High adhesion water-based ink and method for preparing the same

Abstract

The application belongs to the technical field of water-based ink preparation, and provides a high-adhesion water-based ink and a preparation method thereof; due to the strong chemical inertness of melamine resin, the adhesion performance of ordinary water-based ink is limited, the pyrophosphoric acid ester-silane copolymer is obtained by first preparing the pyrophosphoric acid ester through the reaction of phosphorus pentoxide and a polyhydroxy compound, and then introducing a silane compound and a multifunctional compound for copolymerization; then, the water-based nano dispersion liquid is prepared through the sol-gel method, the dispersion stability is regulated by introducing a dispersant and deionized water with metal organic compounds such as silicon, zirconium and aluminum as precursors, and the emulsion containing a plurality of functional monomer structures is prepared through the emulsion polymerization method; finally, the emulsion is mixed with components such as pigments, functional additives, the pyrophosphoric acid ester-silane copolymer and the water-based nano dispersion liquid, and the water-based ink with excellent adhesion is prepared through aging and filtration.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of water-based ink preparation and relates to a high-adhesion water-based ink and a preparation method thereof. BACKGROUND

[0002] Melamine resin is an amino resin formed by the polycondensation of melamine and formaldehyde, can resist high temperature to a certain extent, and has high hardness and rigidity, and is widely used in kitchen utensils, furniture veneer, fire-resistant plates and other fields, has certain resistance to general chemicals, and has good electrical insulation performance. Therefore, melamine resin has mature and wide application in home decoration plates, table surface wear-resistant coatings, daily necessities, electronic device packaging and the like. However, due to the surface properties of melamine resin, which exhibit a certain degree of chemical inertness and high cross-linking density, high requirements are put forward for the adhesion of subsequent ink or coating. When a melamine resin substrate is subjected to pattern printing or surface decoration, traditional ink, mainly solvent-based ink, generally faces the problem that due to the dense surface of melamine resin, the traditional solvent-based ink often has difficulty in obtaining sufficient interfacial bonding force after drying, and peeling, ink dropping and other problems are prone to occur; meanwhile, traditional ink mostly uses organic solvents as volatile carriers, and a large amount of volatile organic compounds will be released in the production and use process, which has potential harm to the environment and human health.

[0003] At this time, water-based ink gradually attracts the attention of the industry and is applied more and more widely in packaging printing, building decoration, consumer electronics and other fields. Compared with solvent-based ink, water-based ink replaces most organic solvents with water, significantly reducing the emission of volatile organic compounds. Although water-based ink has many advantages such as environmental protection and low toxicity, its application on melamine resin still has certain shortcomings. The film-forming mechanism of water-based ink is different from that of traditional solvent-based ink, and the surface energy of melamine resin is low and the chemical inertness is strong. The adhesion performance of ordinary water-based ink on such high-crosslinking substrates is limited, and the surface coating is prone to fall off or be damaged under the action of frequent cleaning, friction or external force. SUMMARY

[0004] In view of the deficiencies of the prior art, the purpose of the present application is to provide a high-adhesion water-based ink and a preparation method thereof. The present application first prepares pyrophosphoric acid ester by the reaction of phosphorus pentoxide and polyhydroxy compound, and further introduces silane compound and polyfunctional compound for copolymerization to form pyrophosphoric acid ester-silane copolymer. Secondly, the water-based nano dispersion liquid is prepared by sol-gel method. Through the hydrolysis and polycondensation reaction of metal organic compound, combined with the stabilizing effect of dispersant, the nano particle dispersion liquid with uniform particle size and good dispersibility is formed. In addition, the emulsion containing various functional monomers is prepared by emulsion polymerization method, which improves the adhesion of the emulsion. Finally, the pyrophosphoric acid ester-silane copolymer, water-based nano dispersion liquid, functional emulsion, pigment, and other components are mixed, aged and filtered to prepare a high-adhesion water-based ink, thereby meeting the needs of actual production.

[0005] To achieve this purpose, the present application adopts the following technical solutions:

[0006] In a first aspect, the present application provides a preparation method of a high-adhesion water-based ink, which comprises:

[0007] S1, mixing phosphorus pentoxide and glycerol to obtain pyrophosphoric acid ester, then adding silane premix liquid to the pyrophosphoric acid ester, stirring, and adding trimethylolpropane to obtain pyrophosphoric acid ester-silane copolymer;

[0008] S2, mixing tetraethoxysilane, tetra-n-butoxyzirconium, acetylacetone aluminum, acetylacetone, and anhydrous ethanol to obtain a precursor liquid, then mixing acetic acid solution, the precursor liquid, and a dispersant to obtain an alcohol phase, mixing deionized water and the alcohol phase, stirring, and filtering to obtain a water-based nano dispersion liquid;

[0009] S3, mixing methyl methacrylate, butyl acrylate, acrylic acid, diacetone acrylamide, hydroxyethyl methacrylate, styrene, and glycidyl methacrylate with an emulsifier, then adding to sodium bicarbonate solution to obtain a pre-emulsion, mixing 1 / 10 of the pre-emulsion mass with 1 / 3 of the ammonium persulfate solution mass to react, then adding the remaining pre-emulsion and ammonium persulfate solution to continue the reaction, and adding adipic acid dihydrazide solution to stir to obtain an emulsion;

[0010] S4, mixing the emulsion, pigment paste, leveling agent, and defoaming agent uniformly, then adding pyrophosphoric acid ester-silane copolymer, water-based nano dispersion liquid, mica powder, and film-forming aid, mixing uniformly, standing for aging, and filtering to obtain a high-adhesion water-based ink.

[0011] Specifically includes:

[0012] S1, mixing phosphorus pentoxide with glycerol, adjusting the temperature to the first temperature, stirring the reaction, obtaining pyrophosphate, then adding silane premix to the pyrophosphate, keeping the first temperature, continuing to stir and adding trimethylolpropane, continuing to stir at the first temperature, obtaining pyrophosphate-silane copolymer;

[0013] S2, mixing tetraethoxysilane, tetra-n-butoxyzirconium, acetylacetone aluminum, acetylacetone with anhydrous ethanol to obtain a precursor solution, then mixing acetic acid solution, precursor solution and dispersant to obtain an alcohol phase, mixing deionized water with the alcohol phase, stirring, filtering to obtain an aqueous nanodispersion;

[0014] S3, mixing methyl methacrylate, butyl acrylate, acrylic acid, diacetone acrylamide, hydroxyethyl methacrylate, styrene, glycidyl methacrylate with emulsifier, then adding to sodium bicarbonate solution, mixing uniformly to obtain pre-emulsion, mixing 1 / 10 of the mass of the pre-emulsion with 1 / 3 of the mass of ammonium persulfate solution, adjusting the temperature to the second temperature, reacting in a nitrogen atmosphere, then adding the remaining pre-emulsion and ammonium persulfate solution to continue the reaction, adjusting the temperature to 60°C, adding adipic acid dihydrazide solution, stirring, adjusting the pH to 8-8.5, filtering to obtain an emulsion;

[0015] S4, mixing the emulsion, pigment paste, leveling agent, defoaming agent, then adding pyrophosphate-silane copolymer, aqueous nanodispersion, mica powder and film-forming aid, mixing uniformly, standing for aging and filtering to obtain a high adhesion water-based ink.

[0016] Phosphorus pentoxide and glycerol form pyrophosphate through esterification reaction. The phosphate groups in the pyrophosphate molecule have strong polarity, which can form a tight interfacial bond with the amino groups on the surface of melamine resin through coordination or hydrogen bonding, thereby enhancing the anchoring ability of the ink to the substrate. The subsequent introduction of the silane component generates active silicon hydroxyl groups through hydrolysis. These silicon hydroxyl groups undergo condensation reaction with the hydroxyl groups in the pyrophosphate, forming a stable silicon-oxygen-phosphorus bond network. At the same time, the organic functional groups (such as epoxy or amino) at the end of the silane molecule provide reaction sites for subsequent chemical crosslinking with the ink resin. The addition of trimethylolpropane regulates the silane chain through its multi-hydroxyl structure, inhibiting the rigidity of the molecule caused by excessive condensation, while introducing flexible side chains to balance the interfacial bonding force and film-forming flexibility of the copolymer, achieving gradient chemical bonding from the surface of the substrate to the ink coating.

[0017] In S2, the composite oxide nanoparticle dispersion system is constructed by the synergistic hydrolysis and condensation reaction of the multi-metallic precursor. The hydrolysis of the alkoxides of silicon, zirconium and aluminum in alcohol solution generates the corresponding metal hydroxyl intermediates. The alkoxide of silicon is first hydrolyzed to form silicon hydroxyl, which has moderate reactivity and forms a stable silicon-oxygen network skeleton; the alkoxide of zirconium has a higher metal electropositivity and a faster hydrolysis rate, but the chelation of acetylacetone stabilizes the zirconium ions and inhibits the rapid condensation reaction, avoiding the formation of large-size agglomerates. The alkoxide of aluminum is hydrolyzed to form aluminum hydroxyl intermediates under the synergistic regulation of acetylacetone, and the condensation process tends to form a sheet structure with rich edge hydroxyl groups, providing heterogeneous nucleation sites for the subsequent hybrid network. The dispersant molecules are adsorbed on the surface of the newly formed nanoparticles through the polar anchoring group, and the long-chain hydrophilic part extends outward to form a steric hindrance layer, effectively blocking the van der Waals force and hydrogen bond interaction between particles. Under acidic catalytic conditions, directional condensation occurs between silicon hydroxyl and zirconium hydroxyl, aluminum hydroxyl, forming a core-shell structure with silicon-oxygen network as the continuous phase and zirconium-oxygen and aluminum-oxygen clusters as the dispersed phase. The silicon-oxygen network provides colloidal stability, the zirconium-oxygen clusters enhance the surface reactivity, and the aluminum-oxygen sheet layer strengthens the network crosslinking degree through the bridging effect of the edge hydroxyl groups. When the alcohol phase and the water phase are gradually mixed, the gradient change of solvent polarity induces the dynamic adjustment of the degree of protonation of the particle surface hydroxyl groups, prompting the rearrangement of dispersant molecules at the particle-water interface, forming a three-dimensional stable structure jointly acted by the chemisorption layer and the physical adsorption layer. This synergistic stabilization mechanism of double electric layer and steric hindrance makes the nanoparticles remain in a monodispersed state, and the residual active hydroxyl and epoxy groups on the surface reserve reaction sites for the subsequent chemical bonding of the ink resin, finally realizing the uniform distribution of the nano-filler in the coating and the interface strengthening effect.

[0018] The rigid segments of methyl methacrylate and the flexible segments of butyl acrylate form a gradient copolymer backbone through free radical polymerization, which endows the coating with a balanced mechanical property. The carboxyl groups of acrylic acid are partially exposed on the surface of latex particles during polymerization, which form a preliminary adsorption with the polar groups of melamine resin through hydrogen bonds, and also provide charge stabilization for the dispersion of subsequent nanofillers. The ketone carbonyl groups of diacetone acrylamide form potential crosslinking sites inside the latex particles, which combine with the hydrazine groups added later through dynamic covalent bonds to construct a reversible crosslinking network, enhancing the solvent resistance and deformation recovery ability of the coating. The epoxy groups of glycidyl methacrylate are enriched on the latex particle-water interface, which undergo ring-opening reaction with the amino groups on the surface of melamine resin to form a covalent bond anchoring layer, and its hydrophobic property also regulates the surface wetting behavior of the latex particles, promoting the spreading and penetration of the coating on the substrate. The introduction of styrene strengthens the compactness of the latex particles through π-π stacking, while the hydroxyl functional monomer optimizes the film-forming continuity of the emulsion through intermolecular hydrogen bonds. The low-temperature post-addition strategy of the crosslinking agent avoids the uncontrolled pre-crosslinking during polymerization, ensuring the selective formation of ketone-hydrazine dynamic bonds during the curing stage of the coating, and finally obtaining a three-dimensional network structure with rigid support and elastic energy dissipation properties, which ensures the interfacial durability of the ink under complex stress.

[0019] On the interface bonding level, the pyrophosphate group and the amino group on the surface of melamine resin form a directional electron pair sharing through coordination, and the strong electronegativity of the phosphate group attracts the lone pair electrons of the amino group to form a local electron cloud rearrangement chemical anchoring point; at the same time, the silicon hydroxyl groups generated by the hydrolysis of the silane component and the hydroxyl groups on the surface of the substrate form a continuous siloxane bond network through condensation reaction, which expands the discrete anchoring points into a three-dimensional chemical bridging layer throughout the interface. This dual-mechanism interface bonding not only overcomes the limitations of a single force, but also the high-strength covalent bond bears the main load, and the reversible coordination bond buffers the stress impact through dynamic dissociation-recombination during deformation.

[0020] The introduction of nano-hybrid particles forms a multiphase reinforcement system inside the coating. The continuous network of silica provides a rigid skeleton for the coating, and the surface enriched zirconium-oxygen clusters form a coordination bond with the carboxyl and epoxy groups in the emulsion through Lewis acid sites, forming an inorganic-organic interface transition layer. The sheet-like structure of alumina is crosslinked with the silica network through edge hydroxyl groups, forming an interlocking structure at the nanoscale and inhibiting crack propagation in a single direction. The ketone-hydrazine dynamic bond in the emulsion system forms reversible crosslinking points in the coating body, and its breaking-reforming characteristics give the material self-repairing ability. The covalent bond between the epoxy group and the amino group in the interface region builds a permanent connection, forming a gradual bonding strength distribution from the substrate to the coating. The core-shell structure of the latex particle is designed by the modulus gradient of the rigid core and the elastic shell. The rigid core maintains the overall morphology of the coating, and the elastic shell absorbs the deformation energy through the stretching and shrinking of the molecular chain. The electrostatic repulsion of the carboxyl group and the synergistic control of the surface charge of the nanoparticles form a double steric hindrance effect, which not only prevents the filler from settling but also optimizes the rheological properties. The layered structure of the mica sheet is arranged in the coating in the direction parallel to the substrate, and the silica skeleton and the pyrophosphate-silane network form a chemical bond through the condensation reaction of the edge hydroxyl groups. The nanoparticles between the layers fill the microvoids and form a dense physical barrier layer.

[0021] As a preferred technical solution of the present application, in S1, the mass ratio of the phosphorus pentoxide, glycerol, silane premix solution and trimethylolpropane is (70-73):(92-97):300:(10-14), for example, it can be (70.0, 70.3, 70.6, 70.9, 71.2, 71.5, 71.8, 72.1, 72.4, 72.7 or 73.0):(92.0, 92.5, 93.0, 93.5, 94.0, 94.5, 95.0, 95.5, 96.0, 96.5 or 97.0):300:(10.0, 10.4, 10.8, 11.2, 11.6, 12.0, 12.4, 12.8, 13.2, 13.6 or 14.0), but not limited to the listed values, other unlisted values within this range are also applicable.

[0022] In some optional examples, the silane premix solution is (3-glycidylpropoxy)trimethoxysilane, (3-aminopropyl)triethoxysilane and anhydrous ethanol, with a mass ratio of 4:1:5.

[0023] In some optional examples, the first temperature is 60-65℃, for example, it can be 60.0℃, 60.5℃, 61.0℃, 61.5℃, 62.0℃, 62.5℃, 63.0℃, 63.5℃, 64.0℃, 64.5℃ or 65.0℃, but not limited to the listed values, other unlisted values within this range are also applicable.

[0024] In some optional examples, the stirring time is 3-4h, for example, it can be 3.0h, 3.1h, 3.2h, 3.3h, 3.4h, 3.5h, 3.6h, 3.7h, 3.8h, 3.9h or 4.0h, but not only limited to the listed values, other values not listed in the range are also applicable.

[0025] In some optional examples, the stirring time is 2-3h, for example, it can be 2.0h, 2.1h, 2.2h, 2.3h, 2.4h, 2.5h, 2.6h, 2.7h, 2.8h, 2.9h or 3.0h, but not only limited to the listed values, other values not listed in the range are also applicable.

[0026] As a preferred technical solution of the present application, in S2, the mass ratio of tetraethoxysilane, tetra-n-butoxyzirconium, aluminum acetylacetonate, acetylacetone, anhydrous ethanol, acetic acid solution, dispersant and deionized water is (70-75):(20-23):(10-13):(5-7):130:(32-35):3:(100-120), for example, it can be (70.0, 70.5, 71.0, 71.5, 72.0, 72.5, 73.0, 73.5, 74.0, 74.5 or 75.0):(20.0, 20.3, 20.6, 20.9, 21.2, 21.5, 21.8, 22.1, 22.4, 22.7 or 23.0):(10.0, 10.3, 10.6, 10.9, 11.2, 11.5, 11.8, 12.1, 12.4, 12.7 or 13.0):(5.0, 5.2, 5.4, 5.6, 5.8, 6.0, 6.2, 6.4, 6.6, 6.8 or 7.0):130:(32.0, 32.3, 32.6, 32.9, 33.2, 33.5, 33.8, 34.1, 34.4, 34.7 or 35.0):3:(100, 102, 104, 106, 108, 110, 112, 114, 116, 118 or 120), but not only limited to the listed values, other values not listed in the range are also applicable.

[0027] In some optional examples, the mass ratio of glacial acetic acid to deionized water in the acetic acid solution is 3:5.

[0028] In some optional examples, the dispersant is BYK-2012.

[0029] As a preferred technical solution of the present application, in S3, the mass ratio of methyl methacrylate, butyl acrylate, acrylic acid, diacetone acrylamide, hydroxyethyl methacrylate, styrene, glycidyl methacrylate, emulsifier, sodium bicarbonate solution, ammonium persulfate solution and adipic acid dihydrazide solution is (210-215):(150-155):(18-20):(30-33):(24-26):(108-113):(30-33):(12-15):(20-22):60:14, for example, it can be (210.0, 210.5, 211.0, 211.5, 212.0, 212.5, 213.0, 213.5, 214.0 or 214.5, 215.0):(150.0, 150.5, 151.0, 151.5, 152.0, 152.5, 153.0, 153.5, 154.0 or 154.5, 155.0):(18.0, 18.2, 18.4, 18.6, 18.8, 19.0, 19.2, 19.4, 19.6, 19.8 or 20.0):(30.0, 30.3, 30.6, 30.9, 31.2, 31.5, 31.8, 32.1, 32.4, 32.7 or 33.0):(24.0, 24.2, 24.4, 24.6, 24.8, 25.0, 25.2, 25.4, 25.6, 25.8 or 26.0):(108.0, 108.5, 109.0, 109.5, 110.0, 110.5, 111.0, 111.5, 112.0, 112.5 or 113.0):(30.0, 30.3, 30.6, 30.9, 31.2, 31.5, 31.8, 32.1, 32.4, 32.7 or 33.0):(12.0, 12.3, 12.6, 12.9, 13.2, 13.5, 13.8, 14.1, 14.4, 14.7 or 15.0):(20.0, 20.2, 20.4, 20.6, 20.8, 21.0, 21.2, 21.4, 21.6, 21.8 or 22.0):60:14, but not limited to the listed values, other unlisted values within the range are also applicable.

[0030] In some optional examples, the mass fraction of the sodium bicarbonate solution is 10wt.%.

[0031] In some optional examples, the mass fraction of the ammonium persulfate solution is 2wt.%.

[0032] In some optional examples, the second temperature is 80-85℃, for example, can be 80.0℃, 80.5℃, 81.0℃, 81.5℃, 82.0℃, 82.5℃, 83.0℃, 83.5℃, 84.0℃, 84.5℃ or 85.0℃, but not only limited to the listed values, other values in the range of values are also applicable.

[0033] In some optional examples, the time of the second temperature reaction is 1-2h, for example, can be 1.0h, 1.1h, 1.2h, 1.3h, 1.4h, 1.5h, 1.6h, 1.7h, 1.8h, 1.9h or 2.0h, but not only limited to the listed values, other values in the range of values are also applicable.

[0034] In some optional examples, the time of the continued reaction is 4-5h, for example, can be 4.0h, 4.1h, 4.2h, 4.3h, 4.4h, 4.5h, 4.6h, 4.7h, 4.8h, 4.9h or 5.0h, but not only limited to the listed values, other values in the range of values are also applicable.

[0035] In some optional examples, the mass ratio of adipic acid dihydrazide to deionized water in the adipic acid dihydrazide solution is 9:5.

[0036] As a preferred technical solution of the present application, in S4, the mass ratio of the emulsion, pigment paste, leveling agent, defoaming agent, pyrophosphate-silane copolymer, aqueous nanodispersion, mica powder and film-forming aid is 100:(15-17):(1-2):(1-2):(5-7):(7-9):(1-2):(2-3), for example, can be 100:(15.0, 15.2, 15.4, 15.6, 15.8, 16.0, 16.2, 16.4, 16.6, 16.8 or 17.0):(1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9 or 2.0):(1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9 or 2.0):(5.0, 5.2, 5.4, 5.6, 5.8, 6.0, 6.2, 6.4, 6.6, 6.8 or 7.0):(7.0, 7.2, 7.4, 7.6, 7.8, 8.0, 8.2, 8.4, 8.6, 8.8 or 9.0):(1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9 or 2.0):(2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9 or 3.0), but not only limited to the listed values, other values in the range of values are also applicable.

[0037] In some optional examples, the leveling agent is 2,4,7,9-tetramethyl-5-decyn-4,7-diol.

[0038] In some optional examples, the preparation method of the mica powder is that mica, KH-550 and ethanol are mixed and ball milled, and the mica powder is obtained by filtration, and the mass ratio of mica to KH-550 is 100:1.

[0039] In some optional examples, the particle size of the mica powder is 5-10 μm, for example, it can be 5.0 μm, 5.5 μm, 6.0 μm, 6.5 μm, 7.0 μm, 7.5 μm, 8.0 μm, 8.5 μm, 9.0 μm, 9.5 μm or 10.0 μm, but is not limited to the listed values, and other values not listed in the range are also applicable.

[0040] In the second aspect, the application provides a high-adhesion water-based ink prepared by the preparation method in the first aspect.

[0041] Compared with the prior art, the application has the following beneficial effects: (1) through the coordination of the pyrophosphate group and the melamine resin amino group, the penetration bonding of the silane condensation network and the synergy of the covalent bond, a multiple chemical bonding network is constructed at the interface, not only breaking through the strength of the traditional single bonding mode, but also realizing stress gradient dissipation through the difference in bond type - the high-strength covalent bond bears the main load, and the dynamic coordination bond buffers the impact through reversible dissociation, thereby improving the anti-peeling ability of the coating under complex stress; (2) the nano-hybrid particles form an interpenetrating structure of rigid inorganic phase and flexible organic phase, and the dense filling effect can block the penetration of corrosive media; at the same time, the Lewis acid sites of the zirconium oxygen cluster passivate the reaction by adsorption, inhibit the chemical corrosion of the coating body by acid / alkali, and the layered orientation of the mica sheet further prolongs the diffusion path of the medium, forming a double protection mechanism with the nanoparticles to improve the adhesion of the ink. DETAILED DESCRIPTION

[0042] The technical solutions of the application will be described in detail below with reference to specific examples. The examples described herein are specific embodiments of the application, which are used to illustrate the concept of the application; all the descriptions are explanatory and exemplary, and should not be understood as limiting the embodiments of the application and the protection scope of the application. In addition to the examples described herein, those skilled in the art can also employ other technical solutions that are obvious based on the disclosure of the claims and the description of the application, which include technical solutions that make any obvious substitutions and modifications to the examples described herein.

[0043] The chemical reagents used in the examples and comparative examples of the application are all commercially available and are not subjected to any further purification.

[0044] Example 1

[0045] The embodiment provides a high-adhesion water-based ink and a preparation method thereof, and the preparation method specifically comprises the following steps:

[0046] S1, 70g of phosphorus pentoxide is mixed with 92g of glycerol, the temperature is adjusted to 60 DEG C, and stirring reaction is carried out for 3h, to obtain a pyrophosphate, then 300g of a silane premix is added into the pyrophosphate, stirring is carried out for 2h at 60 DEG C, 10g of trimethylolpropane is added, and stirring is continuously carried out at 60 DEG C, to obtain a pyrophosphate-silane copolymer;

[0047] S2, 70g of tetraethoxysilane, 20g of tetra-n-butoxyzirconium, 10g of acetylacetone aluminum, 5g of acetylacetone and 130g of anhydrous ethanol are mixed to obtain a precursor solution, then 32g of an acetic acid solution, the precursor solution and 3g of a dispersant are mixed and stirred for 2h to obtain an alcohol phase, 100g of deionized water is mixed with the alcohol phase, stirring and filtration are carried out, and a water-based nano dispersion is obtained;

[0048] S3, 210g of methyl methacrylate, 150g of butyl acrylate, 18g of acrylic acid, 30g of diacetone acrylamide, 24g of hydroxyethyl methacrylate, 108g of styrene, 30g of glycidyl methacrylate and 12g of an emulsifier are uniformly mixed, then the mixture is added into 20g of a 10wt.% sodium bicarbonate solution, uniform mixing is carried out, to obtain a pre-emulsion, 1 / 10 of the mass of the pre-emulsion is mixed with 1 / 3 of the mass of an ammonium persulfate solution, nitrogen atmosphere is formed, the temperature is adjusted to 80 DEG C, reaction is carried out for 1h, then the remaining pre-emulsion and the ammonium persulfate solution are added, and reaction is continuously carried out for 4h, the temperature is adjusted to 60 DEG C, 14g of an adipic acid dihydrazide solution is added and stirred, the pH is adjusted to 8, and filtration is carried out, to obtain an emulsion;

[0049] S4, 100g of the emulsion, 15g of pigment color paste, 1g of a leveling agent and 1g of a defoaming agent are uniformly mixed, then 5g of the pyrophosphate-silane copolymer, 7g of the water-based nano dispersion, 1g of mica powder and 2g of a film-forming aid are added, uniform mixing is carried out, standing and aging are carried out, and filtration is carried out, to obtain a high-adhesion water-based ink.

[0050] Example 2

[0051] The embodiment provides a high-adhesion water-based ink and a preparation method thereof, and the preparation method specifically comprises the following steps:

[0052] S1, 72g of phosphorus pentoxide is mixed with 97g of glycerol, the temperature is adjusted to 65 DEG C, and stirring reaction is carried out for 4h, to obtain a pyrophosphate, then 300g of a silane premix is added into the pyrophosphate, stirring is carried out for 3h at 65 DEG C, 11g of trimethylolpropane is added, and stirring is continuously carried out at 65 DEG C, to obtain a pyrophosphate-silane copolymer;

[0053] S2, 75 g of tetraethoxysilane, 23 g of tetra-n-butoxyzirconium, 12 g of aluminum acetylacetonate, 6 g of acetylacetone and 130 g of anhydrous ethanol are mixed to obtain a precursor solution, then 33 g of acetic acid solution, the precursor solution and 3 g of dispersant are mixed and stirred for 3 h to obtain an alcohol phase, then 110 g of deionized water is mixed with the alcohol phase, stirred and filtered to obtain an aqueous nanodispersion;

[0054] S3, 215 g of methyl methacrylate, 155 g of butyl acrylate, 20 g of acrylic acid, 33 g of diacetone acrylamide, 26 g of hydroxyethyl methacrylate, 113 g of styrene, 32 g of glycidyl methacrylate and 15 g of emulsifier are uniformly mixed and then added to 22 g of 10 wt.% sodium bicarbonate solution, uniformly mixed to obtain a pre-emulsion, 1 / 10 of the mass of the pre-emulsion is mixed with 1 / 3 of the mass of ammonium persulfate solution, the temperature is adjusted to 84°C under nitrogen atmosphere and reacted for 2 h, then the remaining pre-emulsion and ammonium persulfate solution are added and reacted for 5 h, the temperature is adjusted to 60°C, 14 g of adipic acid dihydrazide solution is added and stirred, the pH is adjusted to 8.2, and the emulsion is filtered to obtain a high adhesion water-based ink.

[0055] S4, 100 g of the emulsion, 17 g of pigment paste, 1.3 g of leveling agent, 1.8 g of defoaming agent are uniformly mixed, then 6 g of pyrophosphate-silane copolymer, 9 g of aqueous nanodispersion, 2 g of mica powder and 3 g of film-forming aid are added, uniformly mixed, allowed to stand and mature, and filtered to obtain a high adhesion water-based ink.

[0056] Example 3

[0057] The present embodiment provides a high adhesion water-based ink and a preparation method thereof, and the preparation method specifically comprises the following steps:

[0058] S1, 73 g of phosphorus pentoxide and 95 g of glycerol are mixed, the temperature is adjusted to 63°C, and stirred and reacted for 3.2 h to obtain a pyrophosphate, then 300 g of silane premix is added to the pyrophosphate, stirred at 63°C for 2.2 h, 14 g of trimethylolpropane is added, and the temperature is continuously maintained at 63°C to obtain a pyrophosphate-silane copolymer;

[0059] S2, 74 g of tetraethoxysilane, 22 g of tetra-n-butoxyzirconium, 13 g of aluminum acetylacetonate, 7 g of acetylacetone and 130 g of anhydrous ethanol are mixed to obtain a precursor solution, then 35 g of acetic acid solution, the precursor solution and 3 g of dispersant are mixed and stirred for 2.3 h to obtain an alcohol phase, then 120 g of deionized water is mixed with the alcohol phase, stirred and filtered to obtain an aqueous nanodispersion;

[0060] S3, 211 g of methyl methacrylate, 152 g of butyl acrylate, 19 g of acrylic acid, 32 g of diacetone acrylamide, 25 g of hydroxyethyl methacrylate, 110 g of styrene, 33 g of glycidyl methacrylate and 14 g of emulsifier were uniformly mixed and then added to 21 g of 10 wt.% sodium bicarbonate solution to obtain a pre-emulsion, 1 / 10 of the mass of the pre-emulsion was mixed with 1 / 3 of the mass of ammonium persulfate solution, the temperature was adjusted to 83°C under a nitrogen atmosphere, and the reaction was carried out for 1.3 h, then the remaining pre-emulsion and ammonium persulfate solution were added and the reaction was continued for 4.3 h, the temperature was adjusted to 60°C, 14 g of adipic acid dihydrazide solution was added and stirred, the pH was adjusted to 8.3, and the emulsion was obtained by filtration;

[0061] S4, 100 g of the emulsion, 16 g of pigment paste, 2.0 g of leveling agent, 1.2 g of defoaming agent were uniformly mixed, then 7 g of pyrophosphate-silane copolymer, 8 g of water-based nano dispersion, 1.3 g of mica powder and 2.2 g of film-forming aid were added, and after uniform mixing, standing, aging and filtration, a high-adhesion water-based ink was obtained.

[0062] Example 4

[0063] The embodiment provides a high-adhesion water-based ink and a preparation method thereof, and the preparation method specifically comprises the following steps:

[0064] S1, 71 g of phosphorus pentoxide and 93 g of glycerol were mixed, the temperature was adjusted to 61°C, and the reaction was stirred for 3.7 h to obtain a pyrophosphate, then 300 g of a silane premix was added to the pyrophosphate, the temperature was maintained at 61°C, and the stirring was continued for 2.6 h, and then 13 g of trimethylolpropane was added, and the stirring was continued at 61°C to obtain a pyrophosphate-silane copolymer;

[0065] S2, 71 g of tetraethoxysilane, 21 g of tetra-n-butoxyzirconium, 11 g of aluminum acetylacetonate, 5.5 g of acetylacetone and 130 g of anhydrous ethanol were mixed to obtain a precursor solution, then 34 g of acetic acid solution, the precursor solution and 3 g of dispersant were mixed and stirred for 2.8 h to obtain an alcohol phase, then 115 g of deionized water was mixed with the alcohol phase, and the water-based nano dispersion was obtained by stirring and filtration;

[0066] S3, 214 g of methyl methacrylate, 154 g of butyl acrylate, 18.5 g of acrylic acid, 31 g of diacetone acrylamide, 24.5 g of hydroxyethyl methacrylate, 112 g of styrene, 31 g of glycidyl methacrylate and 13 g of emulsifier were mixed uniformly and then added to 21.5 g of 10 wt.% sodium bicarbonate solution, mixed uniformly to obtain a pre-emulsion, 1 / 10 of the mass of the pre-emulsion was mixed with 1 / 3 of the mass of the ammonium persulfate solution, the temperature was adjusted to 85°C under a nitrogen atmosphere, and the reaction was carried out for 1.7 h, then the remaining pre-emulsion and ammonium persulfate solution were added and the reaction was continued for 4.8 h, the temperature was adjusted to 60°C, 14 g of adipic acid dihydrazide solution was added and stirred, the pH was adjusted to 8.5, and the emulsion was obtained by filtration;

[0067] S4, 100 g of the emulsion, 15.5 g of pigment paste, 1.7 g of leveling agent, 2.0 g of defoaming agent were mixed uniformly, then 5.5 g of pyrophosphate-silane copolymer, 7.5 g of water-based nano dispersion, 1.7 g of mica powder and 2.6 g of film-forming aid were added, mixed uniformly, then aged and filtered to obtain a high-adhesion water-based ink.

[0068] Comparative Example 1

[0069] This comparative example provides a high-adhesion water-based ink and a preparation method thereof, which is different from Example 1 in that no pyrophosphate-silane copolymer is added in S4, and other process parameters and operating conditions are exactly the same as those of Example 1.

[0070] Comparative Example 2

[0071] This comparative example provides a high-adhesion water-based ink and a preparation method thereof, which is different from Example 1 in that no water-based nano dispersion is added in S4, and other process parameters and operating conditions are exactly the same as those of Example 1.

[0072] Comparative Example 3

[0073] This comparative example provides a high-adhesion water-based ink and a preparation method thereof, which is different from Example 1 in that the adipic acid dihydrazide solution in S3 is 4 g, and other process parameters and operating conditions are exactly the same as those of Example 1.

[0074] Adhesion test method: with melamine resin as the base material, referring to GB / T 13217.7-2009, the adhesion of the ink was determined by the tape method. Water resistance test method: after the printed ink was scraped and dried, a sample strip of 2cm x 10cm was cut, half of the sample strip was soaked in water, and after 24h, it was taken out and dried. The degree of change of the ink sample and the water staining degree were rated; level 1: water stains seriously, the sample color changes seriously; level 2: water stains obviously, the sample color changes obviously; level 3: water stains slightly, the sample color changes slightly; level 4: water stains basically, the sample color changes basically; level 5: water is completely colorless, and the sample is completely colorless. The test results are shown in Table 1.

[0075] Table 1 Test results of high adhesion water-based ink of examples 1-4 and comparative examples 1-3

[0076] Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Adhesion 100％ 100％ 100％ 100％ 82％ 85％ 90％ Water Resistance Level 5 Level 5 Level 5 Level 5 Level 3 Level 3 Level 4

[0077] As shown in Table 1, compared with Example 1, the adhesion and water resistance of Comparative Example 1 were reduced; the adhesion and water resistance of Comparative Example 2 were reduced; the adhesion and water resistance of Comparative Example 3 were reduced. This is because in Example 1, pyrophosphate-silane copolymer is not added, which cannot form a strong polar interface anchor through coordination bond with the amino group on the surface of melamine resin, and lacks the three-dimensional hydrophobic network formed by the condensation of silane to block the penetration of water molecules. The Lewis acid sites on the surface of zirconium oxide are coordinated with the carboxyl groups in the resin, enhancing the inorganic-organic interface bonding, and the dense packing of nano-hybrid particles blocks the diffusion channels of water molecules. In Comparative Example 2, water-based nano-dispersion is not added, which cannot achieve the above effect. Adipic acid dihydrazide dissipates interface stress through reversible breaking-recombination, prevents fatigue fracture of chemical bonds in a humid heat environment, and builds a dynamic crosslinking network that can maintain structural integrity after water absorption, inhibiting the peeling of the coating caused by swelling. In Comparative Example 3, the solution of adipic acid dihydrazide is insufficient, resulting in a decrease in performance.

[0078] The above merely provides a specific implementation of the present application, but the protection scope of the present application is not limited thereto. It should be understood by those skilled in the art that any changes or replacements within the technical scope disclosed by the present application can be easily conceived by those skilled in the art, and all fall within the protection scope and disclosure scope of the present application.

Claims

1. A method for preparing a high-adhesion water-based ink, characterized in that, The preparation method includes: S1, Phosphorus pentoxide and glycerol are mixed and reacted to obtain pyrophosphate. Then, silane premix is ​​added to the pyrophosphate, stirred and trimethylolpropane is added to obtain pyrophosphate-silane copolymer. S2, tetraethoxysilane, tetra-n-butoxyzirconium, aluminum acetylacetonate, acetylacetonate and anhydrous ethanol are mixed to obtain a precursor liquid, then acetic acid solution, precursor liquid and dispersant are mixed to obtain an alcohol phase, then deionized water and alcohol phase are mixed, stirred and filtered to obtain an aqueous nano-dispersion. S3, methyl methacrylate, butyl acrylate, acrylic acid, diacetone acrylamide, hydroxyethyl methacrylate, styrene, glycidyl methacrylate and emulsifier are mixed and added to sodium bicarbonate solution to obtain a pre-emulsion. 1 / 10 of the mass of the pre-emulsion is mixed with 1 / 3 of the mass of ammonium persulfate solution and reacted. The remaining pre-emulsion and ammonium persulfate solution are then added and the reaction continues. Adipic acid dihydrazide solution is added and stirred to obtain an emulsion. S4. Mix emulsion, pigment paste, leveling agent, and defoamer evenly, then add pyrophosphate ester-silane copolymer, aqueous nano-dispersion, mica powder, and film-forming aid. After mixing evenly, let stand to mature and filter to obtain a high-adhesion water-based ink.

2. The method for preparing a high-adhesion water-based ink according to claim 1, characterized in that, In S1, The mass ratio of the phosphorus pentoxide, glycerol, silane premix to trimethylolpropane is (70-73):(92-97):300:(10-14).

3. The method for preparing a high-adhesion water-based ink according to claim 1, characterized in that, In S1, The silane premix is ​​(3-glycidylpropoxy)trimethoxysilane, (3-aminopropyl)triethoxysilane and anhydrous ethanol in a mass ratio of 4:1:

5.

4. The method for preparing a high-adhesion water-based ink according to claim 1, characterized in that, In S2, The mass ratio of the tetraethoxysilane, tetrabutoxyzirconium, aluminum acetylacetonate, acetylacetonate, anhydrous ethanol, acetic acid solution, dispersant and deionized water is (70-75):(20-23):(10-13):(5-7):130:(32-35):3:(100-120); The mass ratio of glacial acetic acid to deionized water in the acetic acid solution is 3:

5.

5. The method for preparing a high-adhesion water-based ink according to claim 1, characterized in that, In S3, The mass ratio of the methyl methacrylate, butyl acrylate, acrylic acid, diacetone acrylamide, hydroxyethyl methacrylate, styrene, glycidyl methacrylate, emulsifier, sodium bicarbonate solution, ammonium persulfate solution and adipic acid dihydrazide solution is (210-215):(150-155):(18-20):(30-33):(24-26):(108-113):(30-33):(12-15):(20-22):60:

14.

6. The method for preparing a high-adhesion water-based ink according to claim 1, characterized in that, In S3, The sodium bicarbonate solution has a mass fraction of 10 wt.%. The mass fraction of the ammonium persulfate solution is 2 wt.%. The mass ratio of adipic acid dihydrazide to deionized water in the adipic acid dihydrazide solution is 9:

5.

7. The method for preparing a high-adhesion water-based ink according to claim 1, characterized in that, In S4, The mass ratio of the emulsion, pigment paste, leveling agent, defoamer, pyrophosphate-silane copolymer, aqueous nano-dispersion, mica powder and film-forming aid is 100:(15-17):(1-2):(1-2):(5-7):(7-9):(1-2):(2-3).

8. The method for preparing a high-adhesion water-based ink according to claim 1, characterized in that, In S4, The leveling agent is 2,4,7,9-tetramethyl-5-decyn-4,7-diol.

9. The method for preparing a high-adhesion water-based ink according to claim 1, characterized in that, In S4, The mica powder is prepared by mixing mica, KH-550 and ethanol, ball milling, and filtering to obtain mica powder. The mass ratio of mica to KH-550 is 100:

1. The mica powder has a particle size of 5-10 μm.

10. A high-adhesion water-based ink is obtained by the preparation method according to any one of claims 1-9.