Sun-proof and scratch-resistant intaglio ink and preparation method thereof

Abstract

This application discloses a light-resistant and scratch-resistant gravure inkjet printing ink and its preparation method, belonging to the field of novel ink technology. The light-resistant and scratch-resistant gravure inkjet printing ink comprises the following raw materials in parts by weight: 38-45 parts of fluorosilicone modified polyacrylate emulsion, 7-11 parts of modified composite powder, 6-9 parts of nano carbon black, 1.2-1.8 parts of dispersant, 0.6-1.2 parts of leveling agent, 0.3-0.6 parts of defoamer, 1.5-2 parts of abrasion-resistant agent, 0.4-0.8 parts of AMP-95, and 25-35 parts of deionized water. This application limits the composition and weight of the inkjet ink, and uses fluorosilicone modified polyacrylate emulsion as the film-forming main body to endow the ink with low surface energy, high water resistance and excellent adhesion to film substrates; combined with modified composite powder, it effectively improves the dispersibility of nanoparticles, avoids agglomeration and clogging, and significantly improves the sun resistance and anti-aging performance. Overall, it takes into account high sun resistance, high scratch resistance, strong adhesion, environmental protection and low VOC, and is highly suitable for high-speed gravure inline inkjet printing scenarios.

Description

Technical Field

[0001] This application relates to a light-resistant and scratch-resistant gravure inkjet printing ink and its preparation method, belonging to the field of novel ink technology. Background Technology

[0002] Inline gravure printing is currently the mainstream integrated printing process in flexible packaging, agricultural packaging, food and pharmaceutical packaging, and cigarette packaging. It can simultaneously complete gravure printing of packaging patterns and online printing of variable QR codes, traceability codes, and anti-counterfeiting codes, resulting in extremely high production efficiency. Currently, the inks used for QR code printing in the industry are mainly divided into ordinary solvent-based inks, UV-cured inks, and water-based inks. With the printing industry's increasingly stringent environmental requirements, the application of solvent-based inks is limited due to problems such as environmental pollution, safety risks, health hazards, high costs, and poor ink transfer efficiency. Water-based inks have lower VOC emissions, milder odors, and minimal residual solvents, thus attracting considerable attention in the ink industry.

[0003] However, water-based inks have two major problems. On the one hand, water-based inks are mostly used for paper printing. When used on substrates such as films and aluminum foil, they generally have defects such as low adhesion and poor scratch resistance. During high-speed production and stacking transportation, the ink is easily worn and faded. On the other hand, they have insufficient sun resistance. After outdoor storage and exposure to sunlight, the QR codes fade quickly, turn white, and have large color differences, resulting in the phenomenon that the QR codes cannot be scanned and recognized.

[0004] In order to improve the above-mentioned problems, the industry often uses methods such as adjusting the resin type, adding functional monomers or nanofillers to improve the durability and adhesion of water-based inks. Chinese patent CN 119286305 B discloses a method for preparing abrasion-resistant and scratch-resistant water-based ink, and specifically discloses the addition of nano zinc oxide to improve abrasion resistance and the improvement of its surface to improve its dispersibility. This patent improves the abrasion resistance of the ink, but its sun resistance is limited and it is difficult to meet the high sun resistance requirements of outdoor use. In addition, a large number of inorganic fillers disrupt the film-forming continuity of the water-based system, and the ink film has micropores and decreased density, which leads to poor adhesion and decreased water resistance.

[0005] Therefore, providing a coding ink that combines excellent sun resistance, scratch resistance, substrate adhesion, and environmental friendliness is a technical problem that urgently needs to be solved in this field. Summary of the Invention

[0006] To address the aforementioned issues, this application provides a sun-resistant and scratch-resistant gravure inkjet printing ink and its preparation method. By limiting the components and weight parts of the inkjet printing ink, and using a fluorosilicone-modified polyacrylate emulsion as the film-forming main body, this application endows the ink with low surface energy, high water resistance, and excellent adhesion to film substrates. Combined with modified composite powder, it effectively improves the dispersibility of nanoparticles, avoids agglomeration and clogging, and significantly enhances sun-resistant and anti-aging properties. Overall, it balances high sun resistance, high scratch resistance, strong adhesion, and environmentally friendly low VOC, making it highly suitable for high-speed gravure inline inkjet printing scenarios.

[0007] According to one aspect of this application, a light-resistant and scratch-resistant gravure inkjet printer is provided, comprising the following raw materials in parts by weight: 38-45 parts of fluorosilicone modified polyacrylate emulsion, 7-11 parts of modified composite powder, 6-9 parts of nano carbon black, 1.2-1.8 parts of dispersant, 0.6-1.2 parts of leveling agent, 0.3-0.6 parts of defoamer, 1.5-2 parts of abrasion resistant agent, 0.4-0.8 parts of AMP-95, and 25-35 parts of deionized water.

[0008] Specifically, this application uses fluorosilicone-modified polyacrylate emulsion as the main component, combined with modified composite powder, nano carbon black, and special additives. The components are precisely proportioned and work synergistically. The fluorosilicone-modified polyacrylate emulsion provides low surface energy and film adhesion. The modified composite powder has good compatibility with the main emulsion, improving lightfastness and dispersion stability. Nano carbon black ensures high blackness and contrast of the QR code. Dispersants, leveling agents, defoamers, abrasion-resistant additives, and AMP-95 synergistically optimize rheology, wetting, foam suppression, and pH stability. Deionized water adjusts the viscosity, achieving high lightfastness, high scratch resistance, strong adhesion, and low VOC, making it suitable for high-speed gravure printing.

[0009] Optionally, the fluorosilicone modified polyacrylate emulsion is obtained by graft polymerization of acrylate emulsion with fluorine monomers and siloxane monomers; the modified composite powder is obtained by in-situ polymerization coating of nano-silica and nano-titanium dioxide with acrylic monomers.

[0010] Specifically, this application specifies that the fluorosilicone emulsion is obtained by grafting and polymerizing acrylate emulsion with fluorine monomers and siloxane monomers, and the modified composite powder is prepared by in-situ coating of acrylic monomers with nano-silica and titanium dioxide. In this process, the grafting of fluorine monomers and siloxane monomers introduces low surface energy fluorocarbon chains and crosslinkable siloxane groups, which improves the emulsion's water resistance, weather resistance and adhesion. The in-situ coating of acrylic acid allows organic chains to be grafted onto the surface of the inorganic powder, forming hydrogen bonds and physical entanglement with the fluorosilicone emulsion, solving the problem of powder agglomeration, enhancing interfacial bonding, and taking into account dispersion stability, sun resistance and ink film density.

[0011] Specifically, the fluorine monomer is dodecafluoroheptyl methacrylate, and the siloxane monomer is vinyltrimethoxysilane.

[0012] Optionally, the fluorosilicone modified polyacrylate emulsion is prepared by the following method: adding acrylate emulsion and water into a reaction vessel and stirring evenly to form a diluted acrylate emulsion system for later use; mixing fluorinated monomer and siloxane monomer evenly to obtain a mixed modified monomer; heating the diluted acrylate emulsion system to 60~70℃, adding the mixed modified monomer and initiator solution dropwise, stirring and reacting for 1~2 hours; after the reaction is completed, cooling and filtering to obtain the fluorosilicone modified polyacrylate emulsion.

[0013] Specifically, the initiator is ammonium persulfate.

[0014] Specifically, this application defines the preparation process of fluorosilicone modified polyacrylate emulsion, which efficiently introduces fluorosilicone functional groups without affecting the film-forming properties of the acrylate matrix, taking into account the modification efficiency, system stability and subsequent ink printing compatibility. The process is simple and industrializable.

[0015] Optionally, the amount of water added is 10-15% of the mass of the acrylate emulsion; the amount of fluorine monomer added is 2.5-3% of the mass of the acrylate emulsion; the amount of siloxane monomer added is 1.5-2% of the mass of the acrylate emulsion; and the amount of initiator added is 3-5% of the sum of the masses of the fluorine monomer and the siloxane monomer.

[0016] Specifically, this application specifies the amount of each raw material to achieve precise introduction of fluorosilicone groups, balance low surface energy, weather resistance and emulsion stability, ensure sufficient graft polymerization without excessive side reactions, and achieve efficient fluorosilicone grafting.

[0017] Optionally, the modified composite powder is prepared by the following method: adding nano-silica and nano-titanium dioxide to deionized water, ultrasonically dispersing to obtain a dispersion, heating the dispersion to 55~65℃, adding acrylic monomer and initiator solution, reacting at a constant temperature for 0.5~1h, filtering and drying after the reaction to obtain the modified composite powder.

[0018] Specifically, the initiator is ammonium persulfate.

[0019] Specifically, the acrylic monomer forms a uniform coating layer on the powder surface, transforming the hydrophilic inorganic powder into an organic powder. On the one hand, this can improve the powder agglomeration phenomenon, and on the other hand, it can achieve good compatibility between the powder and the fluorosilicone emulsion, thereby improving the ink dispersion stability and lightfastness.

[0020] Optionally, the amount of acrylic monomer added is 10-15% of the total mass of nano-silica and nano-titanium dioxide, the amount of initiator added is 5-8% of the total mass of acrylic monomer, and the amount of deionized water added is 4-6 times the total mass of nano-silica and nano-titanium dioxide.

[0021] Specifically, this application limits the proportions of each component to ensure sufficient polymerization, stable coating, and uniform and complete coating layer. After the composite powder is coated with acrylic acid, the two inorganic particles are dispersed synergistically to form a stable system with the fluorosilicone emulsion, taking into account the sun resistance, wear resistance, dispersion stability and QR code forming quality.

[0022] Optionally, the mass ratio of the nano-titanium dioxide to the nano-silica is 1:(1.1~1.4).

[0023] Specifically, this application specifies the mass ratio of nano-titanium dioxide to nano-silica. Titanium dioxide provides excellent UV shielding and enhances the ink's resistance to sunlight and aging. Silica enhances the ink film's hardness, abrasion resistance, and thixotropy, improving printing clarity. Under this ratio, it can balance sunlight resistance and abrasion resistance, avoiding the shortcomings of a single powder.

[0024] Optionally, the sun-resistant and scratch-resistant gravure inkjet printing ink further includes 3 to 8 parts of chlorinated ether resin.

[0025] Specifically, this application also specifies the addition of chloroprene resin. Chlorinated ether resin has high polarity and strong cohesion, forming an interpenetrating network structure with fluorosilicone emulsion, which makes up for the shortcoming of fluorosilicone emulsion being relatively soft. Its strong polarity can enhance the adhesion to the substrate, improve the hardness and scratch resistance of the ink film, and chloroprene resin has good compatibility with the system.

[0026] Optionally, the dispersant includes ammonium polyacrylate dispersant or sodium acrylate copolymer dispersant; the leveling agent includes polyether-modified polydimethylsiloxane or polyester-modified polydimethylsiloxane; the defoamer includes polyether-modified polysiloxane defoamer or oil-free silicone defoamer; and the abrasion-resistant additive includes water-dispersible polyethylene wax emulsion.

[0027] Specifically, this application specifies the types of dispersants, leveling agents, defoamers, and abrasion-resistant additives. The dispersant is compatible with fluorosilicone systems, anchoring carbon black and modified composite powders to prevent agglomeration and sedimentation; the leveling agent stabilizes surface tension, improves spreading, inhibits edge shrinkage, and enhances QR code clarity; the defoamer rapidly breaks and suppresses foam without affecting film formation; the water-dispersible polyethylene wax emulsion, as an abrasion-resistant additive, forms a lubricating layer on the ink film surface, enhancing abrasion resistance. The synergistic effect of these additives, compatible with fluorosilicone ink systems, balances dispersion, leveling, foam suppression, and abrasion resistance.

[0028] According to another aspect of this application, a method for preparing the above-mentioned light-resistant and scratch-resistant gravure inkjet printing ink is also provided, comprising the following steps: (1) According to the weight proportions, deionized water, dispersant and defoamer are mixed and stirred evenly, modified composite powder and nano carbon black are added, stirred and dispersed by sand milling to obtain component A; (2) Fluorosilicone modified polyacrylate emulsion, chlorinated ether resin and wear-resistant additive are mixed evenly to obtain component B; (3) Add component A to component B, mix evenly, add leveling agent and AMP-95 to obtain a sun-resistant and scratch-resistant gravure inkjet ink.

[0029] Specifically, this application prepares light-resistant and scratch-resistant gravure inkjet printing ink in steps to avoid direct impact of high-concentration powder on the resin, which helps to reduce flocculation. After mixing components A and B, a leveling agent is added to optimize surface properties and AMP-95 is added to stabilize pH. The steps work together to ensure uniform ink dispersion, system stability, smooth printing, and clear QR codes. The process is suitable for high-speed production and has strong stability.

[0030] The beneficial effects of this application include, but are not limited to: 1. The light-resistant and scratch-resistant gravure inkjet printing ink of this application uses fluorosilicone modified polyacrylate emulsion as the base, and adds chlorinated ether resin to form an interpenetrating network to enhance the hardness and cohesion of the ink film; it is combined with acrylic coated composite powder to provide rigid support, and water-dispersible polyethylene wax abrasion-resistant additive to form a lubricating layer on the surface of the ink film, achieving synergistic wear resistance inside and out. After curing, the ink has high hardness and strong abrasion resistance, and is not easily worn or faded during high-speed production and stacking transportation. The QR code is not easily scratched, which significantly improves the stability of packaging and storage.

[0031] 2. The sun-resistant and scratch-resistant gravure inkjet printing ink of this application uses a composite powder of nano-silica and titanium dioxide, which is modified by in-situ coating with acrylic monomers. Titanium dioxide can effectively shield ultraviolet rays, while silica improves the stability of the system and synergistically endows the ink with excellent sun resistance. At the same time, fluorosilicone modified polyacrylate emulsion is used as the main film-forming agent. The fluorosilicone structure can further improve the weather resistance and anti-aging ability, effectively avoiding problems such as fading, whitening, and excessive color difference of QR codes under outdoor light, and can still remain clear and identifiable after long-term placement.

[0032] 3. According to the sun-resistant and scratch-resistant gravure inkjet ink of this application, the fluorosilicone modified polyacrylate emulsion introduces low surface energy fluorocarbon chains and siloxane groups, which are suitable for non-polar film substrates and have excellent adhesion; the modified composite powder is coated with acrylic acid, which has good compatibility with resin, strengthens the interfacial bonding force, and avoids ink layer peeling; with the help of special dispersants and leveling agents, the rheology and surface tension are optimized, so that there is no edge shrinkage or blurring during printing.

[0033] 4. According to the preparation method of the light-resistant and scratch-resistant gravure inkjet ink of this application, the additives are added in steps to reduce mutual interference between the additives and reduce the risk of bubbles and pinholes. The process is simple and the equipment is highly versatile. It can be completed with only conventional stirring and sand milling equipment. There is no need for high temperature and high pressure or complex reaction devices. It has low energy consumption and easy operation control, and is suitable for large-scale industrial promotion and application. Detailed Implementation

[0034] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments.

[0035] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of skill in the art. The reagents and raw materials used in this invention are readily available through conventional means, and unless otherwise specified, they are used in accordance with conventional methods or product instructions. Furthermore, any methods and materials similar to or equivalent to those described herein may be applied to the methods of this invention. The fluorinated monomer involved in the following examples and comparative examples is dodecylfluoroheptyl methacrylate, and the siloxane monomer is vinyltrimethoxysilane.

[0036] Example 1: A method for preparing a light-resistant and scratch-resistant gravure inkjet printing ink (1) Prepare the raw materials according to the following weight proportions: 38 parts of fluorosilicone modified polyacrylate emulsion, 3 parts of chlorinated ether resin, 7 parts of modified composite powder, 6 parts of nano carbon black, 1.2 parts of dispersant, 0.6 parts of leveling agent, 0.3 parts of defoamer, 1.5 parts of wear-resistant additive, 0.4 parts of AMP-95 and 25 parts of deionized water. Mix the deionized water, dispersant ammonium acrylate dispersant and defoamer polyether modified polysiloxane defoamer evenly. Add the modified composite powder and nano carbon black, stir, and disperse by sand milling to obtain component A. (2) Fluorosilicone modified polyacrylate emulsion, chlorinated ether resin, and abrasion-resistant additive water-dispersible polyethylene wax emulsion are mixed evenly to obtain component B; (3) Add component A to component B, mix evenly, add leveling agent polyether modified polydimethylsiloxane and AMP-95 to obtain a sun-resistant and scratch-resistant gravure inkjet ink.

[0037] Fluorosilicone modified polyacrylate emulsion was prepared by the following method: Acrylic emulsion and water were added to a reaction vessel, with the amount of water being 10% of the mass of the acrylate emulsion. The mixture was stirred until homogeneous to form a diluted acrylate emulsion system for later use. Fluorine monomers and siloxane monomers were mixed until homogeneous, with the amount of fluorine monomers being 2.5% of the mass of the acrylate emulsion and the amount of siloxane monomers being 1.5% of the mass of the acrylate emulsion, to obtain a mixed modified monomer. The diluted acrylate emulsion system was heated to 60°C, and the mixed modified monomer and initiator ammonium persulfate solution were added dropwise, with the amount of initiator being 3% of the combined mass of the fluorine monomer and siloxane monomer. The mixture was stirred and reacted for 1 hour. After the reaction was completed, the mixture was cooled and filtered to obtain the fluorosilicone modified polyacrylate emulsion.

[0038] The modified composite powder was prepared by the following method: nano-silica and nano-titanium dioxide were added to deionized water at a mass ratio of 1:1.1, and the amount of deionized water added was 4 times the sum of the masses of nano-silica and nano-titanium dioxide. The mixture was ultrasonically dispersed to obtain a dispersion. The dispersion was heated to 55°C, and acrylic monomer and ammonium persulfate solution, an initiator, were added. The amount of acrylic monomer added was 10% of the sum of the masses of nano-silica and nano-titanium dioxide, and the amount of initiator added was 5% of the mass of acrylic monomer. The mixture was reacted at a constant temperature for 0.5 h. After the reaction was completed, the mixture was filtered and dried to obtain the modified composite powder.

[0039] Example 2: A method for preparing a light-resistant and scratch-resistant gravure inkjet printing ink (1) Prepare the raw materials according to the following weight proportions: 45 parts of fluorosilicone modified polyacrylate emulsion, 8 parts of chlorinated ether resin, 11 parts of modified composite powder, 9 parts of nano carbon black, 1.8 parts of dispersant, 1.2 parts of leveling agent, 0.6 parts of defoamer, 2 parts of wear-resistant additive, 0.8 parts of AMP-95 and 35 parts of deionized water. Mix the deionized water, dispersant sodium salt of acrylate copolymer, and defoamer oil-free silicone defoamer evenly. Add the modified composite powder and nano carbon black, stir, and disperse by sand milling to obtain component A. (2) Fluorosilicone modified polyacrylate emulsion, chlorinated ether resin, and abrasion-resistant additive water-dispersible polyethylene wax emulsion are mixed evenly to obtain component B; (3) Add component A to component B, mix evenly, add leveling agent polyester modified polydimethylsiloxane and AMP-95 to obtain a sun-resistant and scratch-resistant gravure inkjet ink.

[0040] Fluorosilicone modified polyacrylate emulsion was prepared by the following method: Acrylic emulsion and water were added to a reaction vessel, with the amount of water being 15% of the mass of the acrylate emulsion. The mixture was stirred until homogeneous to form a diluted acrylate emulsion system for later use. Fluorine monomers and siloxane monomers were mixed until homogeneous, with the amount of fluorine monomers being 3% of the mass of the acrylate emulsion and the amount of siloxane monomers being 2% of the mass of the acrylate emulsion, to obtain a mixed modified monomer. The diluted acrylate emulsion system was heated to 70°C, and the mixed modified monomer and initiator ammonium persulfate solution were added dropwise, with the amount of initiator being 5% of the combined mass of the fluorine monomer and siloxane monomer. The mixture was stirred for 2 hours. After the reaction was completed, the mixture was cooled and filtered to obtain the fluorosilicone modified polyacrylate emulsion.

[0041] The modified composite powder was prepared by the following method: nano-silica and nano-titanium dioxide were added to deionized water at a mass ratio of 1:1.4, and the amount of deionized water added was 6 times the sum of the masses of nano-silica and nano-titanium dioxide. The mixture was ultrasonically dispersed to obtain a dispersion. The dispersion was heated to 65°C, and acrylic monomer and ammonium persulfate solution, an initiator, were added. The amount of acrylic monomer added was 15% of the sum of the masses of nano-silica and nano-titanium dioxide, and the amount of initiator added was 8% of the mass of acrylic monomer. The mixture was reacted at a constant temperature for 1 hour. After the reaction was completed, the mixture was filtered and dried to obtain the modified composite powder.

[0042] Example 3: A method for preparing a light-resistant and scratch-resistant gravure inkjet printing ink (1) Prepare the raw materials according to the following weight proportions: 40 parts of fluorosilicone modified polyacrylate emulsion, 5 parts of chlorinated ether resin, 8 parts of modified composite powder, 8 parts of nano carbon black, 1.6 parts of dispersant, 1 part of leveling agent, 0.5 parts of defoamer, 1.7 parts of wear-resistant additive, 0.6 parts of AMP-95 and 30 parts of deionized water. Mix the deionized water, dispersant ammonium acrylate dispersant and defoamer polyether modified polysiloxane defoamer evenly, add the modified composite powder and nano carbon black, stir, and disperse by sand milling to obtain component A; (2) Fluorosilicone modified polyacrylate emulsion, chlorinated ether resin, and abrasion-resistant additive water-dispersible polyethylene wax emulsion are mixed evenly to obtain component B; (3) Add component A to component B, mix evenly, add leveling agent polyether modified polydimethylsiloxane and AMP-95 to obtain a sun-resistant and scratch-resistant gravure inkjet ink.

[0043] Fluorosilicone modified polyacrylate emulsion was prepared by the following method: Acrylic emulsion and water were added to a reaction vessel, with the amount of water being 12% of the mass of the acrylate emulsion. The mixture was stirred until homogeneous to form a diluted acrylate emulsion system for later use. Fluoromonomers and siloxane monomers were mixed homogeneously, with the amount of fluoromonomers being 2.8% of the mass of the acrylate emulsion and the amount of siloxane monomers being 1.7% of the mass of the acrylate emulsion, to obtain a mixed modified monomer. The diluted acrylate emulsion system was heated to 65°C, and the mixed modified monomer and initiator ammonium persulfate solution were added dropwise, with the amount of initiator being 4% of the combined mass of the fluoromonomer and siloxane monomer. The mixture was stirred for 1.5 hours. After the reaction was completed, the mixture was cooled and filtered to obtain the fluorosilicone modified polyacrylate emulsion.

[0044] The modified composite powder was prepared by the following method: nano-silica and nano-titanium dioxide were added to deionized water at a mass ratio of 1:1.2, and the amount of deionized water added was 5 times the sum of the masses of nano-silica and nano-titanium dioxide. The mixture was ultrasonically dispersed to obtain a dispersion. The dispersion was heated to 60°C, and acrylic monomer and ammonium persulfate solution, an initiator, were added. The amount of acrylic monomer added was 12% of the sum of the masses of nano-silica and nano-titanium dioxide, and the amount of initiator added was 6% of the mass of acrylic monomer. The mixture was reacted at a constant temperature for 0.7 h. After the reaction was completed, the mixture was filtered and dried to obtain the modified composite powder.

[0045] Example 4 The difference between Example 4 and Example 3 is that the amount of fluorinated monomer added is 5% of the mass of the acrylate emulsion; the amount of siloxane monomer added is 1% of the mass of the acrylate emulsion, and the rest are the same.

[0046] Example 5 The difference between Example 5 and Example 3 is that the composite powder was modified with KH-560, but all other aspects are the same.

[0047] Example 6 The difference between Example 6 and Example 3 is that the mass ratio of nano-titanium dioxide to nano-silica is 1:3, while all other aspects are the same.

[0048] Example 7 The difference between Example 7 and Example 3 is that Example 7 does not include chlorinated ether resin, but all other aspects are the same.

[0049] Comparative Example 1 The difference between Comparative Example 1 and Example 3 is that ordinary acrylate emulsion was used instead of fluorosilicone modified polyacrylate emulsion, while the rest were the same.

[0050] Comparative Example 2 The difference between Comparative Example 2 and Example 3 is that the composite powder was not modified, but all other aspects are the same.

[0051] Comparative Example 3 The difference between Comparative Example 3 and Example 3 is that the modified powder only includes 8 parts of modified nano-silica, while the rest are the same.

[0052] Comparative Example 4 The difference between Comparative Example 4 and Example 3 is that the modified powder only includes 8 parts of modified nano titanium dioxide, while the rest are the same.

[0053] Experiment Example 1: Sun Protection Performance Test The inks of each embodiment and comparative example were used to print 600dpi variable QR code patterns on the surface of PET film using a gravure inline coding machine; after natural drying at room temperature for 24 hours, test ink films were obtained for later use.

[0054] According to GB / T 1865-2009 "Artificial Climate Aging and Artificial Radiation Exposure (Filtered Xenon Arc Radiation)", the ink film was placed in a xenon lamp aging chamber with an irradiance of 0.51 W / m²@340 nm, a blackboard temperature of 65℃, and a relative humidity of 50%, and was continuously irradiated for 1000 h. The color difference ΔE and 60° gloss retention rate were measured using a spectrophotometer before and after aging. The test results are shown in Table 1.

[0055] Table 1 Results of sun protection performance test

[0056] Table 1 shows that Examples 1-3 exhibit excellent performance with a sun resistance ΔE ≤ 1.7 and gloss retention ≥ 89%, with Example 3 being the best example. Example 4 shows an increase in ΔE to 2.6 and a decrease in gloss, attributed to an excess of fluorine monomers and a deficiency of silicon monomers, resulting in an imbalance of fluorine-silicon synergy. Example 5 shows weakened sun resistance, attributed to the lack of acrylic coating on the powder, leading to poor interfacial compatibility. Example 6 shows a ΔE of 3.3, attributed to an insufficient titanium dioxide content and inadequate UV shielding. Example 7 lacks chlorinated ether resin, resulting in decreased weather resistance. Comparative Examples 1 (without fluorine-silicon modification), 2 (without powder modification), and 3 and 4 (using a single powder) all show a comprehensive deterioration in sun resistance.

[0057] Experiment Example 2: Wear Resistance Test The inks of each embodiment and comparative example were used to print 600dpi variable QR code patterns on the surface of PET film using a gravure inline coding machine; after natural drying at room temperature for 24 hours, test ink films were obtained for later use.

[0058] The wear resistance was evaluated by abrasion test and changes in the water contact angle of the ink surface. The specific operation was as follows: a 7000-grit SiC sandpaper was placed on the ink surface, and a 200g weight was pressed on the sandpaper. The sample was dragged horizontally for 10cm at a constant speed. The sample was then rotated 90° clockwise and dragged horizontally for another 10cm at a constant speed. This was repeated as one cycle, and the abrasion cycle was repeated 30 times. The water contact angle of the ink surface before and after abrasion was measured. The data results are shown in Table 2.

[0059] Table 2. Abrasion resistance test results

[0060] Table 2 shows that the contact angle difference before and after wear in Examples 1-3 was only 3°, indicating stable hydrophobic and wear-resistant performance. In Example 4, the difference increased to 4°, attributed to an imbalance in the fluorine-silicone ratio and uneven surface hydrophobic layer. In Example 5, poor powder compatibility resulted in insufficient ink film density and decreased wear resistance. In Example 6, an excessively high silica content led to insufficient rigidity, resulting in severe damage to the hydrophobic layer after wear. In Example 7, the absence of chlorinated ether resin resulted in low ink film hardness, with a difference of 5°. Comparative Example 1, with its fluorine-silicone-free hydrophobic structure, Comparative Example 2, with powder agglomeration leading to a loose ink film, and Comparative Examples 3 and 4, with their single-powder composition, exhibited significant shortcomings in wear resistance, with differences ≥7° in all cases.

[0061] Experiment Example 3 Adhesion Test The inks of each embodiment and comparative example were used to print 600dpi variable QR code patterns on the surface of PET film using a gravure inline coding machine; after natural drying at room temperature for 24 hours, test ink films were obtained for later use.

[0062] Adhesion performance test: Adhesion was tested according to GB / T13217.7-2023 "Ink Adhesion Test Method", and the test results are shown in Table 3.

[0063] Table 3 Adhesion test results

[0064] Table 3 shows that the adhesion strength of Examples 1-3 all reached 99% or above, with Example 3 being the best example, reaching 99.6%. Examples 4-7 showed varying degrees of decreased adhesion. The reasons for this were: Example 4 had an unbalanced fluorosilicone ratio, resulting in decreased interfacial polarity matching; Example 5 had improper powder coating, leading to poor interfacial compatibility and weakened adhesion; Example 6 had an unbalanced powder ratio, resulting in uneven ink film cohesion and detachment; and Example 7 lacked chlorinated ether resin, resulting in insufficient interfacial bonding strength and decreased adhesion. Comparative Example 1 had the worst adhesion. The reasons for this were: Comparative Example 1 lacked a fluorosilicone low surface energy structure; Comparative Example 2 had powder agglomeration leading to uneven ink film adhesion; and Comparative Examples 3 and 4 had weak interfacial bonding of single powders, with adhesion below 90%.

[0065] Experiment Example 4 Recognition Rate Test The inks of each embodiment and comparative example were used to print 600dpi variable QR code patterns on the surface of PET film using a gravure inline coding machine; after natural drying at room temperature for 24 hours, test ink films were obtained for later use.

[0066] Test method: Scan the barcode scanner 100 times continuously and count the recognition rate.

[0067] The test results are shown in Table 4.

[0068] Table 4 Recognition Rate Test Results

[0069] Table 4 shows that the QR code recognition rate of Examples 1-3 was 100%, while the recognition rate of Examples 4-7 decreased, but remained above 92%. The reasons for this are: Example 4 had an unbalanced fluorine-silicone ratio, resulting in uneven ink film surface tension and slight edge shrinkage, reducing the recognition rate to 96%; Example 5 had powder agglomeration, easily clogging the printhead and causing blurred edges, reducing the recognition rate to 94%; Example 6 had an unbalanced powder ratio, resulting in uneven blackness, with a recognition rate of 92%; Example 7 lacked chlorinated ether resin, causing the ink film to wear easily and become slightly blurred, reducing the recognition rate to 95%. Comparative Examples 1-4 showed a significant decrease in recognition rate. The reasons for this are: Comparative Example 1 lacked fluorine-silicone emulsion, resulting in poor adhesion and easy QR code detachment; Comparative Example 2 had severe powder agglomeration, clogging the printhead and causing blurred edges; and Comparative Examples 3 and 4 had insufficient blackness and stability of the single powder, resulting in recognition rates ≤90%.

[0070] The above description is merely an embodiment of this application, and the scope of protection of this application is not limited to these specific embodiments, but is determined by the claims of this application. Various modifications and variations can be made to this application by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the technical concept and principles of this application should be included within the scope of protection of this application.

Claims

1. A type of sun-resistant and scratch-resistant gravure inkjet printing ink, characterized in that, The raw materials include the following parts by weight: 38-45 parts of fluorosilicone modified polyacrylate emulsion, 7-11 parts of modified composite powder, 6-9 parts of nano carbon black, 1.2-1.8 parts of dispersant, 0.6-1.2 parts of leveling agent, 0.3-0.6 parts of defoamer, 1.5-2 parts of wear-resistant additive, 0.4-0.8 parts of AMP-95, and 25-35 parts of deionized water.

2. The sun-resistant and scratch-resistant gravure inkjet printing ink according to claim 1, characterized in that, The fluorosilicone modified polyacrylate emulsion is obtained by graft polymerization of acrylate emulsion with fluorine monomers and siloxane monomers; the modified composite powder is obtained by in-situ polymerization coating of nano-silica and nano-titanium dioxide with acrylic monomers.

3. The sun-resistant and scratch-resistant gravure inkjet printing ink according to claim 2, characterized in that, The fluorosilicone modified polyacrylate emulsion is prepared by the following method: adding acrylate emulsion and water into a reaction vessel and stirring evenly to form a diluted acrylate emulsion system for later use; mixing fluorinated monomer and siloxane monomer evenly to obtain a mixed modified monomer; heating the diluted acrylate emulsion system to 60~70℃, adding the mixed modified monomer and initiator solution dropwise, stirring and reacting for 1~2 hours; after the reaction is completed, cooling and filtering to obtain the fluorosilicone modified polyacrylate emulsion.

4. The sun-resistant and scratch-resistant gravure inkjet printing ink according to claim 3, characterized in that, The amount of water added is 10-15% of the mass of the acrylate emulsion; the amount of fluorine monomer added is 2.5-3% of the mass of the acrylate emulsion; the amount of siloxane monomer added is 1.5-2% of the mass of the acrylate emulsion; and the amount of initiator added is 3-5% of the sum of the masses of the fluorine monomer and the siloxane monomer.

5. The sun-resistant and scratch-resistant gravure inkjet printing ink according to claim 1, characterized in that, The modified composite powder is prepared by the following method: nano-silica and nano-titanium dioxide are added to deionized water and ultrasonically dispersed to obtain a dispersion. The dispersion is heated to 55~65℃, acrylic monomer and initiator solution are added, and the reaction is carried out at a constant temperature for 0.5~1h. After the reaction is completed, the mixture is filtered and dried to obtain the modified composite powder.

6. The sun-resistant and scratch-resistant gravure inkjet printing ink according to claim 5, characterized in that, The amount of acrylic monomer added is 10-15% of the total mass of nano-silica and nano-titanium dioxide, the amount of initiator added is 5-8% of the total mass of acrylic monomer, and the amount of deionized water added is 4-6 times the total mass of nano-silica and nano-titanium dioxide.

7. The sun-resistant and scratch-resistant gravure inkjet printing ink according to claim 5, characterized in that, The mass ratio of nano-titanium dioxide to nano-silica is 1:(1.1~1.4).

8. The sun-resistant and scratch-resistant gravure inkjet printing ink according to claim 1, characterized in that, The sun-resistant and scratch-resistant gravure inkjet printing ink also includes 3 to 8 parts of chlorinated ether resin.

9. The sun-resistant and scratch-resistant gravure inkjet printing ink according to claim 1, characterized in that, The dispersant includes ammonium polyacrylate dispersant or sodium acrylate copolymer dispersant; the leveling agent includes polyether-modified polydimethylsiloxane or polyester-modified polydimethylsiloxane; the defoamer includes polyether-modified polysiloxane defoamer or oil-free silicone defoamer; and the abrasion-resistant additive includes water-dispersible polyethylene wax emulsion.

10. A method for preparing a light-resistant and scratch-resistant gravure inkjet printing ink according to any one of claims 1 to 9, characterized in that, Includes the following steps: (1) According to the weight proportions, deionized water, dispersant and defoamer are mixed and stirred evenly, modified composite powder and nano carbon black are added, stirred and dispersed by sand milling to obtain component A; (2) Fluorosilicone modified polyacrylate emulsion, chlorinated ether resin and wear-resistant additive are mixed evenly to obtain component B; (3) Add component A to component B, mix evenly, add leveling agent and AMP-95 to obtain a sun-resistant and scratch-resistant gravure inkjet ink.

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