Printable opp glazing film and process for making the same

Abstract

The present application relates to the technical field of glazing film, in particular to a printable OPP glazing film and a preparation process thereof.The present application prepares an isocyanate-terminated polyurethane prepolymer, which is then copolymerized with methyl methacrylate, butyl acrylate, hydroxyethyl acrylate and double-bond-containing silica to form an interpenetrating network structure, and is neutralized by adding triethylamine and combined with the action of various additives to obtain a coating liquid; the polypropylene film is subjected to corona treatment to obtain a corona-treated polypropylene film; the coating liquid is coated on the corona-treated surface of the corona-treated polypropylene film, and after drying, the printable OPP glazing film is obtained.The printable OPP glazing film prepared by the present application has excellent hydrophobic properties, significantly improves the adhesion between the ink and the coating layer, and at the same time, enhances the firmness between the coating layer and the polypropylene film layer.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of glazing film, in particular to a printable OPP glazing film and a preparation process thereof. BACKGROUND

[0002] OPP glazing film is a film made of polypropylene as the main raw material through unidirectional stretching or biaxial stretching process, which has high transparency, good gloss, high mechanical strength, good heat resistance, good chemical stability and other advantages. The printable OPP glazing film is based on the ordinary OPP film, which has good printing suitability through special surface treatment or coating process, can withstand the printing of ink, and at the same time maintains the original performance of the film.

[0003] In the traditional preparation process of OPP glazing film, the glazing coating usually contains a large amount of organic solvents such as toluene and xylene, which will be volatilized into the air during production, causing environmental pollution and also having certain harm to human health. In addition, the wear resistance and scratch resistance of some OPP glazing films are not ideal, and in the use process of printed matter, surface wear and scratches may occur, affecting the appearance and service life of the printed matter. At the same time, some glazing films have insufficient water resistance and chemical resistance, and when they come into contact with water, oil, acid, alkali and other substances, they may have problems such as discoloration, color change and blistering, resulting in a decrease in the quality of the printed matter.

[0004] Therefore, we propose a printable OPP glazing film and a preparation process thereof. SUMMARY

[0005] The purpose of the present application is to provide a printable OPP glazing film and a preparation process thereof to solve the problems in the prior art.

[0006] To achieve the above-mentioned purpose, the present application provides the following technical scheme:

[0007] A preparation process of a printable OPP glazing film, comprising the following steps:

[0008] Step S1: vacuum dehydration of polyether polyol at 110-120℃ for 2-3h, cooling to 60-70℃, adding isophorone diisocyanate and dibutyltin dilaurate under nitrogen protection, mixing uniformly, reacting for 1-3h, adding 2,2-dimethylol butyric acid, modified hyperbranched fluorine-containing polymer, reacting for 3-5h to obtain polyurethane prepolymer;

[0009] Mixing emulsifier and deionized water uniformly, adding methyl methacrylate, butyl acrylate, hydroxyethyl acrylate and double bond-containing silica uniformly, pre-emulsifying for 0.5-1.5h to obtain pre-emulsified monomer;

[0010] Step S2: mixing the polyurethane prepolymer, pre-emulsified monomer and deionized water, heating to 70-80℃, adding ammonium persulfate aqueous solution dropwise, dropping for 1-2h, reacting for 2-4h, continuing to heat to 85-90℃, adding hydroxypropyl methacrylate, reacting for 1-3h; cooling to 30-40℃, adding triethylamine for neutralization, adding defoaming agent, leveling agent and adhesion promoter, mixing uniformly to obtain a coating liquid;

[0011] Step S3: corona treatment of the polypropylene film to obtain a corona polypropylene film; coating the coating liquid on the corona surface of the corona polypropylene film, and drying to obtain a printable OPP optical film.

[0012] Further, the coating liquid comprises the following raw materials in parts by weight: polyurethane prepolymer 30-40 parts, pre-emulsified monomer 60-80 parts, deionized water 400-500 parts, ammonium persulfate aqueous solution 8-12 parts, hydroxypropyl methacrylate 1-3 parts, triethylamine 3-8 parts, leveling agent 0.3-0.6 parts, defoaming agent 0.1-0.5 parts, and adhesion promoter 1-3 parts.

[0013] Further, the concentration of the ammonium persulfate aqueous solution is 3wt%.

[0014] Further, the polyurethane prepolymer comprises the following raw materials in parts by weight: polyether polyol 40-50 parts, isophorone diisocyanate 70-90 parts, dibutyltin dilaurate 1-3 parts, 2,2-dimethylol butyric acid 2-4 parts, and modified hyperbranched fluorine-containing polymer 5-15 parts.

[0015] Further, the preparation method of the modified hyperbranched fluorine-containing polymer comprises the following steps:

[0016] Mixing dodecafluoroheptyl methacrylate, diethanolamine and acetonitrile uniformly under nitrogen protection, reacting for 8-10h at 75-85℃ to obtain fluorine-containing diol; condensation reaction of the fluorine-containing diol with vinyltrimethoxysilane under nitrogen protection, vacuum drying after the reaction is completed to obtain the modified hyperbranched fluorine-containing polymer.

[0017] Further, the molar ratio of dodecafluoroheptyl methacrylate to diethanolamine is 1:(1-1.2).

[0018] Further, the molar ratio of the fluorine-containing diol to vinyltrimethoxysilane is (1-2):1.

[0019] Further, the condensation reaction is carried out in three stages, namely the first reaction stage, the second reaction stage and the third reaction stage.

[0020] Further, the reaction temperature of the first reaction stage is 80-90℃, and the reaction time is 2-3h.

[0021] Further, the reaction temperature of the second reaction stage is 150-170℃, and the reaction time is 0.5-2h.

[0022] Further, the third reaction stage is performed under the condition of natural cooling, and the reaction temperature is reduced from 150-170℃ to 70-90℃.

[0023] Further, the condensation reaction is performed in the presence of a catalyst, and the molar amount of the catalyst is 0.005-0.01% based on 100% of the total molar amount of the vinyltrimethoxysilane and the fluorine-containing diol; and the catalyst comprises at least one of p-toluenesulfonic acid, sulfuric acid, tetramethylammonium hydroxide, or sodium hydroxide.

[0024] Further, the pre-emulsified monomer comprises the following raw materials in the following weight proportions: methyl methacrylate 30-40 parts, butyl acrylate 40-50 parts, hydroxyethyl acrylate 10-20 parts, double bond-containing silica 5-15 parts, emulsifier 3-6 parts, and deionized water 150-300 parts.

[0025] Further, the emulsifier is one or more of sodium dodecyl sulfate (SDS), sodium dodecyl benzene sulfonate (SDBS), sodium salt of ethoxylated alkyl sulfate (CM30), sodium salt of isomeric tridecyl alcohol sulfate (2030S), and rhamnolipid.

[0026] Further, the preparation method of the double bond-containing silica is as follows:

[0027] Step A: ultrasonic dispersion of silica in a mixed solution of anhydrous ethanol and deionized water, addition of γ-aminopropyl triethoxysilane and uniform mixing, reaction at 70-80℃ for 3-5h, centrifugation, washing, and drying to obtain aminated silica;

[0028] Step B: uniform mixing of the aminated silica, linoleic acid, and dimethyl sulfoxide under nitrogen protection, addition of 1-ethyl-(3-dimethylaminopropyl) carbonyl diimide hydrochloride diimide and 4-dimethylamino pyridine, stirring at room temperature for 22-24h, filtration, washing, and drying to obtain double bond-containing silica.

[0029] Further, in step A, the mass ratio of silica, anhydrous ethanol, deionized water, and 3-aminopropyl trimethoxysilane is 1: (10-12): (2-4): (0.3-0.5).

[0030] Further, in step B, the mass ratio of aminated silica, linoleic acid, and dimethyl sulfoxide is 1: (2-4): (5-10).

[0031] Further, the mass ratio of the aminated silicon dioxide, 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride diimide and 4-dimethylamino pyridine is 1: (0.1-0.2): (0.08-0.10).

[0032] Further, the corona treatment process is that the power of the corona machine is 4-8KW, and the speed of the corona machine is 80-120 m / min.

[0033] Compared with the prior art, the present application has the following beneficial effects:

[0034] 1、The present application is a kind of printable OPP film and its preparation process, first prepare the end isocyanate-terminated polyurethane prepolymer, then copolymerize with acrylate monomer and double bond-containing silica to form an interpenetrating network structure;Polyurethane segment provides flexibility and water resistance, acrylate gives hardness and fast drying, significantly improves the adhesion of coating liquid. Specifically, in the scheme, methacrylic acid dodecafluoroheptyl ester (DFHMA) and diethanolamine (DEOA) are used to prepare fluorine-containing diols;Then use fluorine-containing diols and vinyltrimethoxysilane as raw materials to generate A2+B3 type modified hyperbranched fluoropolymer;By introducing modified hyperbranched fluoropolymer into polyurethane prepolymer, fluorine element makes up for the lack of water resistance, oil resistance and weather resistance, the introduction of hyperbranched structure, fluorine-containing segment and siloxane segment effectively reduces the surface tackiness, has excellent anti-sticking performance, prevents film from sticking when winding, the introduction of vinyl provides reaction sites for subsequent chemical reactions, so that the polyurethane material can be further modified or crosslinked.

[0035] 2、The present application is a kind of printable OPP film and its preparation process, the preparation of pre-emulsified monomer uses methyl methacrylate, butyl acrylate, hydroxyethyl acrylate and double bond-containing silica, the hydroxyl group of hydroxyethyl acrylate can form hydrogen bond with corona surface, enhance the adhesion, double bond-containing silica can be used as anti-sticking agent, by grafting linoleic acid, introducing double bond and hydrophobic long chain, so that it can participate in the copolymerization reaction of acrylate, firmly anchored in the polymer network, avoid migration;At the same time, roughness is formed on the surface of the coating, the smoothness is reduced, the printing suitability is significantly improved, and the printable performance is realized. DETAILED DESCRIPTION

[0036] The technical solutions in the embodiments of the present application will be described below in a clear and complete manner. Obviously, the described embodiments are only part of the embodiments of the present application, not all. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application.

[0037] The polyether polyol in this embodiment: the grade is CP450, from Dow Chemical; the leveling agent: the type is Kairui KYC-615; the defoaming agent: the type is BIK BYK-028; the adhesion promoter: the type is TEGO AddBond DS1300; the silicon dioxide: hydroxyl silicon dioxide microsphere powder, the particle size is 5-10 μm; the polypropylene film: the thickness is 50-100 μm, from Foshan Yichong Packaging Products Co., Ltd.

[0038] The following parts are mass parts unless otherwise specified.

[0039] Example 1: a preparation process of a printable OPP glazing film, including the following processes:

[0040] Step S1: 40 parts of polyether polyol are vacuum dehydrated at 110°C for 2h, cooled to 60°C, and then 70 parts of isophorone diisocyanate and 1 part of dibutyltin dilaurate are added and mixed uniformly under the protection of nitrogen, reacted for 1h, 2 parts of 2, 2-dimethylol butyric acid, 5 parts of modified hyperbranched fluorine-containing polymer are added and reacted for 3h, to obtain a polyurethane prepolymer;

[0041] 3 parts of sodium dodecyl sulfate and 150 parts of deionized water are mixed uniformly, 30 parts of methyl methacrylate, 40 parts of butyl acrylate, 10 parts of hydroxyethyl acrylate and 5 parts of double bond-containing silica are mixed uniformly, and pre-emulsification is added for 0.5h to obtain a pre-emulsified monomer;

[0042] Step S2: 30 parts of polyurethane prepolymer, 60 parts of pre-emulsified monomer and 400 parts of deionized water are mixed, heated to 70°C, 8 parts of 3wt% ammonium persulfate aqueous solution is added dropwise, 1h dropwise, reacted for 2h, continue to heat to 85°C, add 1 part of hydroxypropyl methacrylate, react for 1h; cool to 30°C, add 3 parts of triethylamine for neutralization, add 0.1 parts of defoaming agent, 0.3 parts of leveling agent and 1 parts of adhesion promoter, mix uniformly to obtain a coating liquid;

[0043] Step S3: the polypropylene film is subjected to corona treatment (the power of the corona machine is 4KW, and the speed of the corona machine is 80m / min), to obtain a corona polypropylene film; the coating liquid is coated on the corona surface of the corona polypropylene film (the coating amount is 1.8g / m 2 ), and after drying, a printable OPP glazing film is obtained;

[0044] The preparation method of the modified hyperbranched fluorine-containing polymer comprises the following steps:

[0045] The dodecafluoroheptyl methacrylate, diethanolamine and acetonitrile are mixed uniformly under nitrogen protection, and reacted at 75°C for 8h to obtain a fluorine-containing diol; the fluorine-containing diol and vinyltrimethoxysilane are mixed under nitrogen protection, and condensed in the presence of p-toluenesulfonic acid (the reaction temperature of the first reaction stage is 80°C, the reaction time is 2h; the reaction temperature of the second reaction stage is 150°C, the reaction time is 0.5h; the third reaction stage is carried out under the condition of natural cooling, and the reaction temperature is reduced from 150°C to 70°C), after the reaction is completed, vacuum drying is carried out, and a modified hyperbranched fluoropolymer is obtained; the molar ratio of dodecafluoroheptyl methacrylate and diethanolamine is 1:1; the molar ratio of fluorine-containing diol and vinyltrimethoxysilane is 1:1; the molar amount of p-toluenesulfonic acid is 0.005% of the total molar amount of vinyltrimethoxysilane and fluorine-containing diol;

[0046] The preparation method of the double-bond-containing silica is as follows:

[0047] Step A: 5 parts of silica are ultrasonically dispersed in a mixed solution of 50 parts of anhydrous ethanol and 10 parts of deionized water, 1.5 parts of γ-aminopropyl triethoxysilane is added and uniformly mixed, and reacted at 70°C for 3h, after centrifugation, washing and drying, aminated silica is obtained;

[0048] Step B: 5 parts of aminated silica, 10 parts of linoleic acid and 25 parts of dimethyl sulfoxide are mixed uniformly under nitrogen protection, 0.5 parts of 1-ethyl-(3-dimethylaminopropyl) carbonyldiimidazole hydrochloride diimide and 0.4 parts of 4-dimethylaminopyridine are added, and stirred at room temperature for 22h, after filtration, washing and drying, double-bond-containing silica is obtained.

[0049] Example 2: A preparation process of a printable OPP glazing film, including the following processes:

[0050] Step S1: 45 parts of polyether polyol are vacuum dehydrated at 115°C for 2.5h, cooled to 65°C, and then 80 parts of isophorone diisocyanate and 2 parts of dibutyltin dilaurate are added under nitrogen protection, mixed uniformly, reacted for 2h, 3 parts of 2,2-dimethylol butyric acid, 10 parts of modified hyperbranched fluoropolymer are added, and reacted for 4h to obtain a polyurethane prepolymer;

[0051] 5 parts of sodium dodecyl sulfate and 250 parts of deionized water are mixed uniformly, 35 parts of methyl methacrylate, 45 parts of butyl acrylate, 15 parts of hydroxyethyl acrylate and 10 parts of double-bond-containing silica are added and mixed uniformly, and pre-emulsification is carried out for 1h to obtain a pre-emulsified monomer;

[0052] Step S2: 35 parts of polyurethane prepolymer, 70 parts of pre-emulsified monomer and 450 parts of deionized water are mixed, heated to 75℃, 10 parts of 3wt% ammonium persulfate aqueous solution is added dropwise, 1.5h dropwise, reaction for 3h, continue to heat to 87℃, add 2 parts of hydroxypropyl methacrylate, reaction for 2h; cooling to 35℃, adding 5 parts of triethylamine for neutralization, adding 0.3 parts of defoaming agent, 0.5 parts of leveling agent and 2 parts of adhesion promoter, mixing uniformly, then the coating liquid is obtained;

[0053] Step S3: the polypropylene film is subjected to corona treatment (the power of the corona machine is 5KW, and the speed of the corona machine is 100m / min), to obtain a corona polypropylene film; the coating liquid is coated on the corona surface of the corona polypropylene film (the coating amount is 2.5g / m 2 ), and after drying, a printable OPP optical film is obtained;

[0054] The preparation method of the modified hyperbranched fluorine-containing polymer comprises the following steps:

[0055] Under the protection of nitrogen, dodecafluoroheptyl methacrylate, diethanolamine and acetonitrile are uniformly mixed and reacted at 80℃ for 9h to obtain a fluorine-containing diol; under the protection of nitrogen, the fluorine-containing diol is mixed with vinyltrimethoxysilane, and a condensation reaction is carried out in the presence of p-toluenesulfonic acid (the reaction temperature of the first reaction stage is 85℃, the reaction time is 2.5h; the reaction temperature of the second reaction stage is 160℃, the reaction time is 1h; the third reaction stage is carried out under the condition of natural cooling, and the reaction temperature decreases from 160℃ to 80℃); after the reaction is completed, vacuum drying is carried out to obtain the modified hyperbranched fluorine-containing polymer; the molar ratio of dodecafluoroheptyl methacrylate to diethanolamine is 1:1.1; the molar ratio of the fluorine-containing diol to vinyltrimethoxysilane is 1.5:1; the molar amount of p-toluenesulfonic acid is 0.008% of the total molar amount of vinyltrimethoxysilane and the fluorine-containing diol;

[0056] The preparation method of the double bond-containing silica is as follows:

[0057] Step A: 10 parts of silica is ultrasonically dispersed in a mixed solution of 110 parts of anhydrous ethanol and 30 parts of deionized water, 4 parts of γ-aminopropyl triethoxysilane is added and uniformly mixed, and reacted at 80℃ for 4h; after centrifugation, washing and drying, aminated silica is obtained;

[0058] Step B: under the protection of nitrogen, 10 parts of aminated silica, 30 parts of linoleic acid and 80 parts of dimethyl sulfoxide are uniformly mixed, 1.5 parts of 1-ethyl-(3-dimethylaminopropyl) carbonyldiimidazole hydrochloride diimide and 0.9 parts of 4-dimethylaminopyridine are added, and stirred at room temperature for 23h; after filtration, washing and drying, double bond-containing silica is obtained.

[0059] Embodiment 3: a preparation process of a printable OPP glazing film, comprising the following processes:

[0060] Step S1: 50 parts of polyether polyol is vacuum dehydrated at 120℃ for 3h, cooled to 70℃, and then 90 parts of isophorone diisocyanate and 3 parts of dibutyltin dilaurate are added and mixed uniformly under nitrogen protection, reacted for 3h, 4 parts of 2, 2-dimethylol butyric acid, 15 parts of modified hyperbranched fluorine-containing polymer are added and reacted for 5h to obtain a polyurethane prepolymer;

[0061] 6 parts of sodium dodecyl sulfate and 300 parts of deionized water are mixed uniformly, 40 parts of methyl methacrylate, 50 parts of butyl acrylate, 20 parts of hydroxyethyl acrylate and 15 parts of double bond-containing silica are mixed uniformly, and pre-emulsification is carried out for 1.5h to obtain a pre-emulsified monomer;

[0062] Step S2: 40 parts of polyurethane prepolymer, 80 parts of pre-emulsified monomer and 500 parts of deionized water are mixed, heated to 80℃, 12 parts of 3wt% ammonium persulfate aqueous solution is added dropwise, and the dropping is completed in 2h, and the reaction is carried out for 4h, then continue to heat to 90℃, add 3 parts of hydroxypropyl methacrylate, and react for 3h; cooled to 40℃, added 8 parts of triethylamine for neutralization, added 0.5 parts of defoaming agent, 0.6 parts of leveling agent and 3 parts of adhesion promoter, mixed uniformly to obtain a coating liquid;

[0063] Step S3: the polypropylene film is subjected to corona treatment (the power of the corona machine is 4-8KW, and the speed of the corona machine is 120m / min) to obtain a corona polypropylene film; the coating liquid is coated on the corona surface of the corona polypropylene film (the coating amount is 2.8g / m 2 ), and after drying, a printable OPP glazing film is obtained;

[0064] The preparation method of the modified hyperbranched fluorine-containing polymer comprises the following steps:

[0065] Under the protection of nitrogen, dodecafluoroheptyl methacrylate, diethanolamine and acetonitrile are mixed uniformly, and reacted at 85℃ for 10h to obtain a fluorine-containing diol; under the protection of nitrogen, the fluorine-containing diol is mixed with vinyltrimethoxysilane, and a condensation reaction is carried out in the presence of p-toluenesulfonic acid (the reaction temperature of the first reaction stage is 90℃, the reaction time is 3h; the reaction temperature of the second reaction stage is 170℃, the reaction time is 2h; the third reaction stage is carried out under the condition of natural cooling, and the reaction temperature is reduced from 170℃ to 90℃); after the reaction is completed, vacuum drying is carried out to obtain a modified hyperbranched fluorine-containing polymer; the molar ratio of dodecafluoroheptyl methacrylate to diethanolamine is 1:1.2; the molar ratio of fluorine-containing diol to vinyltrimethoxysilane is 2:1; the molar amount of p-toluenesulfonic acid is 0.01% of the total molar amount of vinyltrimethoxysilane and fluorine-containing diol;

[0066] The preparation method of the double bond-containing silica is as follows:

[0067] Step A: 15 parts of silica was ultrasonically dispersed in a mixed solution of 180 parts of anhydrous ethanol and 60 parts of deionized water, 7.5 parts of γ-aminopropyl triethoxysilane was added and uniformly mixed, and reacted at 80°C for 5h, after centrifugation, washing and drying, the aminated silica was obtained;

[0068] Step B: 15 parts of aminated silica, 60 parts of linoleic acid and 150 parts of dimethyl sulfoxide were uniformly mixed, 3 parts of 1-ethyl-(3-dimethylaminopropyl) carbonyl diimide hydrochloride diimide and 1.5 parts of 4-dimethylaminopyridine were added, and stirred at room temperature for 24h, then filtered, washed and dried to obtain the double bond-containing silica.

[0069] Comparative Example 1: A preparation process of a printable OPP glazing film, comprising the following processes:

[0070] Compared with Example 2, Comparative Example 1 does not introduce a modified hyperbranched fluorine-containing polymer, and the other steps are the same as Example 2.

[0071] Comparative Example 2: A preparation process of a printable OPP glazing film, comprising the following processes:

[0072] Compared with Example 2, Comparative Example 2 does not introduce double bond-containing silica, and the other steps are the same as Example 2.

[0073] Comparative Example 3: A preparation process of a printable OPP glazing film, comprising the following processes:

[0074] Compared with Example 2, Comparative Example 3 replaces the pre-emulsified monomer with the same mass of an acrylic water-based resin (brand Soluryl-60L), and the other steps are the same as Example 2.

[0075] Experiment: Take the printable OPP glazing films obtained in Examples 1-3 and Comparative Examples 1-3 to prepare samples, and detect the performance of each sample and record the detection results:

[0076] Water absorption test: According to GB / T 1733-1993 "Paint film water resistance test method", the sample size is 20mm×20mm×1mm, after weighing, it is immersed in deionized water, taken out after 24 hours, then the water on the surface of the cured film is quickly and gently wiped off and weighed, and the water absorption is calculated.

[0077] Coating liquid adhesion test: The grid method is used to evaluate the adhesion according to GB / T 9286-2021, and the number of grids without coating layer falling off is recorded, 100 is the best, indicating that all are not falling off, and 0 is the worst, indicating that all are falling off.

[0078] Ink adhesion test: The adhesion was evaluated by crosshatch method according to GB / T 9286-2021. The specific steps are as follows: the thermosetting ink (brand: Germany Peters SD 2696 TSW) was coated on the printable OPP film, and after drying, an ink coating layer with a thickness of 25 μm was obtained. The crosshatch knife was used to draw the crosshatch on the ink coating layer, and the sample with crosshatch was placed in boiling water, and after boiling for 20 min, it was taken out and dried to room temperature, the adhesion was tested, and the number of unpeeled grids of the ink layer was recorded.

[0079] The test results are shown in Table 1.

[0080] Table 1 Performance test results of printable OPP film

[0081]

[0082] According to the data in the above table, the following conclusions can be clearly obtained:

[0083] 1. Compared with Examples 1-3, the water absorption and adhesion of the products obtained in Comparative Examples 1 and 2 are decreased, which shows that the present application significantly improves the water resistance and adhesion to ink of the coating layer by introducing modified hyperbranched fluorine-containing polymer and double bond-containing silica in a synergistic manner.

[0084] 2. Compared with Examples 1-3, the water absorption and adhesion of the product obtained in Comparative Example 3 are decreased, and compared with the commercially available acrylic water-based resin, the present application significantly improves the crosslinking density and surface micro-roughness of the coating layer by introducing pre-emulsified monomers, thereby improving the hydrophobic performance and bonding force of the material.

[0085] It is obvious to those skilled in the art that the present application is not limited to the details of the above exemplary embodiments, and the present application can be implemented in other specific forms without departing from the spirit or essential characteristics of the present application. Therefore, the examples should be regarded as exemplary and non-limiting in any respect, and the scope of the present application is defined by the appended claims rather than the above description, and therefore all changes falling within the meaning and scope of the equivalent elements of the claims are intended to be included in the present application.

Claims

1. A process for the preparation of a printable OPP glazing film, characterized in that: It comprises the following steps: Step S1: polyether polyol is vacuum dehydrated at 110-120℃ for 2-3h, and then cooled to 60-70℃, and then isophorone diisocyanate and dibutyl tin dilaurate are added under the protection of nitrogen and mixed uniformly, and then reacted for 1-3h, and then 2,2-dimethylol butyric acid and modified hyperbranched fluorine-containing polymer are added and reacted for 3-5h to obtain polyurethane prepolymer; The emulsifier and deionized water are mixed uniformly, and then methyl methacrylate, butyl acrylate, hydroxyethyl acrylate and double bond-containing silica are added and mixed uniformly, and then pre-emulsified for 0.5-1.5h to obtain pre-emulsified monomers; Step S2: the polyurethane prepolymer, the pre-emulsified monomers and the deionized water are mixed, and then heated to 70-80℃, and then ammonium persulfate aqueous solution is added dropwise, and then the dropping is completed in 1-2h, and then reacted for 2-4h, and then heated to 85-90℃, and then hydroxypropyl methacrylate is added and reacted for 1-3h, and then cooled to 30-40℃, and then neutralized by adding triethylamine, and then defoaming agent, leveling agent and adhesion promoter are added and mixed uniformly to obtain coating liquid; Step S3: the polypropylene film is subjected to corona treatment to obtain a corona-treated polypropylene film; and the coating liquid is coated on the corona-treated surface of the corona-treated polypropylene film, and then dried to obtain a printable OPP optical film; The preparation method of the modified hyperbranched fluorine-containing polymer comprises the following steps: Under the protection of nitrogen, dodecafluoroheptyl methacrylate, diethanolamine and acetonitrile are mixed uniformly, and then reacted at 75-85℃ for 8-10h to obtain fluorine-containing dihydric alcohol; and then the fluorine-containing dihydric alcohol is subjected to condensation reaction with vinyltrimethoxysilane under the protection of nitrogen, and then vacuum dried after the reaction to obtain modified hyperbranched fluorine-containing polymer; The preparation method of the double bond-containing silica is as follows: Step A: the silica is ultrasonically dispersed in a mixed solution of anhydrous ethanol and deionized water, and then γ-aminopropyl triethoxysilane is added and mixed uniformly, and then reacted at 70-80℃ for 3-5h, and then centrifuged, washed and dried to obtain aminated silica; Step B: under the protection of nitrogen, the aminated silica, linoleic acid and dimethyl sulfoxide are mixed uniformly, and then 1-ethyl-(3-dimethylaminopropyl) carbonyl diimide hydrochloride and 4-dimethylamino pyridine are added, and then stirred at room temperature for 22-24h, and then filtered, washed and dried to obtain double bond-containing silica.

2. A process for the preparation of a printable OPP glazing film as claimed in claim 1, wherein: The coating liquid comprises the following raw materials in parts by weight: polyurethane prepolymer 30-40 parts, pre-emulsified monomers 60-80 parts, deionized water 400-500 parts, ammonium persulfate aqueous solution 8-12 parts, hydroxypropyl methacrylate 1-3 parts, triethylamine 3-8 parts, leveling agent 0.3-0.6 parts, defoaming agent 0.1-0.5 parts, and adhesion promoter 1-3 parts.

3. A process for the preparation of a printable OPP glazing film as claimed in claim 2, wherein: The polyurethane prepolymer comprises the following raw materials in parts by weight: polyether polyol 40-50 parts, isophorone diisocyanate 70-90 parts, dibutyl tin dilaurate 1-3 parts, 2,2-dimethylol butyric acid 2-4 parts, and modified hyperbranched fluorine-containing polymer 5-15 parts.

4. The process for preparing a printable OPP glazing film according to claim 1, characterized in that: The molar ratio of dodecafluoroheptyl methacrylate to diethanolamine is 1:(1-1.2).

5. The process for preparing a printable OPP glazing film according to claim 1, wherein: The pre-emulsified monomer comprises the following raw materials in parts by weight: methyl methacrylate 30-40 parts, butyl acrylate 40-50 parts, hydroxyethyl acrylate 10-20 parts, double bond-containing silica 5-15 parts, emulsifier 3-6 parts, deionized water 150-300 parts.

6. The process for preparing a printable OPP glazing film according to claim 5, characterized in that: The emulsifier is one or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, ethoxylated alkyl sulfate sodium salt, isomeric tridecanol sulfate sodium salt, rhamnolipid.

7. The process for preparing a printable OPP glazing film according to claim 1, characterized in that: The coating amount of the coating liquid is 1.8-2.8 g / m 2 .

8. A printable OPP gloss film prepared according to the process of any one of claims 1-7.

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