Fluorine release film for high-viscosity silica gel protective film of AF glass screen and preparation method of fluorine release film

Abstract

The invention discloses a fluorine release film for a high-viscosity silica gel protective film of an AF glass screen and a preparation method of the fluorine release film, and belongs to the technical field of unsaturated polyester, raw materials are uniformly mixed and coated on a PET base material, during high-temperature heat preservation, part of double bonds on a modified release agent and a modified filler can react with silicon-hydrogen bonds on hydrogen-containing silicone oil under the action of chloroplatinic acid, so that the fluorine release film is formed. The modified filler and the modified release agent are grafted by residual double bonds on the modified filler and the modified release agent under the action of 2, 4, 6-trimethylbenzoyl-diphenyl phosphine oxide through ultraviolet irradiation, so that the modified filler is more thoroughly contacted with polymer molecules, a stable conductive grid can be formed during raw material curing, and the conductivity of the conductive grid is improved. Meanwhile, under the action of triphenyl sulfonium hexafluorophosphate, an expanding monomer DB-TOSU is subjected to double-ring-opening polymerization to form bicyclic acetal, the bicyclic acetal is converted into carbonyl and hydroxyl, and the carbonyl and hydroxyl are matched with a polyhedral oligomeric silsesquioxane structure on the modified filler, so that the smoothness of the surface of the release film is ensured.

Description

Technical Field

[0001] The invention belongs to the technical field of unsaturated polyesters, and in particular relates to a fluorine release film for a high-viscosity silicone protective film for an AF glass screen and a preparation method thereof. Background Art

[0002] There are many kinds of protective films on the market for protecting AF glass screens, and the most common one is silicone protective film. However, the existing silicone protective film has some shortcomings in daily use: for example, it has strong adhesion, easy to leave adhesive residue, and difficult to clean; it is easy to cause bubbles when it falls off, affecting the use effect; at the same time, the inherent characteristics of silicone make it difficult to ensure long-term stable anti-scratch and anti-wear performance. In order to overcome the shortcomings of silicone protective film, the traditional solution is to combine silicone protective film with fluorine release film. Fluorine release film can effectively reduce the bonding strength of silicone protective film, thereby reducing the phenomenon of bonding residue and falling off, but the current release film is based on PET. Due to the high resistivity of PET, it is very easy to generate static electricity, which causes the release film to easily absorb dust, affecting the normal use of the release film. Summary of the invention

[0003] The purpose of the present invention is to provide a fluorine release film for a high-viscosity silicone protective film for an AF glass screen and a preparation method thereof, so as to solve the problem that the current fluorine release film has a general release effect and poor antistatic effect, resulting in electrostatic adsorption of dust.

[0004] The purpose of the present invention can be achieved through the following technical solutions: A method for preparing a fluorine release film for a high-viscosity silicone protective film for an AF glass screen belongs to the technical field of unsaturated polyesters and specifically comprises the following steps: Step A1: uniformly mix perfluorodecylethylene, tetramethylcyclotetrasiloxane, chloroplatinic acid and DMF, and react for 3-5 hours at a speed of 120-150 r / min and a temperature of 70-80° C. to obtain a modified monomer; uniformly mix the modified monomer, octamethylcyclotetrasiloxane, tetramethylammonium hydroxide, tetramethyldisiloxane and dimethyl sulfoxide, introduce nitrogen protection, and react for 3-5 hours at a speed of 120-150 r / min and a temperature of 105-110° C. to obtain dihydrogenpolysiloxane; Step A2: dihydrogenpolysiloxane, allyl alcohol, chloroplatinic acid and DMF are uniformly mixed, and reacted for 3-5 hours at a speed of 150-200 r / min and a temperature of 80-90° C. to obtain modified silicone; modified silicone, isophorone diisocyanate, dibutyltin dilaurate and tetrahydrofuran are mixed, nitrogen is introduced for protection, and reacted for 3-5 hours at a speed of 120-150 r / min and a temperature of 70-75° C., and then hydroxyethyl methacrylate is added and the reaction is continued for 3-5 hours to obtain a modified release agent; Step A3: Weigh the following raw materials in parts by weight: 30-50 parts of modified release agent, 10-15 parts of hydrogenated silicone oil, 0.1-0.3 parts of chloroplatinic acid, 20-30 parts of modified filler, 0.5-0.8 parts of expansion monomer DB-TOSU, 0.15-0.25 parts of triphenylsulfonium hexafluorophosphate, 0.3-0.5 parts of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and 20-30 parts of ethyl acetate, mix the raw materials evenly and apply them on a PET substrate, keep the temperature at 70-80°C for 2-3 hours, and irradiate with 365nm ultraviolet light for 3-5 minutes to obtain a fluorine release film for a high-viscosity silicone protective film for an AF glass screen.

[0005] Furthermore, the molar ratio of perfluorodecylethylene and tetramethylcyclotetrasiloxane described in step A1 is 4:1, the amount of chloroplatinic acid used is 1‰ of tetramethylcyclotetrasiloxane, and the molar ratio of modified monomer, octamethylcyclotetrasiloxane, tetramethylammonium hydroxide and tetramethyldisiloxane is 0.4:2:2:3.

[0006] Furthermore, the molar ratio of dihydrogenpolysiloxane and allyl alcohol in step A2 is 1:2, the amount of chloroplatinic acid is 1‰ of tetramethylcyclotetrasiloxane, the molar ratio of modified silicone, isophorone diisocyanate and hydroxyethyl methacrylate is 3:4:2, and the amount of dibutyltin dilaurate is 2% of the mass of modified silicone.

[0007] Further, the modified filler is prepared by the following steps: Step B1: adding concentrated sulfuric acid to a reaction kettle, stirring and adding graphene and potassium permanganate at a speed of 800-1000 r / min and a temperature of 20-25° C., stirring for 3-4 hours, heating to 45-50° C., reacting for 3-5 hours, adding deionized water to terminate the reaction and washing to neutrality to obtain graphene oxide, mixing graphene oxide and ammonia water uniformly, reacting for 5-7 hours at a speed of 120-150 r / min and a temperature of 95-100° C., to obtain amination graphene; Step B2: The amino graphene, the amino cage silsesquioxane, the aniline, the hydrochloric acid solution, the isopropanol and the deionized water are mixed evenly, and ammonium persulfate is added under the conditions of a rotation speed of 120-150 r / min and a temperature of 0-3°C, and the reaction is carried out for 5-7 hours, and the filtrate is removed by filtering, and the substrate is added to DMF, and the mixture is heat-treated for 40-45 hours under the conditions of a rotation speed of 200-300 r / min and a temperature of 90-95°C to obtain a modified filler.

[0008] Furthermore, the dosage ratio of concentrated sulfuric acid, graphene and potassium permanganate in step B1 is 110mL:1g:6g, the mass fraction of concentrated sulfuric acid is 98%, the dosage ratio of graphene oxide and ammonia water is 1g:20mL, and the mass fraction of ammonia water is 28%.

[0009] Furthermore, the amount ratio of the amination graphene, amination cage silsesquioxane, aniline, hydrochloric acid solution, isopropanol, deionized water and ammonium persulfate described in step B2 is 1g:3g:1.5g:60mL:40mL:200mL:3g, and the mass fraction of the hydrochloric acid solution is 7%.

[0010] Further, the amino cage-type silsesquioxane is prepared by the following steps: Step C1: Phenyltrimethoxysilane, isopropanol, sodium hydroxide and deionized water are mixed, and the reaction is carried out for 3-5 hours at a speed of 120-150 r / min and a temperature of 85-90° C., and the temperature is lowered to 20-25° C. and the reaction is continued for 10-15 hours to obtain sodium octaphenylcyclotetrasiloxane tetrasiloxide; sodium octaphenylcyclotetrasiloxane tetrasiloxide, methyldichlorosilane, triethylamine and tetrahydrofuran are mixed, and the reaction is carried out for 3-5 hours at a speed of 150-200 r / min and a temperature of 0° C., and the temperature is raised to 20-25° C. and the reaction is continued for 20-22 hours to obtain dihydrogen cage-type silsesquioxane; Step C2: dihydrogen cage silsesquioxane, p-hydroxystyrene, chloroplatinic acid and tetrahydrofuran are uniformly mixed, nitrogen is introduced for protection, and the reaction is carried out for 20-25 hours at a speed of 120-150 r / min and a temperature of 80-85° C. to obtain a functionalized cage silsesquioxane; the functionalized cage silsesquioxane is dissolved in DMF, and concentrated nitric acid and concentrated sulfuric acid are added under stirring at a speed of 60-80 r / min and a temperature of 0-2° C. to react for 1-1.5 hours to obtain a nitrated cage silsesquioxane; Step C3: Mix the nitrated cage-type silsesquioxane, acryloyl chloride, triethylamine and DMF, react for 2-3 hours at a speed of 300-500 r / min and a temperature of 20-25° C. to obtain a modified cage-type silsesquioxane; mix zinc powder, acetic acid, deionized water and DMF, stir and add the modified cage-type silsesquioxane at a speed of 150-200 r / min and a temperature of 80-85° C., react for 1-1.5 hours, adjust the pH to alkaline, and obtain an amino cage-type silsesquioxane.

[0011] Furthermore, the amount ratio of phenyltrimethoxysilane, isopropanol, sodium hydroxide and deionized water in step C1 is 120mmol:120mmol:80mmol:3mL, and the amount ratio of sodium octaphenylcyclotetrasiloxane tetrasiliconate, methyldichlorosilane, triethylamine and tetrahydrofuran is 12g:4.5mL:3.5g:30mL.

[0012] Furthermore, the molar ratio of the dihydrogen cage silsesquioxane and p-hydroxystyrene described in step C2 is 1:2, the amount of chloroplatinic acid used is 1‰ of the mass of p-hydroxystyrene, and the amount ratio of the functionalized cage silsesquioxane, concentrated nitric acid and concentrated sulfuric acid is 10mmol:9mL:10mL.

[0013] Furthermore, the molar ratio of the nitrated cage-type silsesquioxane, acryloyl chloride and triethylamine described in step C3 is 1:2:2.1, and the amount ratio of zinc powder, acetic acid, deionized water, DMF and modified cage-type silsesquioxane is 2.5g:2g:20mL:50mL:1.5g.

[0014] Beneficial effects of the invention: The invention discloses a fluorine release film for a high-viscosity silicone protective film for an AF glass screen, comprising the following raw materials: a modified release agent, hydrogenated silicone oil, chloroplatinic acid, a modified filler, an expansion monomer DB-TOSU, triphenylsulfonium hexafluorophosphate, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and ethyl acetate, the raw materials are uniformly mixed and then coated on a PET substrate for curing to obtain a fluorine release film, the modified release agent is made of perfluorodecylethylene and tetramethylcyclotetrasiloxane as raw materials , allowing the double bond on perfluorodecylethylene to react with the Si-H bond on tetramethylcyclotetrasiloxane to obtain a modified monomer, opening the modified monomer and octamethylcyclotetrasiloxane, and then condensing with tetramethyldisiloxane to obtain dihydrogenpolysiloxane, reacting the dihydrogenpolysiloxane with allyl alcohol, allowing the Si-H bond on the dihydrogenpolysiloxane to react with the double bond on the allyl alcohol to obtain a modified silicone, reacting the modified silicone with isophorone diisocyanate, and then capping with hydroxyethyl methacrylate to obtain a modified release agent.

[0015] The modified filler is prepared by oxidation treatment of graphene as a raw material to obtain graphene oxide, which is treated with ammonia water to obtain aminated graphene, the aminated graphene, amino cage silsesquioxane and aniline are mixed, and polyaniline is formed between the aminated graphene and the amino cage silsesquioxane under the action of ammonium persulfate to obtain the modified filler, the aminated cage silsesquioxane is hydrolyzed and condensed with phenyltrimethoxysilane to obtain sodium octaphenylcyclotetrasiloxane tetrasilanolate, and the sodium octaphenylcyclotetrasiloxane tetrasilanolate is reacted with methyldichlorosilane so that the sodium silanolate on the sodium octaphenylcyclotetrasiloxane tetrasilanolate reacts with the chlorine atom site on the methyldichlorosilane to obtain dihydrogen cage The invention relates to a method for preparing a functionalized cage silsesquioxane, reacting a dihydrogen cage silsesquioxane with p-hydroxystyrene so that the Si-H bond on the dihydrogen cage silsesquioxane reacts with the double bond on the p-hydroxystyrene to obtain a functionalized cage silsesquioxane, treating the functionalized cage silsesquioxane with concentrated sulfuric acid and concentrated nitric acid to form a nitrobenzene structure to obtain a nitrated cage silsesquioxane, reacting the nitrated cage silsesquioxane with propionyl chloride so that the phenolic hydroxyl group on the nitrated cage silsesquioxane reacts with the acyl chloride on the acryloyl chloride to obtain a modified cage silsesquioxane, reducing the modified cage silsesquioxane, and adjusting the pH to be alkaline to obtain an aminated cage silsesquioxane.

[0016] The raw materials are mixed and evenly coated on the PET substrate. When the material is kept at high temperature, part of the double bonds on the modified release agent and the modified filler can react with the silicon-hydrogen bonds on the hydrogen-containing silicone oil under the action of chloroplatinic acid, thereby increasing the release effect of the release film and reducing silicon transfer. After ultraviolet light irradiation, the remaining double bonds on the modified filler and the modified release agent are grafted under the action of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, so that the modified filler and the polymer molecules are more thoroughly contacted. A stable conductive grid can be formed during the curing of the raw materials, thereby improving the antistatic effect of the release film and preventing the electrostatic adsorption of dust. At the same time, under the action of triphenylsulfonium hexafluorophosphate, the expansion monomer DB-TOSU undergoes double ring-opening polymerization to form a bicyclic acetal, which is converted into a carbonyl and a hydroxyl group, and cooperates with the cage-type silsesquioxane structure on the modified filler to prevent the raw material from shrinking during curing and ensure the flatness of the release film surface. DETAILED DESCRIPTION

[0017] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0018] Embodiment 1: A method for preparing a fluorine release film for a high-viscosity silicone protective film for an AF glass screen, comprising the following steps: Step A1: uniformly mix perfluorodecylethylene, tetramethylcyclotetrasiloxane, chloroplatinic acid and DMF, and react for 3 hours at a speed of 120 r / min and a temperature of 70° C. to obtain a modified monomer; uniformly mix the modified monomer, octamethylcyclotetrasiloxane, tetramethylammonium hydroxide, tetramethyldisiloxane and dimethyl sulfoxide, introduce nitrogen protection, and react for 3 hours at a speed of 120 r / min and a temperature of 105° C. to obtain dihydrogenpolysiloxane; Step A2: dihydrogenpolysiloxane, allyl alcohol, chloroplatinic acid and DMF are mixed evenly, and reacted for 3 hours at a speed of 150 r / min and a temperature of 80° C. to obtain modified silicone; modified silicone, isophorone diisocyanate, dibutyltin dilaurate and tetrahydrofuran are mixed, nitrogen is introduced for protection, and reacted for 3 hours at a speed of 120 r / min and a temperature of 70° C., and then hydroxyethyl methacrylate is added and the reaction is continued for 3 hours to obtain a modified release agent; Step A3: Weigh the following raw materials in parts by weight: 30 parts of modified release agent, 10 parts of hydrogenated silicone oil, 0.1 parts of chloroplatinic acid, 20 parts of modified filler, 0.5 parts of expansion monomer DB-TOSU, 0.15 parts of triphenylsulfonium hexafluorophosphate, 0.3 parts of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and 20 parts of ethyl acetate, mix the raw materials evenly and apply them on a PET substrate, keep the temperature at 70°C for 2 hours, and irradiate with 365nm ultraviolet light for 3 minutes to obtain a fluorine release film for AF glass screen high-viscosity silicone protective film.

[0019] The molar ratio of perfluorodecylethylene and tetramethylcyclotetrasiloxane described in step A1 is 4:1, the amount of chloroplatinic acid used is 1‰ of tetramethylcyclotetrasiloxane, and the molar ratio of modified monomer, octamethylcyclotetrasiloxane, tetramethylammonium hydroxide and tetramethyldisiloxane is 0.4:2:2:3.

[0020] The molar ratio of dihydrogenpolysiloxane and allyl alcohol described in step A2 is 1:2, the amount of chloroplatinic acid is 1‰ of tetramethylcyclotetrasiloxane, the molar ratio of modified silicone, isophorone diisocyanate and hydroxyethyl methacrylate is 3:4:2, and the amount of dibutyltin dilaurate is 2% of the mass of modified silicone.

[0021] The model of the hydrogen-containing silicone oil described in step A3 is RH-H502.

[0022] The modified filler is prepared by the following steps: Step B1: Add concentrated sulfuric acid to a reactor, stir and add graphene and potassium permanganate at a speed of 800 r / min and a temperature of 20° C., stir for 3 h, heat to 45° C., react for 3 h, add deionized water to terminate the reaction and wash to neutrality to obtain graphene oxide, mix graphene oxide and ammonia water evenly, react for 5 h at a speed of 120 r / min and a temperature of 95° C. to obtain amination graphene; Step B2: The amino graphene, amino cage silsesquioxane, aniline, hydrochloric acid solution, isopropanol and deionized water are mixed evenly, stirred and ammonium persulfate is added at a speed of 120 r / min and a temperature of 0°C, and the reaction is carried out for 5 hours. The filtrate is removed by filtering, and the substrate is added to DMF. At a speed of 200 r / min and a temperature of 90°C, the mixture is heat-treated for 40 hours to obtain a modified filler.

[0023] The amount ratio of concentrated sulfuric acid, graphene and potassium permanganate described in step B1 is 110mL:1g:6g, the mass fraction of concentrated sulfuric acid is 98%, the amount ratio of graphene oxide and ammonia water is 1g:20mL, and the mass fraction of ammonia water is 28%.

[0024] The amount ratio of the amination graphene, amination cage silsesquioxane, aniline, hydrochloric acid solution, isopropanol, deionized water and ammonium persulfate described in step B2 is 1g:3g:1.5g:60mL:40mL:200mL:3g, and the mass fraction of the hydrochloric acid solution is 7%.

[0025] The amino cage-type silsesquioxane is prepared by the following steps: Step C1: Phenyltrimethoxysilane, isopropanol, sodium hydroxide and deionized water are mixed, and the mixture is reacted at a speed of 120 r / min and a temperature of 85° C. for 3 hours, and then the mixture is cooled to 20° C. and the mixture is reacted for 10 hours to obtain sodium octaphenylcyclotetrasiloxane tetrasiloxide; sodium octaphenylcyclotetrasiloxane tetrasiloxide, methyldichlorosilane, triethylamine and tetrahydrofuran are mixed, and the mixture is reacted at a speed of 150 r / min and a temperature of 0° C. for 3 hours, and then the mixture is heated to 20° C. and the mixture is reacted for 20 hours to obtain dihydrogen cage-type silsesquioxane; Step C2: Dihydrogen cage silsesquioxane, p-hydroxystyrene, chloroplatinic acid and tetrahydrofuran are uniformly mixed, nitrogen is introduced for protection, and the reaction is carried out for 20 hours at a speed of 120 r / min and a temperature of 80° C. to obtain a functionalized cage silsesquioxane; the functionalized cage silsesquioxane is dissolved in DMF, and concentrated nitric acid and concentrated sulfuric acid are added under stirring at a speed of 60 r / min and a temperature of 0° C. to react for 1 hour to obtain a nitrated cage silsesquioxane; Step C3: Mix the nitrated cage-type silsesquioxane, acryloyl chloride, triethylamine and DMF, and react for 2 hours at a speed of 300 r / min and a temperature of 20°C to obtain a modified cage-type silsesquioxane; mix zinc powder, acetic acid, deionized water and DMF, and stir and add the modified cage-type silsesquioxane at a speed of 150 r / min and a temperature of 80°C to react for 1 hour, adjust the pH to alkaline, and obtain an amino cage-type silsesquioxane.

[0026] The amount ratio of phenyltrimethoxysilane, isopropanol, sodium hydroxide and deionized water described in step C1 is 120mmol:120mmol:80mmol:3mL, and the amount ratio of sodium octaphenylcyclotetrasiloxane tetrasiloxide, methyldichlorosilane, triethylamine and tetrahydrofuran is 12g:4.5mL:3.5g:30mL.

[0027] The molar ratio of the dihydrogen cage silsesquioxane and p-hydroxystyrene described in step C2 is 1:2, the amount of chloroplatinic acid used is 1‰ of the mass of p-hydroxystyrene, and the amount ratio of the functionalized cage silsesquioxane, concentrated nitric acid and concentrated sulfuric acid is 10mmol:9mL:10mL.

[0028] The molar ratio of the nitrated cage-type silsesquioxane, acryloyl chloride and triethylamine described in step C3 is 1:2:2.1, and the amount ratio of zinc powder, acetic acid, deionized water, DMF and modified cage-type silsesquioxane is 2.5g:2g:20mL:50mL:1.5g.

[0029] Embodiment 2: A method for preparing a fluorine release film for a high-viscosity silicone protective film for an AF glass screen, comprising the following steps: Step A1: uniformly mix perfluorodecylethylene, tetramethylcyclotetrasiloxane, chloroplatinic acid and DMF, and react at a speed of 120 r / min and a temperature of 75° C. for 4 h to obtain a modified monomer; uniformly mix the modified monomer, octamethylcyclotetrasiloxane, tetramethylammonium hydroxide, tetramethyldisiloxane and dimethyl sulfoxide, introduce nitrogen protection, and react at a speed of 120 r / min and a temperature of 110° C. for 4 h to obtain dihydrogenpolysiloxane; Step A2: dihydrogenpolysiloxane, allyl alcohol, chloroplatinic acid and DMF are mixed evenly, and reacted for 4 hours at a speed of 150 r / min and a temperature of 85° C. to obtain modified silicone; modified silicone, isophorone diisocyanate, dibutyltin dilaurate and tetrahydrofuran are mixed, nitrogen is introduced for protection, and reacted for 4 hours at a speed of 150 r / min and a temperature of 70° C., and then hydroxyethyl methacrylate is added and the reaction is continued for 4 hours to obtain a modified release agent; Step A3: Weigh the following raw materials in parts by weight: 40 parts of modified release agent, 13 parts of hydrogenated silicone oil, 0.2 parts of chloroplatinic acid, 25 parts of modified filler, 0.65 parts of expansion monomer DB-TOSU, 0.2 parts of triphenylsulfonium hexafluorophosphate, 0.4 parts of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and 25 parts of ethyl acetate, mix the raw materials evenly and apply them on a PET substrate, keep the temperature at 75°C for 3 hours, and irradiate with 365nm ultraviolet light for 4 minutes to obtain a fluorine release film for high-viscosity silicone protective film for AF glass screen.

[0030] The molar ratio of perfluorodecylethylene and tetramethylcyclotetrasiloxane described in step A1 is 4:1, the amount of chloroplatinic acid used is 1‰ of tetramethylcyclotetrasiloxane, and the molar ratio of modified monomer, octamethylcyclotetrasiloxane, tetramethylammonium hydroxide and tetramethyldisiloxane is 0.4:2:2:3.

[0031] The molar ratio of dihydrogenpolysiloxane and allyl alcohol described in step A2 is 1:2, the amount of chloroplatinic acid is 1‰ of tetramethylcyclotetrasiloxane, the molar ratio of modified silicone, isophorone diisocyanate and hydroxyethyl methacrylate is 3:4:2, and the amount of dibutyltin dilaurate is 2% of the mass of modified silicone.

[0032] The model of the hydrogen-containing silicone oil described in step A3 is RH-H502.

[0033] The modified filler is prepared by the following steps: Step B1: adding concentrated sulfuric acid to a reactor, stirring and adding graphene and potassium permanganate at a speed of 800 r / min and a temperature of 25° C., stirring for 3 h, heating to 50° C., reacting for 4 h, adding deionized water to terminate the reaction and washing to neutrality to obtain graphene oxide, mixing graphene oxide and ammonia water evenly, reacting for 6 h at a speed of 120 r / min and a temperature of 100° C., to obtain amination graphene; Step B2: The amino graphene, amino cage silsesquioxane, aniline, hydrochloric acid solution, isopropanol and deionized water are mixed evenly, stirred and ammonium persulfate is added at a speed of 120 r / min and a temperature of 3°C, and the reaction is carried out for 6 hours. The filtrate is removed by filtering, and the substrate is added to DMF. At a speed of 200 r / min and a temperature of 95°C, the mixture is heat-treated for 43 hours to obtain a modified filler.

[0034] The amount ratio of concentrated sulfuric acid, graphene and potassium permanganate described in step B1 is 110mL:1g:6g, the mass fraction of concentrated sulfuric acid is 98%, the amount ratio of graphene oxide and ammonia water is 1g:20mL, and the mass fraction of ammonia water is 28%.

[0035] The amount ratio of the amination graphene, amination cage silsesquioxane, aniline, hydrochloric acid solution, isopropanol, deionized water and ammonium persulfate described in step B2 is 1g:3g:1.5g:60mL:40mL:200mL:3g, and the mass fraction of the hydrochloric acid solution is 7%.

[0036] The amino cage-type silsesquioxane is prepared by the following steps: Step C1: Phenyltrimethoxysilane, isopropanol, sodium hydroxide and deionized water are mixed, and the mixture is reacted at a speed of 150 r / min and a temperature of 85° C. for 4 hours, and then the mixture is cooled to 20° C. and the mixture is reacted for 15 hours to obtain sodium octaphenylcyclotetrasiloxane tetrasiloxide; sodium octaphenylcyclotetrasiloxane tetrasiloxide, methyldichlorosilane, triethylamine and tetrahydrofuran are mixed, and the mixture is reacted at a speed of 150 r / min and a temperature of 0° C. for 4 hours, and then the mixture is heated to 20° C. and the mixture is reacted for 22 hours to obtain dihydrogen cage-type silsesquioxane; Step C2: Dihydrogen cage silsesquioxane, p-hydroxystyrene, chloroplatinic acid and tetrahydrofuran are uniformly mixed, nitrogen is introduced for protection, and the reaction is carried out for 20 hours at a speed of 120 r / min and a temperature of 85° C. to obtain functionalized cage silsesquioxane; the functionalized cage silsesquioxane is dissolved in DMF, and concentrated nitric acid and concentrated sulfuric acid are added under stirring at a speed of 80 r / min and a temperature of 0° C. to react for 1.3 hours to obtain nitrated cage silsesquioxane; Step C3: Mix the nitrated cage-type silsesquioxane, acryloyl chloride, triethylamine and DMF, and react for 2 hours at a speed of 500 r / min and a temperature of 20°C to obtain a modified cage-type silsesquioxane; mix zinc powder, acetic acid, deionized water and DMF, stir and add the modified cage-type silsesquioxane at a speed of 200 r / min and a temperature of 80°C, and react for 1.3 hours; adjust the pH to alkaline to obtain an amino cage-type silsesquioxane.

[0037] The amount ratio of phenyltrimethoxysilane, isopropanol, sodium hydroxide and deionized water described in step C1 is 120mmol:120mmol:80mmol:3mL, and the amount ratio of sodium octaphenylcyclotetrasiloxane tetrasiloxide, methyldichlorosilane, triethylamine and tetrahydrofuran is 12g:4.5mL:3.5g:30mL.

[0038] The molar ratio of the dihydrogen cage silsesquioxane and p-hydroxystyrene described in step C2 is 1:2, the amount of chloroplatinic acid used is 1‰ of the mass of p-hydroxystyrene, and the amount ratio of the functionalized cage silsesquioxane, concentrated nitric acid and concentrated sulfuric acid is 10mmol:9mL:10mL.

[0039] The molar ratio of the nitrated cage-type silsesquioxane, acryloyl chloride and triethylamine described in step C3 is 1:2:2.1, and the amount ratio of zinc powder, acetic acid, deionized water, DMF and modified cage-type silsesquioxane is 2.5g:2g:20mL:50mL:1.5g.

[0040] Embodiment 3: A method for preparing a fluorine release film for a high-viscosity silicone protective film for an AF glass screen, comprising the following steps: Step A1: uniformly mix perfluorodecylethylene, tetramethylcyclotetrasiloxane, chloroplatinic acid and DMF, and react at a speed of 150 r / min and a temperature of 80° C. for 5 h to obtain a modified monomer; uniformly mix the modified monomer, octamethylcyclotetrasiloxane, tetramethylammonium hydroxide, tetramethyldisiloxane and dimethyl sulfoxide, introduce nitrogen protection, and react at a speed of 150 r / min and a temperature of 110° C. for 5 h to obtain dihydrogenpolysiloxane; Step A2: Dihydrogen polysiloxane, allyl alcohol, chloroplatinic acid and DMF are mixed evenly, and reacted for 5 hours at a speed of 200 r / min and a temperature of 90° C. to obtain modified silicone; modified silicone, isophorone diisocyanate, dibutyltin dilaurate and tetrahydrofuran are mixed, nitrogen is introduced for protection, and reacted for 5 hours at a speed of 150 r / min and a temperature of 75° C., and then hydroxyethyl methacrylate is added and the reaction is continued for 5 hours to obtain a modified release agent; Step A3: Weigh the following raw materials in parts by weight: 50 parts of modified release agent, 15 parts of hydrogenated silicone oil, 0.3 parts of chloroplatinic acid, 30 parts of modified filler, 0.8 parts of expansion monomer DB-TOSU, 0.25 parts of triphenylsulfonium hexafluorophosphate, 0.5 parts of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and 30 parts of ethyl acetate, mix the raw materials evenly and apply them on a PET substrate, keep the temperature at 80°C for 3 hours, and irradiate with 365nm ultraviolet light for 5 minutes to obtain a fluorine release film for high-viscosity silicone protective film for AF glass screen.

[0041] The molar ratio of perfluorodecylethylene and tetramethylcyclotetrasiloxane described in step A1 is 4:1, the amount of chloroplatinic acid used is 1‰ of tetramethylcyclotetrasiloxane, and the molar ratio of modified monomer, octamethylcyclotetrasiloxane, tetramethylammonium hydroxide and tetramethyldisiloxane is 0.4:2:2:3.

[0042] The molar ratio of dihydrogenpolysiloxane and allyl alcohol described in step A2 is 1:2, the amount of chloroplatinic acid is 1‰ of tetramethylcyclotetrasiloxane, the molar ratio of modified silicone, isophorone diisocyanate and hydroxyethyl methacrylate is 3:4:2, and the amount of dibutyltin dilaurate is 2% of the mass of modified silicone.

[0043] The model of the hydrogen-containing silicone oil described in step A3 is RH-H502.

[0044] The modified filler is prepared by the following steps: Step B1: Add concentrated sulfuric acid to a reactor, stir and add graphene and potassium permanganate at a speed of 1000 r / min and a temperature of 25°C, stir for 4 hours, heat to 50°C, react for 5 hours, add deionized water to terminate the reaction and wash to neutrality to obtain graphene oxide, mix graphene oxide and ammonia water evenly, react for 7 hours at a speed of 150 r / min and a temperature of 100°C to obtain amination graphene; Step B2: The amino graphene, amino cage silsesquioxane, aniline, hydrochloric acid solution, isopropanol and deionized water are mixed evenly, stirred at a speed of 150 r / min and a temperature of 3°C and ammonium persulfate is added, and the reaction is carried out for 7 hours. The filtrate is removed by filtering, and the substrate is added to DMF. At a speed of 300 r / min and a temperature of 95°C, the mixture is heat-treated for 45 hours to obtain a modified filler.

[0045] The amount ratio of concentrated sulfuric acid, graphene and potassium permanganate described in step B1 is 110mL:1g:6g, the mass fraction of concentrated sulfuric acid is 98%, the amount ratio of graphene oxide and ammonia water is 1g:20mL, and the mass fraction of ammonia water is 28%.

[0046] The amount ratio of the amination graphene, amination cage silsesquioxane, aniline, hydrochloric acid solution, isopropanol, deionized water and ammonium persulfate described in step B2 is 1g:3g:1.5g:60mL:40mL:200mL:3g, and the mass fraction of the hydrochloric acid solution is 7%.

[0047] The amino cage-type silsesquioxane is prepared by the following steps: Step C1: Phenyltrimethoxysilane, isopropanol, sodium hydroxide and deionized water are mixed, and the mixture is reacted at a speed of 150 r / min and a temperature of 90° C. for 5 hours, and then the mixture is cooled to 25° C. and the mixture is reacted for 15 hours to obtain sodium octaphenylcyclotetrasiloxane tetrasiloxide. Sodium octaphenylcyclotetrasiloxane tetrasiloxide, methyldichlorosilane, triethylamine and tetrahydrofuran are mixed, and the mixture is reacted at a speed of 200 r / min and a temperature of 0° C. for 5 hours, and then the mixture is heated to 25° C. and the mixture is reacted for 22 hours to obtain dihydrogen cage-type silsesquioxane; Step C2: dihydrogen cage silsesquioxane, p-hydroxystyrene, chloroplatinic acid and tetrahydrofuran are uniformly mixed, nitrogen is introduced for protection, and the reaction is carried out for 25 hours at a speed of 150 r / min and a temperature of 85° C. to obtain a functionalized cage silsesquioxane; the functionalized cage silsesquioxane is dissolved in DMF, and concentrated nitric acid and concentrated sulfuric acid are added under stirring at a speed of 80 r / min and a temperature of 2° C. to react for 1.5 hours to obtain a nitrated cage silsesquioxane; Step C3: Mix the nitrated cage-type silsesquioxane, acryloyl chloride, triethylamine and DMF, and react for 3 hours at a speed of 500 r / min and a temperature of 25°C to obtain a modified cage-type silsesquioxane; mix zinc powder, acetic acid, deionized water and DMF, stir and add the modified cage-type silsesquioxane at a speed of 200 r / min and a temperature of 85°C, and react for 1.5 hours. Adjust the pH to alkaline to obtain an amino cage-type silsesquioxane.

[0048] The amount ratio of phenyltrimethoxysilane, isopropanol, sodium hydroxide and deionized water described in step C1 is 120mmol:120mmol:80mmol:3mL, and the amount ratio of sodium octaphenylcyclotetrasiloxane tetrasiloxide, methyldichlorosilane, triethylamine and tetrahydrofuran is 12g:4.5mL:3.5g:30mL.

[0049] The molar ratio of the dihydrogen cage silsesquioxane and p-hydroxystyrene described in step C2 is 1:2, the amount of chloroplatinic acid used is 1‰ of the mass of p-hydroxystyrene, and the amount ratio of the functionalized cage silsesquioxane, concentrated nitric acid and concentrated sulfuric acid is 10mmol:9mL:10mL.

[0050] The molar ratio of the nitrated cage-type silsesquioxane, acryloyl chloride and triethylamine described in step C3 is 1:2:2.1, and the amount ratio of zinc powder, acetic acid, deionized water, DMF and modified cage-type silsesquioxane is 2.5g:2g:20mL:50mL:1.5g.

[0051] Comparative Example 1: Compared with Example 1, this comparative example does not add the expansion monomer DB-TOSU, and the remaining steps are the same.

[0052] Comparative Example 2: Compared with Example 1, no hydrogen-containing silicone oil was added in this comparative example, and the remaining steps were the same.

[0053] Comparative Example 3: Compared with Example 1, this comparative example does not add amino cage silsesquioxane, and the remaining steps are the same.

[0054] Comparative Example 4: Compared with Example 1, this comparative example uses nitrated cage-type silsesquioxane instead of modified cage-type silsesquioxane, and the remaining steps are the same.

[0055] The surface flatness of the release films prepared in Examples 1-3 and Comparative Examples 1-4 was observed, TESA7475 tape was attached to the release films, and after 24 hours, the films were peeled off at an angle of 180° and 300 mm / min to test the release force. The square resistance of the antistatic release films was measured using a four-point probe instrument. The test results are shown in Table 1 below.

[0056] Table 1 It can be seen from the above table that the present application has good antistatic effect and release effect, and the high surface flatness can ensure the use effect of the release film.

[0057] The above contents are merely examples and explanations of the concept of the present invention. The technicians in this technical field may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the concept of the invention or exceed the scope defined by the claims, they should all fall within the protection scope of the present invention.

Claims

1. A method for preparing a fluorine release film for a high-viscosity silicone protective film for an AF glass screen, characterized in that: The specific steps include: Step A1: perfluorodecylethylene, tetramethylcyclotetrasiloxane, chloroplatinic acid and DMF are mixed and reacted to obtain a modified monomer, and the modified monomer, octamethylcyclotetrasiloxane, tetramethylammonium hydroxide, tetramethyldisiloxane and dimethyl sulfoxide are uniformly mixed, and nitrogen is introduced for protection to react to obtain dihydrogenpolysiloxane; Step A2: dihydrogenpolysiloxane, allyl alcohol, chloroplatinic acid and DMF are mixed to react to obtain modified silicone, and the modified silicone, isophorone diisocyanate, dibutyltin dilaurate and tetrahydrofuran are mixed, nitrogen is introduced to protect, and after the reaction, hydroxyethyl methacrylate is added and the reaction is continued to obtain a modified release agent; Step A3: Weigh the following raw materials in parts by weight: 30-50 parts of modified release agent, 10-15 parts of hydrogenated silicone oil, 0.1-0.3 parts of chloroplatinic acid, 20-30 parts of modified filler, 0.5-0.8 parts of expansion monomer DB-TOSU, 0.15-0.25 parts of triphenylsulfonium hexafluorophosphate, 0.3-0.5 parts of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and 20-30 parts of ethyl acetate, mix the raw materials evenly, apply them on a PET substrate, and cure to obtain a fluorine release film for a high-viscosity silicone protective film for an AF glass screen; The molar ratio of perfluorodecylethylene and tetramethylcyclotetrasiloxane in step A1 is 4:1, and the molar ratio of the modified monomer, octamethylcyclotetrasiloxane, tetramethylammonium hydroxide and tetramethyldisiloxane is 0.4:2:2:3; The molar ratio of dihydrogenpolysiloxane and allyl alcohol in step A2 is 1:2, and the molar ratio of modified silicone, isophorone diisocyanate and hydroxyethyl methacrylate is 3:4:

2.

2. The method for preparing the fluorine release film for the high-viscosity silicone protective film for AF glass screen according to claim 1, characterized in that: The modified filler is prepared by the following steps: Step B1: adding concentrated sulfuric acid to a reactor, stirring, adding graphene and potassium permanganate, reacting, adding deionized water to terminate the reaction and washing to neutrality to obtain graphene oxide, mixing the graphene oxide and ammonia water to react, and obtaining amination graphene; Step B2: Mix and stir the amino graphene, amino cage silsesquioxane, aniline, hydrochloric acid solution, isopropanol and deionized water, add ammonium persulfate, react, filter and remove the filtrate, add the substrate into DMF, keep it at high temperature, and obtain a modified filler.

3. The method for preparing the fluorine release film for the high-viscosity silicone protective film for AF glass screen according to claim 2, characterized in that: The amount ratio of concentrated sulfuric acid, graphene and potassium permanganate described in step B1 is 110mL:1g:6g, and the amount ratio of graphene oxide and ammonia water is 1g:20mL.

4. The method for preparing the fluorine release film for the high-viscosity silicone protective film for AF glass screen according to claim 2, characterized in that: The amount ratio of the amination graphene, amination cage silsesquioxane, aniline, hydrochloric acid solution, isopropanol, deionized water and ammonium persulfate described in step B2 is 1g:3g:1.5g:60mL:40mL:200mL:3g.

5. The method for preparing the fluorine release film for the high-viscosity silicone protective film for AF glass screen according to claim 2, characterized in that: The amino cage-type silsesquioxane is prepared by the following steps: Step C1: Phenyltrimethoxysilane, isopropanol, sodium hydroxide and deionized water are mixed and reacted to obtain sodium octaphenylcyclotetrasiloxane tetrasiloxide, and sodium octaphenylcyclotetrasiloxane tetrasiloxide, methyldichlorosilane, triethylamine and tetrahydrofuran are mixed and reacted to obtain dihydrogen cage-type silsesquioxane; Step C2: uniformly mixing dihydrogen cage silsesquioxane, p-hydroxystyrene, chloroplatinic acid and tetrahydrofuran, introducing nitrogen gas for protection, and reacting to obtain functionalized cage silsesquioxane; dissolving the functionalized cage silsesquioxane in DMF, stirring and adding concentrated nitric acid and concentrated sulfuric acid, and reacting to obtain nitrated cage silsesquioxane; Step C3: Mix the nitrated cage-type silsesquioxane, acryloyl chloride, triethylamine and DMF, and react for 2-3 hours at a rotation speed of 300-500 r / min and a temperature of 20-25° C. to obtain a modified cage-type silsesquioxane. Mix zinc powder, acetic acid, deionized water and DMF, add the modified cage-type silsesquioxane, react, adjust the pH to alkaline, and obtain an amination cage-type silsesquioxane.

6. The method for preparing the fluorine release film for the high-viscosity silicone protective film of the AF glass screen according to claim 5, characterized in that: The amount ratio of phenyltrimethoxysilane, isopropanol, sodium hydroxide and deionized water described in step C1 is 120mmol:120mmol:80mmol:3mL, and the amount ratio of sodium octaphenylcyclotetrasiloxane tetrasiloxide, methyldichlorosilane, triethylamine and tetrahydrofuran is 12g:4.5mL:3.5g:30mL.

7. The method for preparing the fluorine release film for the high-viscosity silicone protective film of the AF glass screen according to claim 5, characterized in that: The molar ratio of the dihydrogen cage silsesquioxane and p-hydroxystyrene described in step C2 is 1:2, and the amount ratio of the functionalized cage silsesquioxane, concentrated nitric acid and concentrated sulfuric acid is 10mmol:9mL:10mL.

8. The method for preparing the fluorine release film for the high-viscosity silicone protective film of the AF glass screen according to claim 5, characterized in that: The molar ratio of the nitrated cage-type silsesquioxane, acryloyl chloride and triethylamine described in step C3 is 1:2:2.1, and the amount ratio of zinc powder, acetic acid, deionized water, DMF and modified cage-type silsesquioxane is 2.5g:2g:20mL:50mL:1.5g.

9. Fluorine release film for AF glass screen high viscosity silicone protective film, characterized by: Prepared according to any one of the preparation methods described in claims 1-8.

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