Two-dimensional code UV spraying ink and preparation method thereof

Abstract

The invention relates to two-dimensional code UV code spraying ink and a preparation method thereof. The two-dimensional code UV code spraying ink comprises a monofunctional UV monomer, a bifunctional UV monomer, a polymerization inhibitor, a photoinitiator, hyperbranched acrylic resin, a flatting agent, color paste and a wear-resistant component, the wear-resistant component comprises graphene oxide and silicon dioxide composite carbon nanotubes. The code spraying ink has the effect of improving the wear resistance of the code spraying ink.

Description

Technical Field

[0001] The present application relates to the field of inkjet coding ink, and in particular to a two-dimensional code UV inkjet coding ink and a preparation method thereof. Background Art

[0002] Application of inkjet inks Inkjet inks are widely used for surface marking of various products, such as production date, batch number, barcode and QR code, etc. Traditional inkjet inks mainly include solvent-based inks and water-based inks, which require a long drying time after printing, have poor adhesion on certain substrates, and are prone to fading, blurring and other problems.

[0003] Advantages of LED-UV curing inkjet inkLED-UV curing inkjet ink is quickly cured by ultraviolet light and has the following advantages: Fast curing: UV ink can be completely cured instantly, meeting the requirements of offset printing and gravure printing, greatly improving production efficiency; Environmental protection: UV ink does not contain volatile organic compounds (VOCs), reducing pollution to the environment; High adhesion: UV ink has good adhesion on a variety of substrates and is not easy to fall off; Chemical resistance and wear resistance: The cured ink has excellent chemical resistance and wear resistance, and is suitable for harsh environments.

[0004] Demand for QR Code Printing As a high-density information encoding method, QR code is widely used in product traceability, anti-counterfeiting and marketing. However, traditional inkjet printing inks have some problems when printing QR codes, such as low resolution, easy blurring and fading, which affect the recognition rate and reliability of QR codes. Summary of the invention

[0005] In order to improve the stability of inkjet coding ink, the present application provides a two-dimensional code UV inkjet coding ink and a preparation method thereof.

[0006] The present application provides a two-dimensional code UV inkjet ink and a preparation method thereof using the following technical solutions: In the first aspect, the present application provides a two-dimensional code UV inkjet ink, which adopts the following technical solution: A two-dimensional code UV inkjet ink comprises a monofunctional UV monomer, a difunctional UV monomer, an inhibitor, a photoinitiator, a hyperbranched acrylic resin, a leveling agent, a color paste and a wear-resistant component; the wear-resistant component comprises graphene oxide and silicon dioxide composite carbon nanotubes.

[0007] By adopting the above technical scheme, the wear-resistant component is prepared by modifying graphene oxide and silicon dioxide composite carbon nanotubes. Graphene oxide is an important derivative of graphene-based materials, which can provide a large specific surface area and has good dispersion performance in the system. The introduction of its oxygen-containing groups not only makes the graphene oxide chemically stable, but also provides surface modification active sites and a large specific surface area, so that the graphene oxide and the silicon dioxide composite carbon nanotubes can be better combined, further improving the stability of the system; after the carbon nanotubes are combined with silicon dioxide, they have good hydrophobic properties and wear resistance. After being compounded with modified graphene oxide, they can synergistically improve the wear resistance and stability of the inkjet ink. At the same time, the inkjet with high stability has good color rendering, further improving the recognition rate of the two-dimensional code obtained by inkjet.

[0008] Preferably, the silicon dioxide composite carbon nanotubes are prepared by the following method: The carboxyl carbon nanotubes, isopropanol and water are mixed, and then ammonia water is added, and after ultrasonic dispersion, ethyl orthosilicate is added to react, and after the reaction, the composite particles are washed and dried to obtain composite particles; the composite particles are hydrophobicized to obtain silicon dioxide composite carbon nanotubes.

[0009] By adopting the above technical scheme, using tetraethyl orthosilicate, carboxyl carbon nanotubes and ammonia water as raw materials, silicon dioxide is in situ grown on the surface of carbon nanotubes to obtain silicon dioxide composite carbon nanotubes. There is a stable bonding performance between silicon dioxide and carbon nanotubes, thereby further improving the stability of the wear-resistant component. After the composite particles are hydrophobic treated, the silicon dioxide composite carbon nanotubes have good hydrophobic properties.

[0010] Preferably, the hydrophobic treatment comprises the following steps: The composite particles are added into ethanol and stirred to obtain a composite particle dispersion; the silane coupling agent is mixed with ethanol and ultrasonically dispersed to obtain a silane coupling agent dispersion; the silane coupling agent dispersion is mixed with the composite particle dispersion, and perfluorodecyltrimethylsilane is added and stirred for reaction. After the reaction, the precipitate is washed and dried to complete the hydrophobic treatment and obtain silicon dioxide composite carbon nanotubes.

[0011] By adopting the above technical scheme, the composite particles are modified by a silane coupling agent and perfluorodecyltrimethylsilane, the ethoxy group in the silane coupling agent undergoes a hydrolysis reaction to generate silanol, and then the silanol molecules undergo a hydrogen bond reaction and condensation with the hydroxyl groups on the surface of the inorganic powder particles to obtain a covering substance with a network structure, which is attached to the surface of the powder particles to modify the composite particles. The modified composite particles have good roughness and improved hydrophobic properties, and the prepared inkjet has good stability.

[0012] Preferably, the mass ratio of the carboxyl carbon nanotubes, tetraethyl orthosilicate and ammonia water is (0.6-0.8):2.5:1.

[0013] By adopting the above technical solution, preferably the mass ratio of tetraethyl orthosilicate, ethanol, water and ammonia water is within the above range, so that the prepared silicon dioxide composite carbon nanotubes have good stability.

[0014] Preferably, the reaction time is 10-14h.

[0015] By adopting the above technical solution, preferably the reaction time is within the above range, the stability of the prepared silicon dioxide composite carbon nanotubes can be further improved.

[0016] Preferably, the mass ratio between the silane coupling agent and perfluorodecyltrimethoxysilane is 1:(1.4-1.6).

[0017] By adopting the above technical solution, preferably the mass ratio between the silane coupling agent and perfluorodecyltrimethylsilane is within the above range, the stability of the prepared silicon dioxide composite carbon nanotubes can be further improved.

[0018] Preferably, the wear-resistant component is prepared by the following method: The graphene oxide is mixed with toluene, bromomethyldimethylsilyl chloride is added, the temperature is raised and refluxed, centrifugal filtration and washing are performed, and the modified graphene oxide is obtained by drying; the modified graphene oxide, silicon dioxide composite carbon nanotubes and dimethylformamide are mixed, ultrasonically dispersed, heated for reaction, centrifugal filtration and washing are performed, and the composite product is obtained by drying; the composite product, tannic acid and ethanol are mixed, vacuumized, centrifuged and washed, and the wear-resistant component is obtained by drying.

[0019] By adopting the above technical scheme, the silicon dioxide composite carbon nanotubes are grafted onto the surface of modified graphene oxide to obtain a wear-resistant component, and the surface of graphene oxide is brominated using bromomethyldimethylsilyl chloride to obtain modified graphene oxide. Finally, the silicon dioxide composite carbon nanotubes are loaded on the layered structure of the modified graphene oxide. The silicon dioxide composite carbon nanotubes have good bonding properties with the modified graphene oxide, and the prepared wear-resistant component has good adhesion, which further improves the stability of the ink.

[0020] Preferably, the mass ratio of the modified graphene oxide to the silicon dioxide composite carbon nanotubes is 1:(1.1-1.3).

[0021] By adopting the above technical solution, the mass ratio of modified graphene oxide, silicon dioxide composite carbon nanotubes and tannic acid is preferably within the above range, which can further improve the stability of the prepared wear-resistant component.

[0022] Preferably, the wear-resistant component accounts for 5-7% of the entire coding ink system.

[0023] By adopting the above technical solution, the added amount of the wear-resistant component is preferably within the above range, which can further improve the stability of the ink.

[0024] In the second aspect, the present application provides a method for preparing a two-dimensional code UV inkjet ink, using the following technical solution: A method for preparing a two-dimensional code UV inkjet ink comprises the following steps: After monofunctional UV monomer, difunctional UV monomer, inhibitor, photoinitiator, hyperbranched acrylic resin, leveling agent, color paste and wear-resistant component are mixed, fully stirred, and then three-stage filtration is performed. The filter elements are 0.8um, 0.5um, and 0.3um respectively. After filtration, the inkjet ink is obtained. In summary, the present application includes at least one of the following beneficial technical effects: 1. Adding a wear-resistant component to the inkjet ink system, the modified graphene oxide in the wear-resistant component is an important derivative of graphene-based materials, and has good dispersibility. The introduction of its oxygen-containing groups not only improves the chemical stability of graphene oxide, but also provides surface modification active sites and a large specific surface area, so that the modified graphene oxide and the silicon dioxide composite carbon nanotubes can be better combined, so that the stability of the system is further improved. After the carbon nanotubes are combined with silicon dioxide, they have good hydrophobic properties and wear resistance. The wear-resistant component prepared after being compounded with the modified graphene oxide can synergistically improve the wear resistance and stability of the system; 2. Using tetraethyl orthosilicate, carboxyl carbon nanotubes and ammonia as raw materials, silica is natively grown on the surface of carbon nanotubes, and then hydrophobic treatment is carried out with silane coupling agent and perfluorodecyltrimethylsilane. The obtained silica composite carbon nanotubes have good binding performance and stability, and also have good hydrophobic properties, which improves the binding performance of the ink and further enhances the stability of the ink. DETAILED DESCRIPTION

[0025] The present application is further described in detail below with reference to the embodiments: Description of raw materials: All raw materials in the examples are commercially available; wherein the polymerization inhibitor is polymerization inhibitor 701; the photoinitiator is; the hyperbranched acrylic resin is a mixture of DT019 acrylic resin and 9180 acrylic resin; the leveling agent is polydimethylsiloxane (CAS No.: 9016-00-6); and the photoinitiator is photoinitiator IHT-PI659.

[0026] Example 1 Preparation of silicon dioxide composite carbon nanotubes: 4.39 g of carboxyl carbon nanotubes, 140 g of isopropanol and 60 g of deionized water were mixed, 7.32 g of ammonia water was added, ultrasonic dispersion was performed for 10 min, and then 18.29 g of tetraethyl orthosilicate was added, and the mixture was reacted at 50 ° C for 10 h. After the reaction, deionized water and ethanol were used for alternating centrifugal washing for 3 times, and then dried in a blast oven at 70 ° C for 18 h, and composite particles were obtained after grinding; 15 g of the composite particles were added to 50 g of ethanol, stirred for 15 min, and composite particles were obtained. The composite particle dispersion was prepared; 3.33 g of a silane coupling agent was mixed with 50 g of ethanol, and the mixture was ultrasonically dispersed for 15 min to obtain a silane coupling agent dispersion; the silane coupling agent dispersion was mixed with the composite particle dispersion, and 4.67 g of perfluorodecyltrimethylsilane was added, and the mixture was reacted with magnetic stirring for 12 h. After the reaction, the mixture was centrifuged, and the obtained precipitate was repeatedly washed 3 times with anhydrous ethanol, and then dried at 80 ° C with a blower for 24 h and ground to complete the hydrophobic treatment to obtain silica composite carbon nanotubes.

[0027] Preparation of wear-resistant components: 15 g of graphene oxide was mixed with 100 ml of toluene, and 15 g of bromomethyldimethylsilyl chloride was added under nitrogen protection and magnetic stirring. The temperature was raised to 70 ° C, refluxed for 4 h, and centrifuged to obtain the product. The product was washed alternately with toluene and ethanol for 3 times, and then dried to obtain modified graphene oxide. 14.29 g of modified graphene oxide, 15.71 g of silicon dioxide composite carbon nanotubes and 200 ml of dimethylformamide were mixed, ultrasonically dispersed for 30 min, and stirred under nitrogen protection and magnetic stirring. Under stirring conditions, the temperature is raised to 110°C, the reaction is carried out for 12 hours, the product is collected by centrifugal filtration, the collected solid is washed three times with dimethylformamide and formaldehyde, and then dried in a drying oven at 70°C for 12 hours to obtain a composite product, the composite product, 75g of tannic acid and 150g of ethanol are mixed, kept under vacuum conditions for 30 minutes, centrifuged at a speed of 8000 / min for 10 minutes, then washed three times with ethanol, dried at 60°C for 12 hours, and ground to obtain a wear-resistant component.

[0028] Preparation of inkjet ink: After monofunctional UV monomer, difunctional UV monomer, inhibitor, photoinitiator, hyperbranched acrylic resin, leveling agent, color paste and wear-resistant component are mixed, fully stirred, and then three-stage filtration is performed, and the filter elements are 0.8um, 0.5um and 0.3um respectively. After filtration, the inkjet ink is obtained, and the monofunctional UV monomer accounts for 30%, the difunctional UV monomer accounts for 7.3%, the inhibitor accounts for 0.2%, the photoinitiator accounts for 12%, the leveling agent accounts for 0.5%, the black paste accounts for 18%, the wear-resistant component accounts for 5%, and the rest is supplemented by hyperbranched acrylic resin; wherein the monofunctional UV monomer is 4-acryloylmorpholine (CAS No.: 5117-12-4); the difunctional UV monomer is dipropylene glycol diacrylate (CAS No.: 57472-68-1).

[0029] Example 2 Preparation of silicon dioxide composite carbon nanotubes: 5.58 g of carboxyl carbon nanotubes, 140 g of isopropanol and 60 g of deionized water were mixed, 6.98 g of ammonia water was added, ultrasonic dispersion was performed for 10 min, and then 17.44 g of tetraethyl orthosilicate was added, and the mixture was reacted at 60 ° C for 14 h. After the reaction, deionized water and ethanol were used for alternating centrifugal washing for 3 times, and then dried in a blast oven at 70 ° C for 18 h, and the composite particles were obtained after grinding; 15 g of the composite particles were added to 50 g of ethanol, stirred for 15 min, and the composite particles were obtained. The composite particle dispersion was prepared; 3.08 g of a silane coupling agent was mixed with 50 g of ethanol, and the mixture was ultrasonically dispersed for 15 min to obtain a silane coupling agent dispersion; the silane coupling agent dispersion was mixed with the composite particle dispersion, and 4.92 g of perfluorodecyltrimethylsilane was added, and the mixture was reacted with magnetic stirring for 12 h. After the reaction, the mixture was centrifuged, and the obtained precipitate was repeatedly washed 3 times with anhydrous ethanol, and then dried at 80 ° C with a blower for 24 h and ground to complete the hydrophobic treatment to obtain silica composite carbon nanotubes.

[0030] Preparation of wear-resistant components: 15 g of graphene oxide was mixed with 100 ml of toluene, and 15 g of bromomethyldimethylsilyl chloride was added under nitrogen protection and magnetic stirring. The temperature was raised to 70 ° C, refluxed for 4 h, and centrifuged to obtain the product. The product was washed alternately with toluene and ethanol for 3 times, and then dried to obtain modified graphene oxide. 13.04 g of modified graphene oxide, 16.96 g of silicon dioxide composite carbon nanotubes and 200 ml of dimethylformamide were mixed, ultrasonically dispersed for 30 min, and stirred under nitrogen protection and magnetic stirring. Under stirring conditions, the temperature is raised to 110°C, the reaction is carried out for 12 hours, the product is collected by centrifugal filtration, the collected solid is washed three times with dimethylformamide and formaldehyde, and then dried in a drying oven at 70°C for 12 hours to obtain a composite product, the composite product, 75g of tannic acid and 150g of ethanol are mixed, kept under vacuum conditions for 30 minutes, centrifuged at a speed of 8000 / min for 10 minutes, then washed three times with ethanol, dried at 60°C for 12 hours, and ground to obtain a wear-resistant component.

[0031] Preparation of inkjet ink: After monofunctional UV monomer, difunctional UV monomer, inhibitor, photoinitiator, hyperbranched acrylic resin, leveling agent, color paste and wear-resistant component are mixed, stirred fully, and then three-stage filtration is performed. The filter elements are 0.8um, 0.5um and 0.3um respectively. After filtration, the inkjet ink is obtained, in which monofunctional UV monomer accounts for 30%, difunctional UV monomer accounts for 7.3%, inhibitor accounts for 0.2%, photoinitiator accounts for 12%, leveling agent accounts for 0.5%, black paste accounts for 18%, wear-resistant component accounts for 7%, and the rest is supplemented by 6-functional hyperbranched acrylic resin. Among them, the monofunctional UV monomer is 1,3-dimethylpentylamine (CAS No.: 105-41-9); the difunctional UV monomer is 1,6-hexanediol diacrylate (CAS No.: 13048-33-4).

[0032] Example 3 Preparation of silicon dioxide composite carbon nanotubes: 5 g of carboxyl carbon nanotubes, 140 g of isopropanol and 60 g of deionized water were mixed, 7.14 g of ammonia water was added, ultrasonic dispersion was performed for 10 min, and then 17.86 g of tetraethyl orthosilicate was added, and the mixture was reacted at 55 ° C for 12 h. After the reaction, deionized water and ethanol were used for alternating centrifugal washing for 3 times, and then dried in a blast oven at 70 ° C for 18 h, and the composite particles were obtained after grinding; 15 g of the composite particles were added to 50 g of ethanol, stirred for 15 min, and the composite particles were obtained. The composite particle dispersion was prepared; 3.2 g of a silane coupling agent was mixed with 50 g of ethanol, and the mixture was ultrasonically dispersed for 15 min to obtain a silane coupling agent dispersion; the silane coupling agent dispersion was mixed with the composite particle dispersion, and 4.8 g of perfluorodecyltrimethylsilane was added, and the mixture was reacted with magnetic stirring for 12 h. After the reaction, the mixture was centrifuged, and the obtained precipitate was repeatedly washed 3 times with anhydrous ethanol, and then dried at 80 ° C with a blower for 24 h and ground to complete the hydrophobic treatment to obtain silica composite carbon nanotubes.

[0033] Preparation of wear-resistant components: 15 g of graphene oxide was mixed with 100 ml of toluene, and 15 g of bromomethyldimethylsilyl chloride was added under nitrogen protection and magnetic stirring. After heating to 70 ° C, refluxed for 4 h, centrifuged to obtain the product, and washed alternately with toluene and ethanol for 3 times, and then dried to obtain modified graphene oxide; 13.64 g of modified graphene oxide, 16.36 g of silicon dioxide composite carbon nanotubes and 200 ml of dimethylformamide were mixed, ultrasonically dispersed for 30 min, and stirred under nitrogen protection and magnetic stirring. Under stirring conditions, the temperature is raised to 110°C, the reaction is carried out for 12 hours, the product is collected by centrifugal filtration, the collected solid is washed three times with dimethylformamide and formaldehyde, and then dried in a drying oven at 70°C for 12 hours to obtain a composite product, the composite product, 75g of tannic acid and 150g of ethanol are mixed, kept under vacuum conditions for 30 minutes, centrifuged at a speed of 8000 / min for 10 minutes, then washed three times with ethanol, dried at 60°C for 12 hours, and ground to obtain a wear-resistant component.

[0034] Preparation of inkjet ink: After monofunctional UV monomer, difunctional UV monomer, inhibitor, photoinitiator, hyperbranched acrylic resin, leveling agent, color paste and wear-resistant component are mixed, stirred fully, and then three-stage filtration is performed. The filter elements are 0.8um, 0.5um, and 0.3um respectively. After filtration, the inkjet ink is obtained, and the monofunctional UV monomer accounts for 30%, the difunctional UV monomer accounts for 7.3%, the inhibitor accounts for 0.2%, the photoinitiator accounts for 12%, the leveling agent accounts for 0.5%, the black paste accounts for 18%, the wear-resistant component accounts for 6%, and the rest is supplemented by 6-functional hyperbranched acrylic resin. Among them, the monofunctional UV monomer is prepared by mixing 1,3-dimethylpentylamine and 4-acryloylmorpholine in a mass ratio of 1:1; the difunctional UV monomer is prepared by mixing 1,6-hexanediol diacrylate and dipropylene glycol diacrylate in a mass ratio of 1:1.

[0035] Example 4 Example 4 is based on Example 3. The difference between Example 4 and Example 3 is that in Example 4, when preparing silicon dioxide composite carbon nanotubes, 3.08 g of carboxyl carbon nanotubes, 19.23 g of ethyl orthosilicate, and 7.69 g of ammonia water are used.

[0036] Example 5 Example 5 is based on Example 3. The difference between Example 5 and Example 3 is that in Example 5, when preparing silicon dioxide composite carbon nanotubes, 6.66 g of carboxyl carbon nanotubes, 16.67 g of ethyl orthosilicate and 6.67 g of ammonia water are used.

[0037] Example 6 Example 6 is based on Example 3. The difference between Example 6 and Example 3 is that in Example 6, when preparing silicon dioxide composite carbon nanotubes, 3.64 g of silane coupling agent and 4.36 g of perfluorodecyltrimethylsilane are used.

[0038] Example 7 Example 7 is based on Example 3. The difference between Example 7 and Example 3 is that in Example 7, when preparing silicon dioxide composite carbon nanotubes, 2.86 g of silane coupling agent and 5.14 g of perfluorodecyltrimethylsilane are used.

[0039] Example 8 Example 8 is based on Example 3. The difference between Example 8 and Example 3 is that in Example 8, when preparing silicon dioxide composite carbon nanotubes, the reaction time after adding tetraethyl orthosilicate is 8 hours.

[0040] Example 9 Example 9 is based on Example 3. The difference between Example 9 and Example 3 is that in Example 9, when preparing silicon dioxide composite carbon nanotubes, the reaction time after adding tetraethyl orthosilicate is 16 hours.

[0041] Example 10 Example 10 is based on Example 3. The difference between Example 10 and Example 3 is that in Example 10, when preparing the wear-resistant component, 14.21 g of silicon dioxide composite carbon nanotubes and 15.79 g of modified graphene oxide are used.

[0042] Embodiment 11 Example 11 is based on Example 3. The difference between Example 11 and Example 3 is that in Example 11, when preparing the wear-resistant component, 18 g of silica composite carbon nanotubes and 12 g of modified graphene oxide are used.

[0043] Example 12 Example 12 is based on Example 3. The difference between Example 12 and Example 3 is that in Example 12, tannic acid is not added when preparing the wear-resistant component.

[0044] Embodiment 13 Example 13 is based on Example 3. The difference between Example 13 and Example 3 is that in Example 13, no hydrophobic treatment is performed when preparing the silicon dioxide carbon nanotubes.

[0045] Comparative Example 1 Comparative Example 1 is based on Example 3, and the modified graphene oxide in the wear-resistant component in Comparative Example 1 is replaced by ordinary graphene oxide.

[0046] Comparative Example 2 Comparative Example 2 is based on Example 3. In the wear-resistant component of Comparative Example 2, the silicon dioxide composite carbon nanotubes are prepared by physically mixing nano silicon dioxide and carboxyl carbon nanotubes.

[0047] Comparative Example 3 Comparative Example 3 is based on Example 3, and no wear-resistant component is added in Comparative Example 3.

[0048] Performance testing The following performance tests were performed on the samples of Examples 1-13 and Comparative Examples 1-3: (1) Viscosity test The viscosity of the sample was tested at a temperature of 25°C. Each sample was tested three times, and the average value was taken. The test results were filled in Table 1.

[0049] (2) Particle size The particle size of the sample was tested three times, each sample was tested three times, the average value was taken, and the test results were filled in Table 1.

[0050] (3) Conductivity test The conductivity of the samples was tested three times, each sample was tested three times, the average value was taken, and the test results were filled in Table 1.

[0051] (4)Lightfastness The light resistance of the samples was tested three times, and the average value was taken. The test results were filled in Table 1.

[0052] (5) Surface tension The surface tension of the samples was tested 3 times for each sample, and the average value was taken. The test results were filled in Table 1.

[0053] (6) Wear resistance The wear resistance of the samples was tested according to GB3960-8. Each sample was tested three times, and the average value was taken. The test results were filled in Table 1.

[0054] (7) Hydrophobic angle The hydrophobic angle of the sample was tested three times, each sample was tested three times, the average value was taken, and the test results were filled in Table 1.

[0055] Table 1 Performance test results of Examples 1-13 and Comparative Examples 1-3 Combined with Table 1, it can be seen that the viscosity of Examples 1-3 is between 12.3-13.2cp, indicating that the inkjet ink prepared in the present application has good adhesion performance; the particle size of Examples 1-3 is 280nm or less, the light resistance is above level 4, and the surface tension is between 28-31, indicating that the inkjet ink prepared in the present application has good stability; the conductivity of Examples 1-3 is 1335μS / cm or less, indicating that the inkjet ink prepared in the present application has good antistatic properties; the wear resistance coefficient of Examples 1-3 is 0.32 or less, indicating that the application itself has good wear resistance; the hydrophobic angle of Examples 1-3 is 136° or more, indicating that the present application has good hydrophobic properties.

[0056] In Examples 4 and 5, when preparing silica composite carbon nanotubes, the mass ratios of carboxyl carbon nanotubes, tetraethyl orthosilicate and ammonia water are not within the range specified in the present application. When the content of tetraethyl orthosilicate is too little, the particle size of the prepared silica composite carbon nanotubes is too small, and serious adhesion occurs, affecting the overall stability of the system; when the content of tetraethyl orthosilicate is too much, the particle size of some of the prepared silica composite carbon nanotubes is too large, which reduces the particle size uniformity of the system and causes agglomeration, affecting the overall stability of the system. Therefore, the performance of Examples 4 and 5 are both reduced.

[0057] In Examples 6 and 7, when preparing silica composite carbon nanotubes, the mass ratio of the coupling agent used to perfluorodecyltrimethylsilane is not within the range specified in the present application. When the content of the silane coupling agent is too much, too little perfluorodecyltrimethylsilane makes it difficult to further coat and modify the system, and the hydrophobic performance of the system decreases. When the content of perfluorodecyltrimethylsilane is too much, the excess fluorosilane will undergo self-polymerization to generate a homopolymer, forming a steric hindrance, which affects the hydrophobic modification of the system and reduces the hydrophobic performance. Therefore, the performance of Examples 6 and 7 decreases.

[0058] In Examples 8 and 9, when preparing silica composite carbon nanotubes, the reaction time is not within the range specified in the present application. When the reaction time is too short, the reaction of tetraethyl orthosilicate is incomplete, the contact and bonding performance between silica and carbon nanotubes is difficult to further improve, and silica is difficult to grow stably on the surface of carbon nanotubes. Therefore, the stability of the prepared silica carbon nanotubes is reduced; when the reaction time is too long, the hydrolysis of tetraethyl orthosilicate causes silica to gel, and the particles agglomerate with each other, affecting the stability of the system. Therefore, the performance of Examples 8 and 9 is reduced.

[0059] In Example 10 and Example 11, when preparing the wear-resistant component, the mass ratio between the silica composite carbon nanotubes and the modified graphene oxide is not within the range specified in the present application. When the silica content is too much, the content of the small balls with a mesoporous structure is reduced, the adsorption performance for tannic acid is reduced, and the antistatic performance of the system is affected; when the silica content is too little, the synergistic effect of the combination between the systems is also reduced, affecting the overall performance of the system. Therefore, the performance of Example 10 and Example 11 is reduced.

[0060] In Example 12, tannic acid was not added when preparing the wear-resistant component. It is difficult to further improve the antistatic properties of the system without adding tannic acid. At the same time, it is difficult to improve the bonding performance between the silica composite carbon nanotubes and the modified graphene oxide. Therefore, the performance of Example 12 is reduced.

[0061] In Example 13, the silica composite carbon nanotubes were not subjected to hydrophobic treatment, and the hydrophobic angle of the silica carbon nanotubes that were not subjected to hydrophobic treatment was difficult to be further improved. Therefore, the overall hydrophobic performance of Example 13 was reduced, and the wear resistance was also affected. Therefore, the performance of Example 13 was reduced.

[0062] In Comparative Example 1, the modified graphene oxide in the wear-resistant component is replaced with ordinary graphene oxide. The binding performance between the unmodified graphene oxide and the silicon dioxide composite carbon nanotubes is reduced, which affects the overall stability of the system. Therefore, the performance of Comparative Example 1 is reduced.

[0063] The silica composite carbon nanotubes in Comparative Example 2 are prepared by simply physically mixing silica and carboxyl carbon nanotubes. The physically mixed silica composite carbon nanotubes have poor binding properties and agglomeration occurs in the system, affecting the overall stability of the system. Therefore, the performance of Comparative Example 2 is reduced.

[0064] In Comparative Example 3, no wear-resistant component is added to the system, and the overall performance of the inkjet ink without the addition of the wear-resistant component is difficult to be further improved, so the performance of Comparative Example 3 is reduced.

[0065] It is difficult to combine the two stably to synergistically improve the performance of the inkjet ink, so the performance of Example 10 and Example 11 are both reduced.

[0066] This specific embodiment is only an explanation of the present application, and it is not a limitation of the present application. Through the above description, relevant staff can make various changes and modifications without deviating from the technical idea of ​​the present application. The technical scope of the present application is not limited to the content in the specification, and its technical scope must be determined according to the scope of the claims.

Claims

1. A two-dimensional code UV inkjet ink, characterized by: The invention comprises a monofunctional UV monomer, a difunctional UV monomer, an inhibitor, a photoinitiator, a hyperbranched acrylic resin, a leveling agent, a color paste and a wear-resistant component; the wear-resistant component comprises graphene oxide and silicon dioxide composite carbon nanotubes.

2. A two-dimensional code UV inkjet ink according to claim 1, characterized in that: The silicon dioxide composite carbon nanotubes are prepared by the following method: The carboxyl carbon nanotubes, isopropanol and water are mixed, and then ammonia water is added, and after ultrasonic dispersion, ethyl orthosilicate is added to react, and after the reaction, the composite particles are washed and dried to obtain composite particles; the composite particles are hydrophobicized to obtain silicon dioxide composite carbon nanotubes.

3. A two-dimensional code UV inkjet ink according to claim 2, characterized in that: The hydrophobic treatment comprises the following steps: The composite particles are added into ethanol and stirred to obtain a composite particle dispersion; the silane coupling agent is mixed with ethanol and ultrasonically dispersed to obtain a silane coupling agent dispersion; the silane coupling agent dispersion is mixed with the composite particle dispersion, and perfluorodecyltrimethylsilane is added and stirred for reaction. After the reaction, the precipitate is washed and dried to complete the hydrophobic treatment and obtain silicon dioxide composite carbon nanotubes.

4. A two-dimensional code UV inkjet ink according to claim 2, characterized in that: The mass ratio of the carboxyl carbon nanotubes, tetraethyl orthosilicate and ammonia water is (0.6-0.8):2.5:

1.

5. The two-dimensional code UV inkjet ink according to claim 2, characterized in that: The reaction time is 10-14h.

6. A two-dimensional code UV inkjet ink according to claim 3, characterized in that: The mass ratio between the silane coupling agent and perfluorodecyltrimethoxysilane is 1:(1.4-1.6).

7. The two-dimensional code UV inkjet ink according to claim 1, characterized in that: The wear-resistant component is prepared by the following method: The graphene oxide is mixed with toluene, bromomethyldimethylsilyl chloride is added, the temperature is raised and refluxed, centrifugal filtration and washing are performed, and the modified graphene oxide is obtained by drying; the modified graphene oxide, silicon dioxide composite carbon nanotubes and dimethylformamide are mixed, ultrasonically dispersed, heated for reaction, centrifugal filtration and washing are performed, and the composite product is obtained by drying; the composite product, tannic acid and ethanol are mixed, vacuumized, centrifuged and washed, and the wear-resistant component is obtained by drying.

8. The two-dimensional code UV inkjet ink according to claim 7, characterized in that: The mass ratio between the modified graphene oxide and the silicon dioxide composite carbon nanotubes is 1:(1.1-1.3).

9. The two-dimensional code UV inkjet ink according to claim 1, characterized in that: The wear-resistant component content accounts for 5-7% of the entire inkjet ink system.

10. A method for preparing the two-dimensional code UV inkjet ink according to any one of claims 1 to 9, characterized in that: The steps include: After monofunctional UV monomer, difunctional UV monomer, inhibitor, photoinitiator, hyperbranched acrylic resin, leveling agent, color paste and wear-resistant component are mixed, fully stirred, and then three-stage filtration is performed. The filter elements are 0.8um, 0.5um, and 0.3um respectively. After filtration, the inkjet ink is obtained.

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