturated brine. Combine the organic phases, dry with anhydrous sodium sulfate and concentrate in vacuum. Use petroleum ether / ethyl acetate with a volume ratio of 45:2 as the mobile phase and purify by flash column chromatography to obtain fluorinated hydroxyaniline.

[0053] S3: Add 90 g of graphene oxide powder, 40 g of fluorinated hydroxyaniline, 120 mL of absolute ethanol, and 500 mL of deionized water into a reaction kettle. Stir at 120 °C and 500 r / min for 14 h, naturally cool to room temperature, filter, and wash the filter cake 3 times with absolute ethanol and deionized water to obtain fluorinated modified graphene oxide.

[0054] S4: Add 80 g of fluorinated modified graphene oxide, 60 mL of acrylic acid solution, and 0.8 g of hydroquinone as an inhibitor. Stir at 25 °C and 500 r / min for 40 min, then add 4 mL of concentrated sulfuric acid solution with a mass fraction of 98%, heat to 90 °C, and continue the reaction for 2 h. Naturally cool to room temperature, filter, wash the filter cake 3 times with deionized water, and dry in vacuum at 80 °C for 2 h to obtain acrylic acid modified graphene oxide.

[0055] S5: Add 80 g of acrylic acid modified graphene oxide, 5 L of toluene, 30 g of hydrogen-containing silicone oil, and 120 mL of a 1% chloroplatinic acid-isopropanol solution. Stir at 100 °C and 500 r / min for 8 h under a nitrogen atmosphere, and perform vacuum distillation to obtain functionalized silicone oil.

[0056] S6: Mix 400 g of silicone resin, 180 g of polyacrylate, 20 g of functionalized silicone oil, 3 g of 1-hydroxy-cyclohexyl phenyl ketone as a photoinitiator, 0.7 g of fatty alcohol polyoxyethylene ether as an antifoaming agent, and 0.5 g of sodium polyacrylate as a leveling agent evenly, let it stand for defoaming to obtain a release coating; corona-treat one side of the optical-grade PET film, coat the release coating on the corona-treated side of the optical-grade PET film, and then cure it to obtain a release layer, thus obtaining an optical-grade PET release film.

[0057] In the examples, the silicone resin was purchased from Elkem Silicones (Shanghai) Co., Ltd.; the polyacrylate was purchased from Jinan Feiyue Chemical Co., Ltd.

[0058] Comparative Example 1: Referring to the modified silicone oil described in Paragraph 12 of the specification of the Chinese invention patent with the publication number CN118406354B, on the basis of Example 3 of the present invention, replace the functionalized silicone oil in Step S6 with the modified silicone oil, and keep the rest of the steps unchanged to prepare an optical-grade PET release film.

[0059] Comparative Example 2: On the basis of Example 3, replace 2-chloro-4-iodoaniline in Step S1 with commercially available o-chloroiodobenzene to prepare fluorinated chlorobenzene powder, and replace fluorinated hydroxyaniline in Step S2, and keep the rest of the steps unchanged to prepare an optical-grade PET release film.

[0060] Comparative Example 3: On the basis of Example 3, without going through the treatment of Step S4, replace the fluorinated modified graphene oxide obtained in Step S3 with acrylic acid modified graphene oxide in Step S5, and keep the rest of the steps unchanged to prepare an optical-grade PET release film.

[0061] The surface resistance was tested with a ZC-36 type high resistance meter referring to GB / T 1410-2006; the peel strength was tested with a TESA7475 standard tape at a peeling rate of 300 mm / min and 180° peeling referring to GB / T 25256-2010; the residual adhesion rate of the release layer was tested referring to GB / T25256-2010, with a peeling rate of 300 mm / min. The larger the residual adhesion rate, the higher the curing rate of the silicone oil and the more perfect the curing of the release film; the abrasion resistance was tested referring to GB / T 1768-2006. When the weight loss of the film was less than 10%, the abrasion resistance was qualified. The release coating was applied to a sample plate with a diameter of 200 mm and a center hole diameter of 9 mm, and after drying, it was ground and rotated 50 times. The abrasion resistance = loss amount / coating amount × 100%; the water contact angle was tested with a PZ-200SD type contact angle measuring instrument. The results are shown in Table 1:

[0062] Table 1 Performance test results of optical-grade PET release film

[0063]

[0064]

[0065] As can be seen from Table 1, for the optical-grade PET release films prepared in Examples 1-3, the peel force and residual adhesion rate are stable, the wear resistance and water contact angle are significantly higher than those of the comparative examples, and the surface resistance is significantly lower than that of the comparative examples, indicating that the optical-grade PET release film prepared by the present invention has significant antistatic performance, stable peelability, excellent light transmittance and stability, high residual adhesion rate, no performance impact on the bonding material, and good wear resistance and waterproofness, effectively ensuring its use under harsh environmental conditions.

[0066] In Comparative Example 1, referring to the Chinese invention patent with the publication number CN118406354B, glycidyl methacrylate was used to modify graphene oxide. The epoxy group of glycidyl methacrylate binds to the carboxyl group on the surface of graphene oxide. In this process, only the carboxyl group is consumed. Then, through the hydrosilylation reaction of the carbon-carbon double bond on the surface of the modified graphene oxide, the carbon-carbon double bond on the surface of dodecafluoroheptyl methacrylate, and the silicon-hydrogen bond on the surface of the hydrogen-containing silicone oil, in the modified silicone oil obtained in this step, there are relatively many residual oxygen-containing functional groups on the surface of the modified graphene oxide, which cannot meet the requirements of the release film for the conductive ability.

[0067] In Comparative Example 2, 2-chloro-4-iodoaniline was replaced with o-chloroiodobenzene. O-chloroiodobenzene does not contain an amino group, and the amino group can reduce the oxygen-containing functional groups on the surface of graphene oxide, reducing the hindrance of the oxygen-containing functional groups to the conductive ability of graphene oxide.

[0068] In Comparative Example 3, fluorinated modified graphene oxide was replaced with acrylic acid modified graphene oxide. The hydroxyl group in fluorinated hydroxyaniline, under the action of a catalyst, reacts with the carboxyl group of acrylic acid through an esterification reaction to graft acrylic acid onto the fluorinated modified graphene oxide, and the carboxyl group of acrylic acid can also react with the residual hydroxyl group on graphene oxide to form an ester group. The polarity of the ester group is lower than that of the hydroxyl group, and the degree of damage to the π electron cloud is smaller, further improving the conductive performance of the overall material.

[0069] Although the embodiments of the present invention have been shown and described, it will be understood by those of ordinary skill in the art that various changes, modifications, substitutions, and variations can be made to these embodiments without departing from the principles and spirit of the present invention.

Claims

1. A preparation method of an optical-grade PET release film, characterized in that, It includes the following steps: Step 1: Mix acrylic acid modified graphene oxide, toluene, hydrogen-containing silicone oil, and a 1% chloroplatinic acid-isopropanol solution, and stir at 90 - 100 °C and 400 - 500 r / min for 7 - 8 h under a nitrogen atmosphere, then perform vacuum distillation to obtain functionalized silicone oil; Step 2: Mix silicone resin, polyacrylate, functionalized silicone oil, 1-hydroxy-cyclohexyl phenyl ketone, fatty alcohol polyoxyethylene ether, and sodium polyacrylate evenly, let it stand to defoam to obtain a release coating; corona-treat one side of an optical-grade PET film, coat the release coating on the corona-treated side of the optical-grade PET film, and then cure to obtain a release layer, thus obtaining an optical-grade PET release film.

2. The preparation method of an optical grade PET release film according to claim 1, characterized in that, In Step 1, the dosage ratio of the acrylic acid modified graphene oxide, toluene, hydrogen-containing silicone oil, and chloroplatinic acid-isopropanol solution is 70 - 80 g : 4 - 5 L : 20 - 30 g : 100 - 120 mL.

3. The preparation method of an optical grade PET release film according to claim 1, characterized in that, In Step 2, the dosage ratio of the silicone resin, polyacrylate, functionalized silicone oil, 1-hydroxy-cyclohexyl phenyl ketone, fatty alcohol polyoxyethylene ether, and sodium polyacrylate is 300 - 400 g : 170 - 180 g : 15 - 20 g : 2 - 3 g : 0.5 - 0.7 g : 0.3 - 0.5 g.

4. The preparation method of an optical-grade PET release film according to claim 1, characterized in that, The acrylic acid modified graphene oxide in Step 1 is prepared through the following steps: Mix fluorinated modified graphene oxide, acrylic acid solution, and hydroquinone as a polymerization inhibitor, stir at 20 - 25 °C and 400 - 500 r / min for 30 - 40 min, then add 98 wt% sulfuric acid solution, heat to 80 - 90 °C, continue to react for 1 - 2 h, naturally cool to room temperature, filter, wash, and perform vacuum drying to obtain acrylic acid modified graphene oxide; The dosage ratio of the fluorinated modified graphene oxide, acrylic acid solution, hydroquinone, and sulfuric acid solution is 70 - 80 g : 50 - 60 mL : 0.5 - 0.8 g : 3 - 4 mL.

5. The preparation method of an optical grade PET release film according to claim 4, wherein, The fluorinated modified graphene oxide is prepared through the following steps: Add graphene oxide powder, fluorinated hydroxyaniline, absolute ethanol, and deionized water into a reaction kettle, stir at 100 - 120 °C and 400 - 500 r / min for 12 - 14 h, naturally cool to room temperature, filter, and wash to obtain fluorinated modified graphene oxide; The dosage ratio of the graphene oxide powder, fluorinated hydroxyaniline, absolute ethanol, and deionized water is 80 - 90 g : 30 - 40 g : 100 - 120 mL : 400 - 500 mL.

6. The preparation method of an optical grade PET release film according to claim 5, characterized in that, The fluorinated hydroxyaniline is prepared through the following steps: Copper hexadecafluorophthalocyanine, sodium hydroxide, dimethyl sulfoxide and deionized water are added into a reaction kettle. Under an argon atmosphere, stir at 20 - 25 °C and 400 - 500 r / min for 30 - 40 min, then add 4-chloro-2-fluoroaniline powder, heat to 130 - 140 °C, and continue to react for 4 - 6 h. Naturally cool to room temperature, add hydrochloric acid with a concentration of 1 mol / L to adjust the pH value to 6 - 7, then extract with ethyl acetate and wash with saturated brine 2 - 3 times. Combine the organic phases, dry with anhydrous sodium sulfate and concentrate under vacuum. Use petroleum ether / ethyl acetate with a volume ratio of 40 - 45:1 - 2 as the mobile phase and purify by flash column chromatography to obtain 4-chloro-2-fluoroaniline.

7. The preparation method of an optical-grade PET release film according to claim 6, wherein, The dosage ratio of the copper hexadecafluorophthalocyanine, sodium hydroxide, dimethyl sulfoxide, deionized water and 4-chloro-2-fluoroaniline powder is 0.1 - 0.2 g:3 - 4 g:100 - 120 mL:100 - 120 mL:80 - 90 g.

8. The preparation method of an optical grade PET release film according to claim 7, characterized in that, The 4-chloro-2-fluoroaniline powder is prepared by the following steps: Perfluorooctyl iodide, 2-chloro-4-iodoaniline and dimethyl sulfoxide are added into a reaction kettle. Stir at 20 - 25 °C and 400 - 500 r / min for 30 - 40 min, then add copper powder, heat to 120 - 130 °C, and continue to react for 12 - 14 h. Filter by suction, wash, and dry under vacuum to obtain the 4-chloro-2-fluoroaniline powder; The dosage ratio of the perfluorooctyl iodide, 2-chloro-4-iodoaniline, dimethyl sulfoxide and copper powder is 80 - 90 g:40 - 50 g:2 - 3 L:30 - 40 g.

9. An optical grade PET release film, characterized in that, Prepared by the preparation method according to any one of claims 1 - 8.

10. Use of an optical grade PET release film according to claim 9 in a flexible OLED manufacturing module.

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