A functional ink for glass cover plates and its preparation method

Abstract

The present invention relates to the technical field of inks, and discloses a functional ink for glass covers and a preparation method thereof. The ink comprises the following raw materials: styrene, butyl acrylate, methyl methacrylate, methacrylic acid; BEM, deionized water, initiator, emulsifier, chain transfer agent, inorganic modified additive, pigment, tributyl phosphate, polyethylene glycol; wherein the inorganic modified additive is obtained by modifying a rosin-based polymeric substance on the surface of nano-zinc oxide. Zinc oxide has good light transmittance. By using the chemical grafting method, the light transmittance of the ink is increased. In addition, the unsaturated alkenyl functional group can crosslink with the substrate, enabling the prepared ink to have high adhesion. Moreover, the contained ether bonds and rosin structure can further improve the adhesion between the ink and the glass cover, enhancing the competitiveness of the product.

Description

Technical Field

[0001] The present invention relates to the technical field of inks, and particularly relates to a functional ink for glass covers and a preparation method thereof. Background Art

[0002] The artistic beauty of automotive interiors plays a key role in enhancing the overall quality and grade of vehicles. With the application of display screens, by creating a wood grain effect on the glass cover, the artistic beauty of a simple screen-off and a technological screen-on is achieved. The wood grain glass cover provides a unique decorative option for the interior of automobiles. It combines the natural beauty of wood grain and the modernity of glass materials. Compared with traditional automotive decoration materials, the wood grain glass cover exhibits more innovation and fashion, attracting consumers' attention and giving an integrated visual effect on the appearance. These characteristics give the wood grain glass cover significant advantages in the field of automotive decoration. The wood grain glass cover can be applied to multiple positions in automotive interiors. For example, as a decorative material for the center console panel, the wood grain glass cover can provide an elegant appearance for the cockpit and attract the attention of drivers and passengers; the wood grain glass cover used on the door trim can enhance the luxury and comfort inside the vehicle, creating a warm driving and riding experience; applying the wood grain glass cover on the instrument panel and control panel can make the driver feel more comfortable during driving. There are various manufacturing processes for wood grain glass covers. Among them, the screen printing method mainly forms the required patterns and color effects by attaching the ink to the surface of the glass cover.

[0003] Inks are mainly composed of binders, pigments, fillers, and additives, etc. With the development of social technology, there are also various requirements for the performance of inks used for glass covers. Compared with ordinary inks, the inks used for glass covers need to have high adhesion to prevent interface damage or delamination between the ink layer and the glass cover during use due to poor adhesion of the ink, and bubbles may be generated, affecting the normal use of the glass cover. In addition, when the wood grain glass cover is applied to the automotive center console, wood grain traces may be found to remain when the screen is lit. Therefore, the inks used for glass covers need to have good light transmittance to avoid the remaining of wood grain traces under light and improve the competitiveness of products.

[0004] Based on this, the present invention provides a functional ink with good adhesion and light transmittance, which can be directly applied to glass covers. Summary of the Invention

[0005] In order to solve the problems mentioned in the background art, the purpose of the present invention is to provide a functional ink for glass covers and a preparation method thereof.

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

[0007] A preparation method of a functional ink for a glass cover plate, wherein the ink comprises the following raw materials in parts by weight: 25 - 40 parts of styrene, 30 - 40 parts of butyl acrylate, 30 - 55 parts of methyl methacrylate, 10 - 20 parts of methacrylic acid; 8 - 15 parts of BEM (dodecyl polyoxyethylene ether methacrylate), 145 - 190 parts of deionized water, 1 - 2.5 parts of initiator, 0.5 - 1.5 parts of emulsifier, 0.2 - 0.8 parts of chain transfer agent, 4 - 8 parts of inorganic modification additive, 8 - 12 parts of pigment, 1 - 2 parts of tributyl phosphate, 1 - 3 parts of polyethylene glycol;

[0008] The preparation method comprises the following steps:

[0009] (1) Add styrene, butyl acrylate, methyl methacrylate, and methacrylic acid into a mixer, and stir and mix at a rate of 300 - 500 r / min for 10 - 30 min to obtain a mixed monomer; mix BEM, methyl methacrylate, and deionized water evenly to obtain a BEM mixed solution; disperse the initiator in deionized water to obtain an initiator solution;

[0010] (2) Place the emulsifier and deionized water in a reaction kettle, stir evenly mechanically, add the mixed monomer, mix well, continue to add the BEM mixed solution and the chain transfer agent into the kettle, and continue to stir for 45 - 55 min to obtain an emulsion;

[0011] (3) Add the emulsifier and deionized water into the reaction kettle, stir evenly mechanically, control the temperature in the kettle at 70 - 90 °C, add styrene, methyl methacrylate, and 5% - 15% by weight of the initiator solution, keep warm and stir for 10 - 20 min to obtain a polystyrene seed emulsion;

[0012] (4) Add deionized water into the reaction kettle, raise the temperature to 80 - 90 °C, add the polystyrene seed emulsion obtained in step (3), stir for 5 - 10 min, add 25% - 35% by weight of the initiator solution, continue to stir for 5 - 10 min, then add the emulsion obtained in step (2), the inorganic modification additive, and the remaining initiator solution, keep warm and stir for 1 - 2 h to obtain a mixed material;

[0013] (5) Add the pigment, tributyl phosphate, and polyethylene glycol into the mixed material, after adding, adjust the rotation speed to 600 - 900 r / min, stir and mix for 15 - 25 min, then stand for 10 - 20 min, and discharge to obtain the ink.

[0014] Further, the initiator is ammonium persulfate; the emulsifier is sodium dodecylbenzenesulfonate; the chain transfer agent is n-dodecyl mercaptan.

[0015] Specifically, the long-chain alkyl group structure of BEM can endow the BEM mixed solution with a low surface energy, enabling it to migrate to the surface of the ink layer during the drying process, causing uneven shrinkage of the ink layer and forming a microscopically rough surface. When light irradiates the ink layer, due to the uneven surface, the light undergoes diffuse reflection rather than specular reflection, achieving a matting effect; styrene and acrylate copolymerize to form an interpenetrating network structure. The unique topological structure enables it to maintain the light transmittance of acrylate while having light scattering properties and self-matting properties. When used as a binder, it can better capture small molecule substances such as pigments and additives, thereby reducing the amount of materials used and lowering costs; adding polystyrene as scattering particles to the matrix, scattering light by the interfaces of materials with different refractive indices, disrupting the secondary wave interference, generating scattered light, and using the emulsion copolymerization technology to integrate various performance materials to make them composite-molded, realizing the integrated visual effect of the wood grain ink under light and enhancing the comprehensive application performance of the materials.

[0016] Further, the preparation method of the inorganic modified additive includes the following steps:

[0017] S1: Add nano-zinc oxide into deionized water and ultrasonicate until a uniform dispersion is formed. Under nitrogen protection, add 2-chloroacrylic acid and catalyst A into the dispersion. Under stirring conditions, raise the temperature of the system to 90 - 95 °C, keep it warm for 5 - 8 h, then filter and separate the solid material, and after washing and drying, obtain modified nano-zinc oxide;

[0018] S2: Ultrasonically disperse the modified nano-zinc oxide in dimethyl sulfoxide to form a dispersion. Under continuous nitrogen conditions, add a rosin-based polymeric substance and catalyst B into the dispersion, mix evenly, raise the temperature to 70 - 80 °C, stir at this temperature for 4 - 8 h, then filter, collect the product, wash and dry the product to obtain the inorganic modified additive.

[0019] Further, in step S1, the average particle size of the nano-zinc oxide is 4 μm.

[0020] Further, in step S1, the catalyst A is any one of p-toluenesulfonic acid, trifluoromethanesulfonic acid, or sulfamic acid.

[0021] Further, in step S1, the mass ratio of the nano-zinc oxide to 2-chloroacrylic acid is 1:0.1 - 0.3.

[0022] Further, in step S2, the catalyst B is any one of pyridine or triethylamine.

[0023] It can be speculated that the principle of the above solution is as follows: In step S1, the surface of nano-zinc oxide contains active hydroxyl groups, which can react with the carboxyl groups in the structure of 2-chloroacrylic acid under the action of high temperature and catalyst A, thereby introducing unsaturated alkenyl functional groups and halogen functional groups on the surface of nano-zinc oxide to obtain modified nano-zinc oxide; in step S2, catalyst B is used for catalysis to enable the halogen functional groups on the surface of the modified nano-zinc oxide to undergo a substitution reaction with the hydroxyl groups in the structure of the rosin-based polymeric substance, thereby modifying the rosin-based polymeric substance on the surface of nano-zinc oxide by means of chemical connection to prepare an inorganic modified additive.

[0024] Furthermore, the preparation method of the rosin-based polymeric substance includes the following steps:

[0025] Maleic rosin and N,N-dimethylformamide are added to a reaction kettle protected by nitrogen. After stirring evenly, hydroquinone di(2-hydroxyethyl) ether and p-toluenesulfonic acid are continuously added to the kettle. After adding, heating is started until the temperature in the reaction kettle reaches 90-95 °C, and stirring is carried out for 4-6 h while maintaining the temperature. The solvent is removed by vacuum distillation to obtain the rosin-based polymeric substance.

[0026] It can be speculated that the principle of the above solution is as follows: Under the action of p-toluenesulfonic acid, hydroquinone di(2-hydroxyethyl) ether can react with maleic rosin. By controlling the dosage ratio of hydroquinone di(2-hydroxyethyl) ether and maleic rosin, the molecular chain is continuously extended, and finally a rosin derivative containing two equivalent hydroxyl groups in the structure, that is, the rosin-based polymeric substance, is formed.

[0027] Furthermore, the pigment is any one of pigment yellow 14, phthalocyanine blue B, magenta 8B, pigment carbon black or titanium dioxide.

[0028] A functional ink for a glass cover plate is prepared by the above preparation method.

[0029] The beneficial effects of the present invention:

[0030] The present invention prepares an inorganic modified additive by modifying the surface of nano-zinc oxide with a rosin-based polymeric substance. On the one hand, through the organic modification of nano-zinc oxide, the dispersibility of the inorganic modified additive in the matrix can be improved, enabling it to be evenly distributed in various regions of the ink. In addition, nano-zinc oxide has good light transmittance. By using the chemical grafting method, the refractive index matching degree between zinc oxide and the matrix is increased, reducing light scattering, thereby increasing the light transmittance of the ink. On the other hand, the unsaturated alkenyl functional groups in the inorganic modified additive can crosslink with the matrix, promoting the formation of a crosslinked network structure, making the prepared ink have high adhesion. Moreover, the inorganic modified additive contains a large number of ether bonds and rosin structures, which can further improve the adhesion between the ink layer and the glass cover plate, avoiding interface damage or delamination between the ink layer and the glass cover plate during use, and improving the durability of the glass cover plate.

[0031] Of course, it is not necessary for any product implementing the present invention to achieve all the above-mentioned advantages simultaneously. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following will briefly introduce the drawings required for describing the embodiments. Obviously, the drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can be obtained based on these drawings.

[0033] Figure 1 It is an infrared spectrum test chart of the modified nano-zinc oxide and the inorganic modified additive prepared in Example 1 of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0034] The following will clearly and completely describe the technical solutions in the embodiments of the present invention with reference to the drawings in the embodiments of the present invention. Obviously, the described embodiments are only some, rather than all, of the embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the protection scope of the present invention.

[0035] Example 1

[0036] I. Preparation of the inorganic modified additive

[0037] S1: Add 2 g of maleic rosin and N,N-dimethylformamide into a reaction kettle under nitrogen protection. After stirring evenly, continue to add 3.6 g of hydroquinone dihydroxyethyl ether and 0.05 g of p-toluenesulfonic acid into the kettle. After adding, start heating until the temperature in the reaction kettle reaches 93 °C, keep stirring for 5 h, and remove the solvent by reduced pressure distillation to obtain a rosin-based polymeric substance;

[0038] S2: Add 5 g of nano-zinc oxide with an average particle size of 4 μm to deionized water, and ultrasonicate until a homogeneous dispersion is formed. Under nitrogen protection, add 1.2 g of 2-chloroacrylic acid and 0.08 g of p-toluenesulfonic acid to the dispersion. Under stirring conditions, raise the temperature of the system to 93 °C, keep it warm for 7 h, then filter and separate the solid material, and after washing and drying, obtain modified nano-zinc oxide;

[0039] S3: Ultrasonically disperse 5 g of modified nano-zinc oxide in dimethyl sulfoxide to form a dispersion. Under continuous nitrogen conditions, add 3.4 g of rosin-based polymeric substance and 0.1 g of pyridine to the dispersion, mix well, raise the temperature to 75 °C, stir at this temperature for 6 h, then filter, collect the product, wash and dry the product to obtain an inorganic modified additive.

[0040] Use a TENSOR 27 Fourier transform infrared spectrometer produced by BRUKER of Germany to perform infrared spectral analysis on the modified nano-zinc oxide and the inorganic modified additive, as Figure 1 shown. It can be seen from Figure 1 that in the infrared spectrum of the modified nano-zinc oxide, an absorption peak of the ester group C=O appears at 1750 cm -1 , an absorption peak of the carbon-hydrogen bond in the carbon-carbon double bond appears at 3040 cm -1 , and an absorption peak of C-Cl appears at 710 cm -1 ; in the infrared spectrum of the inorganic modified additive, an absorption peak of the ether bond C-O-C appears at 1030 cm -1 , an absorption peak of the carbon-hydrogen bond in the benzene ring appears at 3066 cm -1 , an absorption peak of the carbon-hydrogen bond in the carbon-carbon double bond appears at 3011 cm -1 , an absorption peak of the ester group C=O appears at 1735 cm -1 , and the absorption peak of the ester group is enhanced.

[0041] II. Preparation of Ink

[0042] (1) Add 15 g of styrene, 30 g of butyl acrylate, 15 g of methyl methacrylate, and 10 g of methacrylic acid to a mixer, stir and mix at a rate of 300 r / min for 10 min to obtain a mixed monomer; mix 8 g of BEM (dodecyl polyoxyethylene ether methacrylate), 5 g of methyl methacrylate, and 5 g of deionized water evenly to obtain a BEM mixed solution; disperse 0.5 g of ammonium persulfate in 15 g of deionized water to obtain an initiator solution;

[0043] (2) Place 0.5 g of sodium dodecylbenzenesulfonate and 55 g of deionized water in a reaction kettle, stir evenly by mechanical stirring, add the mixed monomers, mix well, continue to add the BEM mixed solution and 0.2 g of n-dodecyl mercaptan to the kettle, and continue stirring for 45 min to obtain an emulsion.

[0044] (3) Add 0.5 g of sodium dodecylbenzenesulfonate and 40 g of deionized water to the reaction kettle, stir evenly by mechanical stirring, control the temperature in the kettle at 70 °C, add 10 g of styrene, 10 g of methyl methacrylate and 5% of the mass of the initiator solution, and stir while maintaining the temperature for 10 min to obtain a polystyrene seed emulsion.

[0045] (4) Add 30 g of deionized water to the reaction kettle, raise the temperature to 80 °C, add the polystyrene seed emulsion obtained in step (3), stir for 5 min, add 25% of the mass of the initiator solution, continue to stir for 5 min, then add the emulsion obtained in step (2), 4 g of inorganic modification additive and the remaining initiator solution, and stir while maintaining the temperature for 1 h to obtain a mixed material.

[0046] (5) Add 8 g of titanium dioxide, 1 g of tributyl phosphate and 1 g of polyethylene glycol to the mixed material. After adding, adjust the rotation speed to 600 r / min, stir and mix for 15 min, then let it stand for 10 min, and discharge to obtain the ink.

[0047] Example 2

[0048] Preparation of Ink

[0049] (1) Add 20 g of styrene, 35 g of butyl acrylate, 20 g of methyl methacrylate and 15 g of methacrylic acid to a mixer, stir and mix at a rate of 400 r / min for 20 min to obtain mixed monomers; mix 12 g of BEM (dodecyl polyoxyethylene ether methacrylate), 7 g of methyl methacrylate and 9 g of deionized water evenly to obtain a BEM mixed solution; disperse 1 g of ammonium persulfate in 20 g of deionized water to obtain an initiator solution.

[0050] (2) Place 1 g of sodium dodecylbenzenesulfonate and 60 g of deionized water in a reaction kettle, stir evenly by mechanical stirring, add the mixed monomers, mix well, continue to add the BEM mixed solution and 0.6 g of n-dodecyl mercaptan to the kettle, and continue stirring for 50 min to obtain an emulsion.

[0051] (3) Add 0.8 g of sodium dodecylbenzenesulfonate and 45 g of deionized water to the reaction kettle, stir evenly by mechanical stirring, control the temperature in the kettle at 80 °C, add 12 g of styrene, 15 g of methyl methacrylate and 10% of the mass of the initiator solution, and stir while maintaining the temperature for 15 min to obtain a polystyrene seed emulsion.

[0052] (4) Add 35 g of deionized water to the reaction kettle, raise the temperature to 85 °C, add the polystyrene seed emulsion obtained in step (3), stir for 5 - 10 min, add 30% of the mass of the initiator solution, continue stirring for 8 min, then add the emulsion obtained in step (2), 7 g of inorganic modification additive and the remaining initiator solution, keep warm and stir for 1.5 h to obtain a mixed material;

[0053] (5) Add 10 g of titanium dioxide, 1.5 g of tributyl phosphate and 2 g of polyethylene glycol to the mixed material. After adding, adjust the rotation speed to 800 r / min, stir and mix for 20 min, then let it stand for 15 min, and discharge to obtain the ink.

[0054] The preparation method of the inorganic modification additive is the same as that in Example 1.

[0055] Example 3

[0056] Preparation of Ink

[0057] (1) Add 25 g of styrene, 40 g of butyl acrylate, 25 g of methyl methacrylate, and 20 g of methacrylic acid to a mixer, stir and mix at a rate of 500 r / min for 30 min to obtain a mixed monomer; mix 15 g of BEM (dodecyl polyoxyethylene ether methacrylate), 10 g of methyl methacrylate and 10 g of deionized water evenly to obtain a BEM mixed solution; disperse 1.5 g of ammonium persulfate in 25 g of deionized water to obtain an initiator solution;

[0058] (2) Place 1.5 g of sodium dodecylbenzenesulfonate and 65 g of deionized water in the reaction kettle, stir mechanically and evenly, add the mixed monomer, mix well, continue to add the BEM mixed solution and 0.8 g of n-dodecyl mercaptan to the kettle, and continue stirring for 55 min to obtain an emulsion;

[0059] (3) Add 1 g of sodium dodecylbenzenesulfonate and 50 g of deionized water to the reaction kettle, stir mechanically and evenly, control the temperature in the kettle at 90 °C, add 15 g of styrene, 20 g of methyl methacrylate and 15% of the mass of the initiator solution, keep warm and stir for 20 min to obtain a polystyrene seed emulsion;

[0060] (4) Add 40 g of deionized water to the reaction kettle, raise the temperature to 90 °C, add the polystyrene seed emulsion obtained in step (3), stir for 10 min, add 35% of the mass of the initiator solution, continue stirring for 10 min, then add the emulsion obtained in step (2), 8 g of inorganic modification additive and the remaining initiator solution, keep warm and stir for 2 h to obtain a mixed material;

[0061] (5) Add 12 g of titanium dioxide, 2 g of tributyl phosphate, and 3 g of polyethylene glycol to the mixed material. After adding, adjust the rotation speed to 900 r / min, stir and mix for 25 min, then let it stand for 20 min, and discharge to obtain the ink.

[0062] The preparation method of the inorganic modified additive is the same as that in Example 1.

[0063] Comparative Example 1

[0064] Preparation of Ink

[0065] (1) Add 20 g of styrene, 35 g of butyl acrylate, 20 g of methyl methacrylate, and 15 g of methacrylic acid to a mixer, and stir and mix at a rate of 400 r / min for 20 min to obtain a mixed monomer; mix 12 g of BEM (dodecyl polyoxyethylene ether methacrylate), 7 g of methyl methacrylate, and 9 g of deionized water evenly to obtain a BEM mixed solution; disperse 1 g of ammonium persulfate in 20 g of deionized water to obtain an initiator solution.

[0066] (2) Place 1 g of sodium dodecylbenzenesulfonate and 60 g of deionized water in a reaction kettle, stir mechanically until evenly mixed, add the mixed monomer, mix well, then continue to add the BEM mixed solution and 0.6 g of n-dodecyl mercaptan to the kettle, and continue to stir for 50 min to obtain an emulsion.

[0067] (3) Add 0.8 g of sodium dodecylbenzenesulfonate and 45 g of deionized water to the reaction kettle, stir mechanically until evenly mixed, control the temperature in the kettle at 80 °C, add 12 g of styrene, 15 g of methyl methacrylate, and 10% of the initiator solution, and keep stirring for 15 min to obtain a polystyrene seed emulsion.

[0068] (4) Add 35 g of deionized water to the reaction kettle, raise the temperature to 85 °C, add the polystyrene seed emulsion obtained in step (3), stir for 5 - 10 min, add 30% of the initiator solution, continue to stir for 8 min, then add the emulsion obtained in step (2), 7 g of nano-zinc oxide with an average particle size of 4 μm, and the remaining initiator solution, and keep stirring at a constant temperature for 1.5 h to obtain a mixed material.

[0069] (5) Add 10 g of titanium dioxide, 1.5 g of tributyl phosphate, and 2 g of polyethylene glycol to the mixed material. After adding, adjust the rotation speed to 800 r / min, stir and mix for 20 min, then let it stand for 15 min, and discharge to obtain the ink.

[0070] Comparative Example 2

[0071] Preparation of Ink

[0072] (1) Add 20 g of styrene, 35 g of butyl acrylate, 20 g of methyl methacrylate, and 15 g of methacrylic acid to a mixer, and stir and mix at a rate of 400 r / min for 20 min to obtain a mixed monomer; mix 12 g of BEM (dodecyl polyoxyethylene ether methacrylate), 7 g of methyl methacrylate, and 9 g of deionized water evenly to obtain a BEM mixed solution; disperse 1 g of ammonium persulfate in 20 g of deionized water to obtain an initiator solution;

[0073] (2) Place 1 g of sodium dodecylbenzenesulfonate and 60 g of deionized water in a reaction kettle, stir mechanically until evenly mixed, add the mixed monomer, mix well, continue to add the BEM mixed solution and 0.6 g of n-dodecyl mercaptan to the kettle, and continue to stir for 50 min to obtain an emulsion;

[0074] (3) Add 0.8 g of sodium dodecylbenzenesulfonate and 45 g of deionized water to the reaction kettle, stir mechanically until evenly mixed, control the temperature in the kettle at 80 °C, add 12 g of styrene, 15 g of methyl methacrylate, and 10% of the mass of the initiator solution, and keep stirring for 15 min to obtain a polystyrene seed emulsion;

[0075] (4) Add 35 g of deionized water to the reaction kettle, raise the temperature to 85 °C, add the polystyrene seed emulsion obtained in step (3), stir for 5 - 10 min, add 30% of the mass of the initiator solution, continue to stir for 8 min, then add the emulsion obtained in step (2), 7 g of rosin-based polymeric substance, and the remaining initiator solution, and keep stirring for 1.5 h to obtain a mixed material;

[0076] (5) Add 10 g of titanium dioxide, 1.5 g of tributyl phosphate, and 2 g of polyethylene glycol to the mixed material. After adding, adjust the rotation speed to 800 r / min, stir and mix for 20 min, then let stand for 15 min, and discharge to obtain the ink.

[0077] The preparation method of the rosin-based polymeric substance is the same as that in Example 1.

[0078] Comparative Example 3

[0079] Preparation of Ink

[0080] (1) Add 20 g of styrene, 35 g of butyl acrylate, 20 g of methyl methacrylate, and 15 g of methacrylic acid to a mixer, and stir and mix at a rate of 400 r / min for 20 min to obtain a mixed monomer; mix 12 g of BEM (dodecyl polyoxyethylene ether methacrylate), 7 g of methyl methacrylate, and 9 g of deionized water evenly to obtain a BEM mixed solution; disperse 1 g of ammonium persulfate in 20 g of deionized water to obtain an initiator solution;

[0081] (2) Place 1 g of sodium dodecylbenzenesulfonate and 60 g of deionized water in a reaction kettle, stir evenly by mechanical stirring, add the mixed monomers, mix well, continue to add the BEM mixed solution and 0.6 g of n-dodecyl mercaptan to the kettle, and continue stirring for 50 min to obtain an emulsion;

[0082] (3) Add 0.8 g of sodium dodecylbenzenesulfonate and 45 g of deionized water to the reaction kettle, stir evenly by mechanical stirring, control the temperature in the kettle at 80 °C, add 12 g of styrene, 15 g of methyl methacrylate and 10% of the mass of the initiator solution, and keep stirring for 15 min to obtain a polystyrene seed emulsion;

[0083] (4) Add 35 g of deionized water to the reaction kettle, raise the temperature to 85 °C, add the polystyrene seed emulsion obtained in step (3), stir for 5 - 10 min, add 30% of the mass of the initiator solution, continue stirring for 8 min, then add the emulsion obtained in step (2) and the remaining initiator solution, and keep stirring for 1.5 h to obtain a mixed material;

[0084] (5) Add 10 g of titanium dioxide, 1.5 g of tributyl phosphate and 2 g of polyethylene glycol to the mixed material. After adding, adjust the rotation speed to 800 r / min, stir and mix for 20 min, then let it stand for 15 min, and discharge to obtain the ink.

[0085] Performance testing:

[0086] Evenly coat the inks prepared in Examples 1 - 3 and Comparative Examples 1 - 3 on the surface of a glass cover plate to make samples that meet the specifications. After thorough drying, conduct performance tests. Conduct adhesion tests on the samples according to GB / T 5210 - 2006 "Paints and varnishes - Pull-off adhesion test"; Conduct according to the provisions of Method A in GB / T 2410 - 2008 "Determination of light transmittance and haze of transparent plastics". The light source is a C light source. First, test the light transmittance of the glass cover plate without coating the ink, make marks around the test area, then evenly coat the ink on the surface of the glass cover plate, and test the light transmittance of the glass cover plate and the ink layer in the test area. Calculate the light transmittance of the ink layer according to the formula T = 100 - T1 + T2, where T is the light transmittance of the ink layer, %; T1 is the light transmittance of the glass cover plate without coating the ink, %; T2 is the light transmittance of the glass cover plate and the ink layer, %. The specific test results are shown in Table 1:

[0087] Table 1 - Performance testing

[0088] Adhesion force (MPa) Light transmittance (%) Example 1 12 93.8 Example 2 14 98.3 Example 3 13 96.4 Comparative example 1 5 88.1 Comparative example 2 9 82.5 Comparative example 3 4 81.9

[0089] From the test results in Table 1, it can be seen that the samples prepared in Examples 1 to 3 have good light transmittance and high adhesion; in the sample prepared in Comparative Example 1, zinc oxide is used to replace the inorganic modified additive. Compared with the examples, the adhesion of the sample is relatively poor. This may be because without organic modification, nano-zinc oxide agglomerates in the matrix, resulting in a decrease in the light transmittance of the sample; in the sample prepared in Comparative Example 2, a rosin-based polymeric substance is used to replace the inorganic modified additive. Compared with the examples, the light transmittance of the sample is relatively poor, probably because it cannot crosslink with the matrix, resulting in a decrease in the adhesion of the sample; in the sample prepared in Comparative Example 3, no inorganic modified additive is added, so the light transmittance and adhesion of the sample are both the worst.

[0090] The above content is only an example and illustration of the concept of the present invention. Those skilled in the art of the present technology can make various modifications or supplements to the described specific embodiments or use similar methods for substitution. As long as they do not deviate from the concept of the invention or exceed the scope defined by this claims, they should all fall within the protection scope of the present invention.

Claims

1. A method for preparing a functional ink for a glass cover plate, characterized in that: The ink comprises the following raw materials in parts by weight: 25-40 parts of styrene, 30-40 parts of butyl acrylate, 30-55 parts of methyl methacrylate, 10-20 parts of methacrylic acid; 8-15 parts of BEM, wherein the BEM is behenyl polyoxyethylene ether methacrylate, 145-190 parts of deionized water, 1-2.5 parts of initiator, 0.5-1.5 parts of emulsifier, 0.2-0.8 parts of chain transfer agent, 4-8 parts of inorganic modified additives, 8-12 parts of pigment, 1-2 parts of tributyl phosphate, and 1-3 parts of polyethylene glycol; The preparation method comprises the following steps: (1) Add styrene, butyl acrylate, methyl methacrylate and methacrylic acid into a mixer, stir and mix at a rate of 300 to 500 r / min for 10 to 30 minutes to obtain a mixed monomer; mix BEM, methyl methacrylate and deionized water evenly to obtain a BEM mixed solution; disperse an initiator in deionized water to obtain an initiator solution; (2) Place the emulsifier and deionized water in a reaction kettle, stir mechanically to obtain an emulsion, add the mixed monomer, mix well, continue to add the BEM mixed solution and chain transfer agent to the kettle, continue stirring for 45 to 55 minutes, and obtain an emulsion; (3) Add an emulsifier and deionized water to a reaction kettle, stir mechanically to obtain a uniform mixture, control the temperature in the kettle to 70 to 90° C., add styrene, methyl methacrylate and 5% to 15% by weight of an initiator solution, and stir at this temperature for 10 to 20 minutes to obtain a polystyrene seed emulsion; (4) Add deionized water to the reaction kettle, raise the temperature to 80-90° C., add the polystyrene seed emulsion obtained in step (3), stir for 5-10 min, add 25%-35% by weight of the initiator solution, continue stirring for 5-10 min, add the emulsion obtained in step (2), the inorganic modified additive and the remaining initiator solution, keep warm and stir for 1-2 h, and obtain a mixed material; (5) Add the pigment, tributyl phosphate and polyethylene glycol to the mixed material. After the addition is completed, adjust the rotation speed to 600-900 r / min, stir and mix for 15-25 minutes, let it stand for 10-20 minutes, and discharge the material to obtain ink; The preparation method of the inorganic modified additive comprises the following steps: S1: Add nano zinc oxide to deionized water, perform ultrasonic treatment to form a uniform dispersion, add 2-chloroacrylic acid and catalyst A to the dispersion under nitrogen protection, raise the system temperature to 90-95°C under stirring conditions, keep the temperature for 5-8 hours, filter and separate the solid material, wash and dry it, and obtain modified nano zinc oxide; S2: Ultrasonic dispersion of modified nano zinc oxide in dimethyl sulfoxide to form a dispersion, adding rosin-based polymeric material and catalyst B to the dispersion under continuous nitrogen conditions, mixing, raising the temperature to 70-80° C., stirring at this temperature for 4-8 hours, then filtering, collecting the product, washing the product, and drying it to obtain an inorganic modified additive; The preparation method of the rosin-based polymeric material comprises the following steps: Maleic rosin and N,N-dimethylformamide are added to a nitrogen-protected reactor, and after stirring evenly, hydroquinone dihydroxyethyl ether and p-toluenesulfonic acid are continuously added to the reactor. After the addition is completed, heating is turned on until the temperature in the reactor reaches 90-95°C, and the reaction mixture is stirred for 4-6 hours. The solvent is removed by reduced pressure distillation to obtain a rosin-based polymeric substance.

2. The method for preparing a functional ink for a glass cover plate according to claim 1, characterized in that: The initiator is ammonium persulfate; the emulsifier is sodium dodecylbenzene sulfonate; and the chain transfer agent is n-dodecyl mercaptan.

3. The method for preparing a functional ink for a glass cover plate according to claim 1, characterized in that: In step S1, the average particle size of the nano zinc oxide is 4 μm.

4. The method for preparing a functional ink for a glass cover plate according to claim 1, characterized in that: In step S1, the catalyst A is any one of p-toluenesulfonic acid, trifluoromethanesulfonic acid or aminosulfonic acid.

5. The method for preparing a functional ink for a glass cover plate according to claim 1, characterized in that: In step S1, the mass ratio of the nano zinc oxide to 2-chloroacrylic acid is 1:0.1-0.

3.

6. The method for preparing a functional ink for a glass cover plate according to claim 1, characterized in that: In step S2, the catalyst B is any one of pyridine or triethylamine.

7. The method for preparing a functional ink for a glass cover plate according to claim 1, characterized in that: The pigment is any one of pigment yellow 14, phthalocyanine blue B, magenta 8B, carbon black or titanium dioxide.

8. A functional ink for a glass cover plate, characterized in that: The method is as claimed in claim 1.

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