Corrosion-resistant diffusion adhesive based on semi-transparent polaroid and preparation method of corrosion-resistant diffusion adhesive

Abstract

The invention discloses a corrosion-resistant diffusion adhesive based on a semi-transparent polaroid and a preparation method of the corrosion-resistant diffusion adhesive, and relates to the technical field of diffusion adhesives. The material C and the material A are mixed to prepare the corrosion-resistant diffusion adhesive. The acrylic resin is prepared, hexafluorobutyl methacrylate and vinyltriethoxysilane are added to perform fluorosilicone modification on the acrylic resin, so that the hydrophobicity of the modified acrylic resin is enhanced, and the corrosion resistance of the modified acrylic resin is improved. When the diffusion adhesive prepared by the invention is used for preparing the semi-transparent polaroid, the semi-transparent polaroid cannot be corroded when being used in a moisture environment, and the anti-corrosion capability of the semi-transparent polaroid is improved.

Description

Technical Field

[0001] The present invention relates to the technical field of diffusion adhesives, and particularly to a corrosion-resistant diffusion adhesive based on a semi-transmissive polarizer and a preparation method thereof. Background Art

[0002] In modern display technologies, polarizers are one of the key optical components and are widely used in liquid crystal displays, optical display modules, and other optical devices. However, under harsh environments or long-term use conditions, semi-transmissive polarizers face problems of corrosion and degradation. Traditional semi-transmissive polarizers may experience a decline in performance in certain corrosive environments, which is usually related to the insufficient corrosion resistance of the adhesive. Therefore, developing a diffusion adhesive with excellent corrosion resistance and capable of effectively bonding with semi-transmissive polarizers is the key to improving their durability and stability.

[0003] However, existing diffusion adhesives generally have certain limitations in terms of corrosion resistance and cannot meet the requirements for durability and stability in high-end displays and optical devices.

[0004] To solve the above problems and improve the corrosion resistance of the diffusion adhesive, the present invention provides a corrosion-resistant diffusion adhesive based on a semi-transmissive polarizer and a preparation method thereof. Summary of the Invention

[0005] The purpose of the present invention is to provide a corrosion-resistant diffusion adhesive based on a semi-transmissive polarizer and a preparation method thereof to solve the problems raised in the prior art.

[0006] To achieve the above purpose, the present invention provides the following technical solutions:

[0007] A preparation method of a corrosion-resistant diffusion adhesive based on a semi-transmissive polarizer, comprising the following steps:

[0008] Step 1: Add modified nanofibers to a modified acrylic resin, melt and blend the modified acrylic resin and the modified nanofibers at 140 - 145 °C, and then hot press at 195 - 200 °C to obtain a resin mixture; take the resin mixture and acetone, heat to 85 - 95 °C, stir evenly, and cool to obtain Material A;

[0009] Step 2: Take tannic acid, polyethylene glycol diglycidyl ether, dibutyltin dilaurate, and deionized water, pass nitrogen, stir for 30 - 40 min, heat to 100 °C and react for 22 - 26 h, cool to 25 - 30 °C, and stir evenly to obtain Material B;

[0010] Step 3: Take Material B and glycine, stir and heat to 165 - 170 °C, add p-toluenesulfonic acid and anhydrous sodium sulfate, pass nitrogen, and react for 5 - 7 h. After the reaction is completed, stir evenly to obtain Material C;

[0011] Step 4: Take ethylenediamine and acetone, stir evenly, heat up to 85 - 90 °C to obtain an ethylenediamine solution, add Material A and Material C, and stir evenly to obtain a corrosion-resistant diffusion glue.

[0012] More optimally, in Step 1, the preparation method of the modified acrylic resin is as follows: Take styrene, methyl methacrylate, hydroxypropyl methacrylate, butyl acrylate, hexafluorobutyl methacrylate, dimethylaminoethyl methacrylate, vinyltriethoxysilane, and initiator azobisisobutyronitrile, stir evenly to obtain a mixed solution; Take initiator azobisisobutyronitrile and ethylene glycol monobutyl ether, stir evenly to obtain an azobisisobutyronitrile solution; Take ethylene glycol monobutyl ether, heat up to 90 - 95 °C, dropwise add the mixed solution, react for 3 - 4 h, add the azobisisobutyronitrile solution, react for 2 - 3 h, then cool down to 60 - 65 °C, add glacial acetic acid, and react for 30 - 40 min to obtain the modified acrylic resin.

[0013] More optimally, in Step 1, the preparation method of the modified nanofibers is as follows: Take corrosion-resistant nanofibers and toluene, disperse them by ultrasonic treatment, add amino-functionalized cage-like octasilsesquioxane, stir evenly, add Tris buffer solution, react at 75 - 85 °C for 5 - 6 h, cool, filter, and dry to obtain the modified nanofibers.

[0014] More optimally, the preparation method of the corrosion-resistant nanofibers includes the following steps:

[0015] S1: Take copper acetate and N, N-dimethylformamide, stir evenly, add polyacrylonitrile, and stir for 12 - 14 h to obtain a mixed solution; Inject the mixed solution into a syringe and then perform electrospinning to obtain nanofibers;

[0016] S2: Take the nanofibers, heat up to 190 - 200 °C in a nitrogen atmosphere, keep warm for 1 - 2 h, and then heat up to 650 - 680 °C at a rate of 5 °C / min to obtain the corrosion-resistant nanofibers.

[0017] More optimally, the preparation method of the amino-functionalized cage-like octasilsesquioxane is as follows: Take deionized water, propanol, acetonitrile, and tetraethylammonium hydroxide, stir evenly, add KH550, stir for 15 - 20 min, then heat up to 60 - 65 °C, stir for 22 - 26 h, cool to 25 - 30 °C, cool the obtained product in tetrahydrofuran, precipitate, filter, and dry to obtain the amino-functionalized cage-like octasilsesquioxane.

[0018] More optimally, during electrospinning, the working voltage is 12 kV and the injection rate is 0.02 mm / min.

[0019] More optimally, in Step 1, the mass ratio of the modified nanofibers to the modified acrylic resin is (0.8 - 0.85):2.

[0020] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0021] 1. The present invention mixes material C with material A to prepare a corrosion-resistant diffusion adhesive. The present invention prepares an acrylic resin, and fluorosilicon modification is carried out on it by adding hexafluorobutyl methacrylate and vinyltriethoxysilane, so that the hydrophobicity of the modified acrylic resin is enhanced and its corrosion resistance is improved.

[0022] 2. Material A is prepared by adding modified nanofibers to the modified acrylic resin. Nanofibers are prepared by adding copper acetate, and metallic copper is loaded on the nanofibers, and then the nanofibers are carbonized to improve the corrosion resistance of the nanofibers. The nanofibers are further modified with aminated cage-like silsesquioxane, which further improves the corrosion resistance of the nanofibers and loads amino groups on the modified nanofibers.

[0023] 3. Glycine is used to further modify the polyether polyol. While improving the corrosion resistance of the polyether polyol, the polyether polyol is also aminated. Therefore, material C with amino groups can be better compatible with material A also with amino groups, improving the corrosion resistance of the diffusion adhesive. Using the diffusion adhesive prepared by the present invention to prepare a semi-transmissive polarizer can enable the semi-transmissive polarizer to be used in a water-vapor humid environment without corrosion problems, improving the anti-corrosion ability of the semi-transmissive polarizer. Specific Embodiments

[0024] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0025] There are no special restrictions on the purchasing manufacturers of all raw materials involved in the present invention. Exemplarily, they include: polyacrylonitrile: can be purchased from Merck, model: 181315; polyethylene glycol diglycidyl ether: can be purchased from Merck, model: 731803.

[0026] Example 1: A preparation method of a corrosion-resistant diffusion adhesive based on a semi-transmissive polarizer, comprising the following steps:

[0027] Step 1: Preparation of the modified acrylic resin:

[0028] Take 12 g of styrene, 12 g of methyl methacrylate, 12.5 g of hydroxypropyl methacrylate, 16 g of butyl acrylate, 4 g of hexafluorobutyl methacrylate, 9 g of dimethylaminoethyl methacrylate, 2.5 g of vinyltriethoxysilane, and 1 g of initiator azobisisobutyronitrile, stir evenly to obtain a mixed solution; take 0.2 g of initiator azobisisobutyronitrile and 10 g of ethylene glycol monobutyl ether, stir evenly to obtain an azobisisobutyronitrile solution; take 28 g of ethylene glycol monobutyl ether, heat up to 93 °C, dropwise add the mixed solution, react for 3.5 h, add the azobisisobutyronitrile solution, react for 2.5 h, then cool down to 62 °C, add 2.8 g of glacial acetic acid, and react for 35 min to obtain a modified acrylic resin;

[0029] Step 2: Preparation of corrosion-resistant nanofibers:

[0030] Take 1.5 g of copper acetate and 30 mL of N,N-dimethylformamide, stir evenly, add 1.3 g of polyacrylonitrile, and stir for 13 h to obtain a mixed solution; inject the mixed solution into a syringe and perform electrospinning to obtain nanofibers; the spinning needle head model is 20, the working voltage is 12 kV, and the injection speed is 0.02 mm / min;

[0031] Take the nanofibers, heat up to 195 °C in a nitrogen atmosphere, keep warm for 1.5 h, and then heat up to 670 °C at a rate of 5 °C / min to obtain corrosion-resistant nanofibers;

[0032] Step 3: Preparation of amino-functionalized cage-like silsesquioxane:

[0033] Take 45 mL of deionized water, 20 mL of propanol, 5 mL of acetonitrile, and 1 mL of tetraethylammonium hydroxide, stir evenly, add 100 g of KH550, stir for 17 min, then heat up to 62 °C and stir for 24 h, cool to 27 °C, cool the obtained product in tetrahydrofuran at 0 °C, precipitate, filter, and dry to obtain amino-functionalized cage-like silsesquioxane;

[0034] Step 4: Preparation of modified nanofibers:

[0035] Take 1 g of corrosion-resistant nanofibers and 200 mL of toluene, disperse them by ultrasonic wave, add 0.1 g of amino-functionalized cage-like silsesquioxane, stir evenly, add 60 mL of Tris buffer solution, react at 80 °C for 5.5 h, cool, filter, and dry to obtain modified nanofibers;

[0036] Step 5: Preparation of Material A:

[0037] Add modified nanofibers to the modified acrylic resin, melt-blend the modified acrylic resin and the modified nanofibers at 142 °C, and then hot-press them at 198 °C to obtain a resin mixture; take 50 g of the resin mixture and 500 mL of acetone, heat it to 90 °C, stir evenly, and cool to obtain Material A;

[0038] The mass ratio of the modified nanofibers to the modified acrylic resin is 0.82:2;

[0039] Step Six: Preparation of Material C:

[0040] Take 3.5 g of tannic acid, 75 g of polyethylene glycol diglycidyl ether, 0.5 g of dibutyltin dilaurate, and 160 g of deionized water, pass nitrogen, stir for 35 min, heat up to 100 °C and react for 24 h, cool to 28 °C, and stir evenly to obtain Material B;

[0041] Take 300 g of Material B and 50 g of glycine, stir and heat up to 167 °C, add 2 g of p-toluenesulfonic acid and 2 g of anhydrous sodium sulfate, pass nitrogen, react for 6 h, after the reaction is completed, stir evenly to obtain Material C;

[0042] Step Seven: Preparation of the corrosion-resistant diffusion adhesive:

[0043] Take 1 g of ethylenediamine and 100 mL of acetone, stir evenly, heat up to 88 °C to obtain an ethylenediamine solution, add 75 g of Material A and 2 g of Material C, and stir evenly to obtain the corrosion-resistant diffusion adhesive.

[0044] Example 2: A method for preparing a corrosion-resistant diffusion adhesive based on a semi-permeable polarizer, comprising the following steps:

[0045] Step One: Preparation of the modified acrylic resin:

[0046] Take 12 g of styrene, 12 g of methyl methacrylate, 12.5 g of hydroxypropyl methacrylate, 16 g of butyl acrylate, 4 g of hexafluorobutyl methacrylate, 9 g of dimethylaminoethyl methacrylate, 2.5 g of vinyltriethoxysilane, and 1 g of initiator azobisisobutyronitrile, stir evenly to obtain a mixed solution; take 0.2 g of initiator azobisisobutyronitrile and 10 g of ethylene glycol monobutyl ether, stir evenly to obtain an azobisisobutyronitrile solution; take 28 g of ethylene glycol monobutyl ether, heat up to 90 °C, dropwise add the mixed solution, react for 3 h, add the azobisisobutyronitrile solution, react for 2 h, then cool to 60 °C, add 2.8 g of glacial acetic acid, and react for 30 min to obtain the modified acrylic resin;

[0047] Step Two: Preparation of the corrosion-resistant nanofibers:

[0048] Take 1.5 g of copper acetate and 30 mL of N,N-dimethylformamide, stir evenly, add 1.3 g of polyacrylonitrile, and stir for 12 h to obtain a mixed solution; inject the mixed solution into a syringe and then perform electrospinning to obtain nanofibers; the spinning needle model is 20, the working voltage is 12 kV, and the injection speed is 0.02 mm / min;

[0049] Take the nanofibers, heat them up to 190 °C in a nitrogen atmosphere, keep them at this temperature for 1 h, and then heat them up to 650 °C at a rate of 5 °C / min to obtain corrosion-resistant nanofibers;

[0050] Step 3: Preparation of amino-functionalized cage-like silsesquioxane:

[0051] Take 45 mL of deionized water, 20 mL of propanol, 5 mL of acetonitrile, and 1 mL of tetraethylammonium hydroxide, stir evenly, add 100 g of KH550, stir for 15 min, then heat up to 60 °C and stir for 22 h, cool to 25 °C, cool the obtained product in tetrahydrofuran at 0 °C, precipitate, filter, and dry to obtain amino-functionalized cage-like silsesquioxane;

[0052] Step 4: Preparation of modified nanofibers:

[0053] Take 1 g of corrosion-resistant nanofibers and 200 mL of toluene, disperse them by ultrasonic treatment, add 0.1 g of amino-functionalized cage-like silsesquioxane, stir evenly, add 60 mL of Tris buffer solution, react at 75 °C for 5 h, cool, filter, and dry to obtain modified nanofibers;

[0054] Step 5: Preparation of Material A:

[0055] Add modified nanofibers to the modified acrylic resin, melt-blend the modified acrylic resin and the modified nanofibers at 140 °C, and then hot-press them into a mold at 195 °C to obtain a resin mixture; take 50 g of the resin mixture and 500 mL of acetone, heat up to 85 °C, stir evenly, and cool to obtain Material A;

[0056] The mass ratio of the modified nanofibers to the modified acrylic resin is 0.8:2;

[0057] Step 6: Preparation of Material C:

[0058] Take 3.5 g of tannic acid, 75 g of polyethylene glycol diglycidyl ether, 0.5 g of dibutyltin dilaurate, and 160 g of deionized water, pass nitrogen, stir for 30 min, heat up to 100 °C and react for 22 h, cool to 25 °C, and stir evenly to obtain Material B;

[0059] Take 300 g of material B and 50 g of glycine, stir and heat up to 165 °C, add 2 g of p-toluenesulfonic acid and 2 g of anhydrous sodium sulfate, introduce nitrogen, react for 5 h, after the reaction is completed, stir evenly to obtain material C;

[0060] Step 7: Preparation of the corrosion-resistant diffusion glue:

[0061] Take 1 g of ethylenediamine and 100 mL of acetone, stir evenly, heat up to 85 °C to obtain an ethylenediamine solution, add 75 g of material A and 2 g of material C, stir evenly to obtain the corrosion-resistant diffusion glue.

[0062] Example 3: A preparation method of a corrosion-resistant diffusion glue based on a semi-permeable polarizing film, comprising the following steps:

[0063] Step 1: Preparation of the modified acrylic resin:

[0064] Take 12 g of styrene, 12 g of methyl methacrylate, 12.5 g of hydroxypropyl methacrylate, 16 g of butyl acrylate, 4 g of hexafluorobutyl methacrylate, 9 g of dimethylaminoethyl methacrylate, 2.5 g of vinyltriethoxysilane, and 1 g of initiator azobisisobutyronitrile, stir evenly to obtain a mixed solution; take 0.2 g of initiator azobisisobutyronitrile and 10 g of ethylene glycol monobutyl ether, stir evenly to obtain an azobisisobutyronitrile solution; take 28 g of ethylene glycol monobutyl ether, heat up to 95 °C, dropwise add the mixed solution, react for 4 h, add the azobisisobutyronitrile solution, react for 3 h, then cool down to 65 °C, add 2.8 g of glacial acetic acid, react for 40 min to obtain the modified acrylic resin;

[0065] Step 2: Preparation of the corrosion-resistant nanofibers:

[0066] Take 1.5 g of copper acetate and 30 mL of N,N-dimethylformamide, stir evenly, add 1.3 g of polyacrylonitrile, stir for 14 h to obtain a mixed solution; inject the mixed solution into a syringe and perform electrospinning to obtain nanofibers; the spinning needle head model is 20, the working voltage is 12 kV, and the injection speed is 0.02 mm / min;

[0067] Take the nanofibers, heat up to 200 °C in a nitrogen atmosphere, keep warm for 2 h, and then heat up to 680 °C at a rate of 5 °C / min to obtain the corrosion-resistant nanofibers;

[0068] Step 3: Preparation of the amino-functionalized cage-like silsesquioxane:

[0069] Take 45 mL of deionized water, 20 mL of propanol, 5 mL of acetonitrile, and 1 mL of tetraethylammonium hydroxide, stir evenly, add 100 g of KH550, stir for 20 min, then heat up to 65 °C, stir for 26 h, cool to 30 °C, cool the obtained product in tetrahydrofuran at 0 °C, precipitate, filter, and dry to obtain amino-functionalized cage-shaped silsesquioxane;

[0070] Step 4: Preparation of modified nanofibers:

[0071] Take 1 g of corrosion-resistant nanofibers and 200 mL of toluene, disperse them by ultrasonic treatment, add 0.1 g of amino-functionalized cage-shaped silsesquioxane, stir evenly, add 60 mL of Tris buffer solution, react at 85 °C for 6 h, cool, filter, and dry to obtain modified nanofibers;

[0072] Step 5: Preparation of Material A:

[0073] Add modified nanofibers to the modified acrylic resin, melt-blend the modified acrylic resin and the modified nanofibers at 145 °C, and then hot-press them at 200 °C to obtain a resin mixture; take 50 g of the resin mixture and 500 mL of acetone, heat up to 95 °C, stir evenly, and cool to obtain Material A;

[0074] The mass ratio of the modified nanofibers to the modified acrylic resin is 0.85:2;

[0075] Step 6: Preparation of Material C:

[0076] Take 3.5 g of tannic acid, 75 g of polyethylene glycol diglycidyl ether, 0.5 g of dibutyltin dilaurate, and 160 g of deionized water, purge with nitrogen, stir for 40 min, heat up to 100 °C and react for 26 h, cool to 30 °C, and stir evenly to obtain Material B;

[0077] Take 300 g of Material B and 50 g of glycine, stir and heat up to 170 °C, add 2 g of p-toluenesulfonic acid and 2 g of anhydrous sodium sulfate, purge with nitrogen, and react for 7 h. After the reaction is completed, stir evenly to obtain Material C;

[0078] Step 7: Preparation of corrosion-resistant diffusion glue:

[0079] Take 1 g of ethylenediamine and 100 mL of acetone, stir evenly, heat up to 90 °C to obtain an ethylenediamine solution, add 75 g of Material A and 2 g of Material C, and stir evenly to obtain corrosion-resistant diffusion glue.

[0080] Comparative Example 1: Do not load copper on the nanofibers, and the rest is the same as in Example 1:

[0081] Step 1: Preparation of modified acrylic resin:

[0082] Take 12 g of styrene, 12 g of methyl methacrylate, 12.5 g of hydroxypropyl methacrylate, 16 g of butyl acrylate, 4 g of hexafluorobutyl methacrylate, 9 g of dimethylaminoethyl methacrylate, 2.5 g of vinyltriethoxysilane, and 1 g of initiator azobisisobutyronitrile, stir evenly to obtain a mixed solution; take 0.2 g of initiator azobisisobutyronitrile and 10 g of ethylene glycol monobutyl ether, stir evenly to obtain an azobisisobutyronitrile solution; take 28 g of ethylene glycol monobutyl ether, heat up to 93 °C, dropwise add the mixed solution, react for 3.5 h, add the azobisisobutyronitrile solution, react for 2.5 h, then cool down to 62 °C, add 2.8 g of glacial acetic acid, react for 35 min to obtain a modified acrylic resin;

[0083] Step Two: Preparation of corrosion-resistant nanofibers:

[0084] Take 1.3 g of polyacrylonitrile and 30 mL of N,N-dimethylformamide, stir for 13 h to obtain a mixed solution; inject the mixed solution into a syringe and then perform electrospinning to obtain nanofibers; the spinning needle head model is 20, the working voltage is 12 kV, and the pushing speed is 0.02 mm / min;

[0085] Take the nanofibers, heat up to 195 °C in a nitrogen atmosphere, keep warm for 1.5 h, and then heat up to 670 °C at a rate of 5 °C / min to obtain corrosion-resistant nanofibers;

[0086] Step Three: Preparation of amino-functionalized cage-like silsesquioxane:

[0087] Take 45 mL of deionized water, 20 mL of propanol, 5 mL of acetonitrile, and 1 mL of tetraethylammonium hydroxide, stir evenly, add 100 g of KH550, stir for 17 min, then heat up to 62 °C, stir for 24 h, cool down to 27 °C, cool the obtained product in tetrahydrofuran at 0 °C, precipitate, filter, and dry to obtain amino-functionalized cage-like silsesquioxane;

[0088] Step Four: Preparation of modified nanofibers:

[0089] Take 1 g of corrosion-resistant nanofibers and 200 mL of toluene, ultrasonically disperse, add 0.1 g of amino-functionalized cage-like silsesquioxane, stir evenly, add 60 mL of Tris buffer solution, react at 80 °C for 5.5 h, cool, filter, and dry to obtain modified nanofibers;

[0090] Step Five: Preparation of Material A:

[0091] Add modified nanofibers to the modified acrylic resin, melt-blend the modified acrylic resin and the modified nanofibers at 142 °C, and then hot-press and mold at 198 °C to obtain a resin mixture; take 50 g of the resin mixture and 500 mL of acetone, heat up to 90 °C, stir evenly, and cool to obtain Material A;

[0092] The mass ratio of the modified nanofibers to the modified acrylic resin is 0.82:2;

[0093] Step Six: Preparation of Material C:

[0094] Take 3.5 g of tannic acid, 75 g of polyethylene glycol diglycidyl ether, 0.5 g of dibutyltin dilaurate, and 160 g of deionized water. Pass nitrogen and stir for 35 min. Heat up to 100 °C and react for 24 h. Cool to 28 °C and stir evenly to obtain Material B;

[0095] Take 300 g of Material B and 50 g of glycine. Stir and heat up to 167 °C. Add 2 g of p-toluenesulfonic acid and 2 g of anhydrous sodium sulfate. Pass nitrogen and react for 6 h. After the reaction is completed, stir evenly to obtain Material C;

[0096] Step Seven: Preparation of the corrosion-resistant diffusion glue:

[0097] Take 1 g of ethylenediamine and 100 mL of acetone. Stir evenly and heat up to 88 °C to obtain an ethylenediamine solution. Add 75 g of Material A and 2 g of Material C and stir evenly to obtain the corrosion-resistant diffusion glue.

[0098] Comparative Example 2: The corrosion-resistant nanofibers are not modified with amino-functionalized cage-like silsesquioxane, and the rest is the same as in Example 1:

[0099] Step One: Preparation of the modified acrylic resin:

[0100] Take 12 g of styrene, 12 g of methyl methacrylate, 12.5 g of hydroxypropyl methacrylate, 16 g of butyl acrylate, 4 g of hexafluorobutyl methacrylate, 9 g of dimethylaminoethyl methacrylate, 2.5 g of vinyltriethoxysilane, and 1 g of initiator azobisisobutyronitrile. Stir evenly to obtain a mixed solution; take 0.2 g of initiator azobisisobutyronitrile and 10 g of ethylene glycol monobutyl ether. Stir evenly to obtain an azobisisobutyronitrile solution; take 28 g of ethylene glycol monobutyl ether, heat up to 93 °C, dropwise add the mixed solution, react for 3.5 h, add the azobisisobutyronitrile solution, react for 2.5 h, then cool down to 62 °C, add 2.8 g of glacial acetic acid, and react for 35 min to obtain the modified acrylic resin;

[0101] Step Two: Preparation of the corrosion-resistant nanofibers:

[0102] Take 1.5 g of copper acetate and 30 mL of N,N-dimethylformamide. Stir evenly, add 1.3 g of polyacrylonitrile, and stir for 13 h to obtain a mixed solution; inject the mixed solution into a syringe and perform electrospinning to obtain nanofibers; the spinning needle head model is 20, the working voltage is 12 kV, and the injection speed is 0.02 mm / min;

[0103] Take nanofibers, heat them to 195 °C in a nitrogen atmosphere, hold for 1.5 h, and then heat them to 670 °C at a rate of 5 °C / min to obtain corrosion-resistant nanofibers;

[0104] Step 3: Preparation of Material A:

[0105] Add corrosion-resistant nanofibers to the modified acrylic resin, melt-blend the modified acrylic resin and the corrosion-resistant nanofibers at 142 °C, and then hot-press them at 198 °C to obtain a resin mixture; take 50 g of the resin mixture and 500 mL of acetone, heat them to 90 °C, stir evenly, and cool to obtain Material A;

[0106] The mass ratio of the modified nanofibers to the modified acrylic resin is 0.82:2;

[0107] Step 4: Preparation of Material C:

[0108] Take 3.5 g of tannic acid, 75 g of polyethylene glycol diglycidyl ether, 0.5 g of dibutyltin dilaurate, and 160 g of deionized water, introduce nitrogen, stir for 35 min, heat to 100 °C and react for 24 h, cool to 28 °C, and stir evenly to obtain Material B;

[0109] Take 300 g of Material B and 50 g of glycine, stir and heat to 167 °C, add 2 g of p-toluenesulfonic acid and 2 g of anhydrous sodium sulfate, introduce nitrogen, react for 6 h, and after the reaction is completed, stir evenly to obtain Material C;

[0110] Step 5: Preparation of the corrosion-resistant diffusion adhesive:

[0111] Take 1 g of ethylenediamine and 100 mL of acetone, stir evenly, heat to 88 °C to obtain an ethylenediamine solution, add 75 g of Material A and 2 g of Material C, and stir evenly to obtain the corrosion-resistant diffusion adhesive.

[0112] Comparative Example 3: Without adding glycine, the rest is the same as in Example 1:

[0113] Step 1: Preparation of the modified acrylic resin:

[0114] Take 12 g of styrene, 12 g of methyl methacrylate, 12.5 g of hydroxypropyl methacrylate, 16 g of butyl acrylate, 4 g of hexafluorobutyl methacrylate, 9 g of dimethylaminoethyl methacrylate, 2.5 g of vinyltriethoxysilane, and 1 g of initiator azobisisobutyronitrile, stir evenly to obtain a mixed solution; take 0.2 g of initiator azobisisobutyronitrile and 10 g of ethylene glycol monobutyl ether, stir evenly to obtain an azobisisobutyronitrile solution; take 28 g of ethylene glycol monobutyl ether, heat to 93 °C, dropwise add the mixed solution, react for 3.5 h, add the azobisisobutyronitrile solution, react for 2.5 h, then cool to 62 °C, add 2.8 g of glacial acetic acid, and react for 35 min to obtain the modified acrylic resin;

[0115] Step 2: Preparation of corrosion-resistant nanofibers:

[0116] Take 1.5 g of copper acetate and 30 mL of N,N-dimethylformamide, stir evenly, add 1.3 g of polyacrylonitrile, and stir for 13 h to obtain a mixed solution; inject the mixed solution into a syringe and perform electrospinning to obtain nanofibers; the spinning needle model is 20, the working voltage is 12 kV, and the injection speed is 0.02 mm / min.

[0117] Take the nanofibers, heat them up to 195 °C in a nitrogen atmosphere, keep them warm for 1.5 h, and then heat them up to 670 °C at a rate of 5 °C / min to obtain corrosion-resistant nanofibers.

[0118] Step 3: Preparation of amino-functionalized cage-like silsesquioxane:

[0119] Take 45 mL of deionized water, 20 mL of propanol, 5 mL of acetonitrile, and 1 mL of tetraethylammonium hydroxide, stir evenly, add 100 g of KH550, stir for 17 min, then heat up to 62 °C and stir for 24 h, cool to 27 °C, cool the obtained product in tetrahydrofuran at 0 °C, precipitate, filter, and dry to obtain amino-functionalized cage-like silsesquioxane.

[0120] Step 4: Preparation of modified nanofibers:

[0121] Take 1 g of corrosion-resistant nanofibers and 200 mL of toluene, disperse them by ultrasonic wave, add 0.1 g of amino-functionalized cage-like silsesquioxane, stir evenly, add 60 mL of Tris buffer solution, react at 80 °C for 5.5 h, cool, filter, and dry to obtain modified nanofibers.

[0122] Step 5: Preparation of Material A:

[0123] Add modified nanofibers to the modified acrylic resin, melt-blend the modified acrylic resin and modified nanofibers at 142 °C, and then hot-press them at 198 °C to obtain a resin mixture; take 50 g of the resin mixture and 500 mL of acetone, heat up to 90 °C, stir evenly, and cool to obtain Material A.

[0124] The mass ratio of the modified nanofibers to the modified acrylic resin is 0.82:2.

[0125] Step 6: Preparation of Material C:

[0126] Take 3.5 g of tannic acid, 75 g of polyethylene glycol diglycidyl ether, 0.5 g of dibutyltin dilaurate, and 160 g of deionized water. Pass nitrogen gas, stir for 35 min, heat up to 100 °C and react for 24 h, then cool to 28 °C and stir evenly to obtain Material B; Take 300 g of Material B, heat up to 167 °C, add 2 g of p-toluenesulfonic acid and 2 g of anhydrous sodium sulfate, pass nitrogen gas, react for 6 h, and after the reaction is completed, stir evenly to obtain Material C;

[0127] Step 7: Preparation of the corrosion-resistant diffusion adhesive:

[0128] Take 1 g of ethylenediamine and 100 mL of acetone, stir evenly, heat up to 88 °C to obtain an ethylenediamine solution, add 75 g of Material A and 2 g of Material C, and stir evenly to obtain the corrosion-resistant diffusion adhesive.

[0129] Experiment:

[0130] Take the corrosion-resistant diffusion adhesives prepared in Examples 1 - 3 and Comparative Examples 1 - 3 for performance testing. Use a 55-μm-thick PET film as the reflective film; Combine the protective film, reflective film, polarizer original plate, corrosion-resistant diffusion adhesive, and release film from top to bottom to obtain a semi-transmissive polarizer; The reflective film and the polarizer original plate are bonded through the corrosion-resistant diffusion adhesive, and the polarizer original plate and the release film are bonded through the corrosion-resistant diffusion adhesive; Place the prepared semi-transmissive polarizer in a sodium chloride salt spray environment with a temperature of 35 °C, a relative humidity of 85%, and a concentration of 5%, and record the peeling situation and time of the corrosion-resistant diffusion adhesive layer of the polarizer to characterize its corrosion resistance;

[0131] Corrosion resistance Example 1 The adhesive layer does not blister after 1548h Example 2 The adhesive layer does not blister after 1548h Example 3 The adhesive layer does not blister after 1548h Comparative Example 1 Blistering and peeling phenomena occur in the adhesive layer after 1500h Comparative Example 2 Blistering and peeling phenomena occur in the adhesive layer after 1512h Comparative Example 3 Blistering and peeling phenomena occur in the adhesive layer after 1522h

[0132] Conclusion: In Comparative Example 1, copper is not loaded on the nanofibers, and the corrosion resistance of the nanofibers deteriorates. In Comparative Example 2, the corrosion-resistant nanofibers are not modified with amino-functionalized cage-like octasilsesquioxane, and the corrosion resistance of the nanofibers deteriorates. At this time, the corrosion resistance of the diffusion adhesive deteriorates, and the reflective film has a perforation phenomenon. In Comparative Example 3, glycine is not added, and the compatibility between Material C and Material A deteriorates, and the corrosion resistance of the diffusion adhesive deteriorates. Using the diffusion adhesives prepared in Examples 1 - 3 of the present invention to prepare semi-transmissive polarizers will not cause corrosion problems even when used in a humid environment, improving the anti-corrosion ability of the semi-transmissive polarizers.

[0133] For those skilled in the art, it is obvious that the present invention is not limited to the details of the above-described exemplary embodiments, and can be implemented in other specific forms without departing from the spirit or basic characteristics of the present invention. Therefore, from any point of view, the embodiments should be regarded as exemplary and non-limiting. The scope of the present invention is defined by the appended claims rather than the above description. Therefore, all changes falling within the meaning and scope of the equivalent elements of the claims are intended to be included in the present invention.

Claims

1. A preparation method of a corrosion-resistant diffusion adhesive based on a semi-permeable polarizer, characterized in that: It includes the following steps: Step 1: Add modified nanofibers to the modified acrylic resin. Melt and blend the modified acrylic resin and the modified nanofibers at 140 - 145 °C, and then hot press and mold at 195 - 200 °C to obtain a resin mixture. Take the resin mixture and acetone, heat up to 85 - 95 °C, stir evenly, and cool to obtain Material A; Step 2: Take tannic acid, polyethylene glycol diglycidyl ether, dibutyltin dilaurate, and acetone, pass nitrogen, stir for 30 - 40 min, heat up to 100 °C and react for 22 - 26 h, cool to 25 - 30 °C, and stir evenly to obtain Material B; Step 3: Take Material B and glycine, stir and heat up to 165 - 170 °C, add p-toluenesulfonic acid and anhydrous sodium sulfate, pass nitrogen, and react for 5 - 7 h. After the reaction is completed, stir evenly to obtain Material C; Step 4: Take ethylenediamine and acetone, stir evenly, heat up to 85 - 90 °C to obtain an ethylenediamine solution, add Material A and Material C, and stir evenly to obtain a corrosion-resistant diffusion glue.

2. The preparation method of a corrosion-resistant diffusion adhesive based on a semi-transparent polarizing film according to claim 1, characterized in that: In Step 1, the preparation method of the modified acrylic resin is as follows: Take styrene, methyl methacrylate, hydroxypropyl methacrylate, butyl acrylate, hexafluorobutyl methacrylate, dimethylaminoethyl methacrylate, vinyltriethoxysilane, and initiator azobisisobutyronitrile, stir evenly to obtain a mixed solution; Take azobisisobutyronitrile and ethylene glycol monobutyl ether, stir evenly to obtain an azobisisobutyronitrile solution; Take ethylene glycol monobutyl ether, heat up to 90 - 95 °C, dropwise add the mixed solution, react for 3 - 4 h, add the azobisisobutyronitrile solution, react for 2 - 3 h, then cool down to 60 - 65 °C, add glacial acetic acid, and react for 30 - 40 min to obtain the modified acrylic resin.

3. The preparation method of a corrosion-resistant diffusion adhesive based on a semi-permeable polarizer according to claim 1, wherein: In Step 1, the preparation method of the modified nanofibers is as follows: Take corrosion-resistant nanofibers and toluene, ultrasonically disperse, add amino-functionalized cage-like octasilsesquioxane, stir evenly, add Tris buffer solution, react at 75 - 85 °C for 5 - 6 h, cool, filter, and dry to obtain the modified nanofibers.

4. The preparation method of a corrosion-resistant diffusion adhesive based on a semi-transparent polarizer according to claim 3, characterized in that: The preparation method of the corrosion-resistant nanofibers is as follows: It includes the following steps: S1: Take copper acetate and N,N-dimethylformamide, stir evenly, add polyacrylonitrile, and stir for 12 - 14 h to obtain a mixed solution; Inject the mixed solution into a syringe and perform electrospinning to obtain nanofibers; S2: Take the nanofibers, heat up to 190 - 200 °C in a nitrogen atmosphere, keep warm for 1 - 2 h, and then heat up to 650 - 680 °C at a rate of 5 °C / min to obtain corrosion-resistant nanofibers.

5. The preparation method of a corrosion-resistant diffusion adhesive based on a semi-transparent polarizer according to claim 3, characterized in that: The preparation method of the amino-functionalized cage-like octasilsesquioxane is as follows: Take deionized water, propanol, acetonitrile, and tetraethylammonium hydroxide, stir evenly, add KH550, stir for 15 - 20 min, then heat up to 60 - 65 °C and stir for 22 - 26 h, cool to 25 - 30 °C, cool the obtained product in tetrahydrofuran, precipitate, filter, and dry to obtain the amino-functionalized cage-like octasilsesquioxane.

6. The preparation method of a corrosion-resistant diffusion adhesive based on a semi-permeable polarizer according to claim 4, characterized in that: During electrospinning, the working voltage is 12 kV and the injection speed is 0.02 mm / min.

7. The preparation method of a corrosion-resistant diffusion adhesive based on a semi-permeable polarizing film according to claim 1, characterized in that: In Step 1, the mass ratio of the modified nanofibers to the modified acrylic resin is (0.8 - 0.85):

2.

8. A corrosion-resistant diffusion adhesive based on a semi-transmissive polarizer, prepared by the method for preparing a corrosion-resistant diffusion adhesive based on a semi-transmissive polarizer according to any one of claims 1 - 7.