Cross-linked polymer micronized wax powder for printing ink and preparation method of cross-linked polymer micronized wax powder

Abstract

The invention relates to the field of printing ink, and discloses cross-linked polymer micronized wax powder for printing ink and a preparation method thereof.According to the printing ink, a wax monomer is introduced into epoxy acrylate, and a core-shell polymer emulsion is prepared through a soap-free core-shell emulsion polymerization method, a polymer formed by butyl acrylate, acrylic acid, a functionalized silane coupling agent and a comonomer is taken as a shell, and the cross-linked polymer micronized wax powder for the ink is prepared by adopting a spray drying process; the functionalized silane coupling agent is prepared by reacting a modified silane coupling agent obtained by reacting vinyltrimethoxysilane with tetramethyldisiloxane with eugenol to prepare an eugenol-based modified silane coupling agent, and then reacting the eugenol-based modified silane coupling agent with isocyano ethyl methacrylate; the comonomer is prepared by reacting eugenol, cardanol and 1, 4-p-xylylene dichloride, and the obtained product has the antibacterial property, water resistance and adhesive force of a shell layer monomer and the mechanical property, heat resistance and antibacterial property of a core layer monomer.

Description

Technical Field

[0001] The invention belongs to the technical field of inks, and in particular relates to a cross-linked polymer micro wax powder for ink and a preparation method thereof. Background Art

[0002] In the field of ink technology, natural and synthetic wax additives play an important role in the performance quality of the products, contributing to the surface properties of the final coated product, improving coating integrity and surface appearance, as well as facilitating downstream processing of the coated product and extending its service life. Natural wax is composed of long-chain fatty acid esters with a low softening point, and high-temperature coatings are prone to failure and uneven gloss; low-molecular synthetic wax has a low molecular weight, low melting point, low hardness, poor high-temperature resistance, and poor compatibility with resins. A slightly higher addition amount will easily cause fogging and fail to meet high performance and functional requirements; polytetrafluoroethylene wax has a high melting point, good high-temperature resistance and wear resistance, and is suitable for high-end industrial paints, but it is expensive and difficult to disperse; and traditional wax cannot take into account the multifunctional requirements of slipperiness and scratch resistance, wear resistance, and touch, which limits the application range of the coating. In addition, water-based polyurethane is used as a binder resin in existing water-based inks. Water-based polyurethane is widely used in water-based inks due to its good film-forming properties, flexibility and chemical stability, but water-based polyurethane has slightly poor wear resistance, antibacterial properties, and scratch resistance. Moreover, because it contains a large number of hydrophilic groups, its water resistance and heat resistance need to be further improved. Summary of the Invention

[0003] In order to solve the deficiencies mentioned in the above-mentioned background technology, the purpose of the present invention is to provide a cross-linked polymer micro-wax powder for ink and a preparation method thereof. The obtained cross-linked polymer micro-wax powder not only has the excellent antibacterial properties, water resistance, adhesion and film-forming properties of the shell monomer, but also has the mechanical properties, heat resistance, antibacterial and weather resistance of the core monomer, and combines the smoothness and lubricity of the wax monomer and the functionality of the core-shell polymer emulsion.

[0004] The purpose of the present invention can be achieved through the following technical solutions: A method for preparing cross-linked polymer micro wax powder for ink, comprising the following steps: A. Epoxy resin and styrene are placed in a reactor, stirred evenly, and then wax monomer and hydroquinone are added. The mixture is placed in an oil bath at 105-115°C and stirred for 8-12 minutes. Acrylic acid and triethylamine are then mixed evenly and added dropwise to the reactor within 30-40 minutes. After the addition is completed, the mixture is kept at a constant temperature for 2-2.5 hours to prepare a modified wax monomer. B. Take two parts of the emulsifier SE-10N dissolved in deionized water, place them at 60-65°C, add modified wax monomer and butyl acrylate respectively for pre-emulsification, and obtain core pre-emulsion and shell pre-emulsion, respectively. Then, reduce the temperature of the core pre-emulsion to 40-45°C, introduce nitrogen, add acrylic acid, functionalized silane coupling agent, comonomer and acrylamide, and continue to react for 0.5-1 hour. Then, add initiators sodium bisulfite and ammonium persulfate, and drop the shell pre-emulsion into the core pre-emulsion within 1.5-2 hours. After the addition is completed, place them at 65-70°C and continue to react for 2-2.5 hours to prepare a core-shell polymer emulsion; C. Add a defoamer to the core-shell polymer emulsion and continue stirring until uniform. Filter the resulting dispersion at room temperature and pressure and then spray dry it to prepare a cross-linked polymer microwax powder for ink. The functionalized silane coupling agent is prepared by subjecting vinyltrimethoxysilane and tetramethyldisiloxane to a hydrosilylation reaction, and then subjecting the prepared modified silane coupling agent to a further hydrosilylation reaction with eugenol to prepare a eugenol-modified silane coupling agent, which is then subjected to a nucleophilic addition reaction with isocyanoethyl methacrylate; the comonomer is prepared by subjecting eugenol and cardanol to a substitution reaction with the chlorine atoms at both ends of 1,4-dichlorobenzyl, respectively.

[0005] Preferably, the wax monomer is one or more of oxidized polyethylene wax, maleic anhydride grafted polyethylene wax, maleic anhydride grafted polypropylene wax, and oxidized Fischer-Tropsch wax.

[0006] Preferably, in step A, the mass ratio of epoxy resin, wax monomer and hydroquinone is 50:0.4-0.9:0.08.

[0007] Preferably, in step B, the mass ratio of the modified wax monomer, butyl acrylate, acrylic acid, functionalized silane coupling agent, and comonomer is 10:18-20:0.8-1:0.5-0.7:3-4.

[0008] Preferably, the process parameters of the spray drying in step C are: inlet air temperature of 155-170°C, outlet air temperature of 75-90°C, and atomizer speed of 12000-15000 r / min.

[0009] Preferably, the epoxy resin is E44; and the defoaming agent is BYK-011.

[0010] Preferably, the preparation method of the functionalized silane coupling agent in step B comprises the following steps: B1. Vinyltrimethoxysilane and tetramethyldisiloxane were placed in a reactor filled with toluene, and the temperature was raised to 75-80° C. under a nitrogen atmosphere. Wilkinson catalyst was then added and the reaction was continued at a constant temperature for 5-6 hours. After the reaction was completed, the solvent was removed by rotary evaporation. The reaction product was poured into a chromatography column filled with silica gel, and the eluent was prepared with n-hexane and ethyl acetate. After elution, the column was vacuum-evaporated to prepare a modified silane coupling agent. B2. Place eugenol and Custer's catalyst into a reactor containing toluene, raise the temperature to 55-60° C. under a nitrogen atmosphere, then add a modified silane coupling agent and stir to react for 20-24 hours. After the reaction is complete, remove the unreacted product by rotary evaporation to prepare a eugenol-based modified silane coupling agent; B3. Take eugenol-modified silane coupling agent, isocyanoethyl methacrylate and dibutyltin dilaurate, put them into a reactor filled with acetone, heat to 45-50°C, stir and react for 10-12 hours. After the reaction is completed, carry out rotary evaporation, wash and dry to prepare a functionalized silane coupling agent.

[0011] Preferably, in step B1, the molar ratio of vinyltrimethoxysilane to tetramethyldisiloxane is 1-1.1:1.

[0012] Preferably, the method for preparing the comonomer comprises the following steps: taking eugenol and placing it in a reactor filled with N,N-dimethylformamide, heating it to 50-60°C under a nitrogen atmosphere, then adding sodium hydroxide and 1,4-dichlorobenzyl, stirring and reacting for 2-3 hours, then adding cardanol, heating it to 75-80°C and continuing the reaction for 3-4 hours, and after the reaction is completed, filtering, washing, and drying to prepare the comonomer.

[0013] A cross-linked polymer micro wax powder for ink is prepared by the above-mentioned preparation method.

[0014] Beneficial effects of the present invention: The present invention utilizes a hydrosilylation reaction between a molecule of vinyltrimethoxysilane and tetramethyldisiloxane to prepare a modified silane coupling agent. Eugenol then undergoes a hydrosilylation reaction with the ungrafted silane-hydrogen bonds in the modified silane coupling agent to produce a eugenol-modified silane coupling agent. This eugenol-modified silane coupling agent then undergoes a nucleophilic addition reaction with isocyanoethyl methacrylate to produce a functionalized silane coupling agent. This silane coupling agent incorporates the natural antibacterial agent eugenol, a highly heat-resistant and water-resistant organosilicon chain segment, and a rigid benzene ring into its structure, imparting excellent water and wear resistance, heat resistance, and antibacterial properties to the core monomer. In addition, the present invention utilizes eugenol and cardanol to undergo substitution reactions with the chlorine atoms at both ends of 1,4-dichlorobenzyl, respectively, to prepare a comonomer containing a double bond and a hydrophobic alkyl long chain. Eugenol and cardanol are both green and environmentally friendly raw materials with low cost and are renewable. The comonomers are introduced into the emulsion polymerization system to give the shell monomer good antibacterial properties, adhesion and water resistance.

[0015] The present invention introduces a wax monomer into epoxy acrylate. The hydroxyl or carboxyl groups in the wax monomer and the epoxy groups in the epoxy acrylate can form hydrogen bonds, thereby enhancing intermolecular interactions and further promoting the occurrence of crosslinking reactions. A core-shell polymer emulsion is prepared using a soap-free core-shell emulsion polymerization method, wherein the modified wax monomer serves as the core and a polymer formed by butyl acrylate, acrylic acid, a functionalized silane coupling agent, and a comonomer serves as the shell. A spray drying process is then used to prepare a crosslinked polymer microwax powder for ink. The crosslinked polymer microwax powder prepared by the present invention combines the slipperiness and lubricity of the wax monomer with the functionality of the polymer emulsion. The encapsulated wax monomer facilitates uniform distribution in the ink system, has good compatibility with polar resins (such as water-based systems, epoxies, and polyurethanes), and is gradually released during the printing or drying process, continuously providing lubrication and protection. In addition, the crosslinked polymer microwax powder obtained by the present invention combines the excellent mechanical properties, antibacterial properties, heat resistance, water resistance, and adhesion of the shell monomer. DETAILED DESCRIPTION

[0016] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts shall fall within the scope of protection of the present invention.

[0017] Example 1 A method for preparing a functionalized silane coupling agent comprises the following steps: B1. 3.7 g of vinyltrimethoxysilane and 3.3 g of tetramethyldisiloxane were placed in a reactor containing 50 mL of toluene, and the temperature was raised to 80 ° C. under a nitrogen atmosphere. Then, 0.005 g of Wilkinson catalyst was added and the reaction was continued at a constant temperature for 6 h. After the reaction was completed, the solvent was removed by rotary evaporation. The reaction product was poured into a chromatography column filled with silica gel, and the eluent was prepared using 60 mL of n-hexane and 30 mL of ethyl acetate. After elution, vacuum rotary evaporation was performed to prepare a modified silane coupling agent; B2, taking 3.5g of eugenol and 0.08g of Custer catalyst into a reactor filled with 20mL of toluene, heating to 60°C under a nitrogen atmosphere, then adding 6.1g of modified silane coupling agent and stirring to react for 24h. After the reaction is completed, the unreacted material is removed by rotary evaporation to prepare a eugenol-based modified silane coupling agent; B3. Take 8.8 g of eugenol-modified silane coupling agent, 3.2 g of isocyanoethyl methacrylate and a drop of dibutyltin dilaurate, put them into a reactor filled with 40 mL of acetone, heat to 45°C, stir and react for 12 hours, and after the reaction is completed, remove the unreacted materials by rotary evaporation to prepare a functionalized silane coupling agent.

[0018] Example 2 A method for preparing a comonomer comprises the following steps: 2.5 g of eugenol was placed in a reactor containing 50 mL of N,N-dimethylformamide, and the temperature was raised to 55 ° C under a nitrogen atmosphere. Then 1.3 g of sodium hydroxide and 2.7 g of 1,4-dichlorobenzyl were added and stirred for 2 h. Subsequently, 4.8 g of cardanol was added and the temperature was raised to 80 ° C and the reaction was continued for 3.5 h. After the reaction was completed, the comonomer was prepared by filtration, washing, and drying.

[0019] Example 3 A method for preparing a cross-linked polymer wax powder for ink comprises the following steps: A. Take 50g of epoxy resin E44 and 75g of styrene in a reactor, stir evenly, add 0.45g of oxidized polyethylene wax and 0.08g of hydroquinone, place in an oil bath at 110°C and stir for 10 minutes, then mix 16.5g of acrylic acid and 0.25g of triethylamine evenly and add dropwise to the reactor within 40 minutes. After the addition is completed, react at a constant temperature for 2 hours to prepare a modified wax monomer; B. Dissolve 3g of emulsifier SE-10N in 150mL of deionized water and dissolve 4g of emulsifier SE-10N in 200mL of deionized water. Place 100g of modified wax monomer and 180g of butyl acrylate at 65°C for pre-emulsification to obtain core pre-emulsion and shell pre-emulsion, respectively. Then, reduce the temperature of the core pre-emulsion to 45°C, introduce nitrogen, add 10g of acrylic acid, 5g of functionalized silane coupling agent, 40g of comonomer and 3g of acrylamide, and continue to react for 0.5h. Then, add 0.8g of initiator sodium bisulfite and 1.2g of ammonium persulfate, and add the shell pre-emulsion dropwise to the core pre-emulsion within 2h. After the addition is completed, place at 65°C and continue to react for 2h to prepare a core-shell polymer emulsion. C. Add defoamer BYK-011 to the core-shell polymer emulsion and continue stirring evenly. Filter the obtained dispersion at room temperature and pressure and then spray dry it. The inlet air temperature is 155°C, the outlet air temperature is 78°C, and the atomizer speed is 12000 r / min to prepare a cross-linked polymer micro wax powder for ink.

[0020] Example 4 A method for preparing a cross-linked polymer wax powder for ink comprises the following steps: A. Take 50g of epoxy resin E44 and 75g of styrene in a reactor, stir evenly, add 0.78g of oxidized polyethylene wax and 0.08g of hydroquinone, place in an oil bath at 110°C and stir for 10 minutes, then mix 16.5g of acrylic acid and 0.25g of triethylamine evenly and add dropwise to the reactor within 40 minutes. After the addition is completed, react at a constant temperature for 2 hours to prepare a modified wax monomer; B. Dissolve 3g of emulsifier SE-10N in 150mL of deionized water and dissolve 4g of emulsifier SE-10N in 200mL of deionized water. Place 100g of modified wax monomer and 200g of butyl acrylate at 65°C for pre-emulsification to obtain core pre-emulsion and shell pre-emulsion, respectively. Then, reduce the temperature of the core pre-emulsion to 45°C, introduce nitrogen, add 9g of acrylic acid, 5.5g of functionalized silane coupling agent, 35g of comonomer and 3g of acrylamide, and continue to react for 0.5h. Then, add 0.8g of initiator sodium bisulfite and 1.2g of ammonium persulfate, and add the shell pre-emulsion dropwise to the core pre-emulsion within 2h. After the addition is completed, place at 65°C and continue to react for 2h to prepare a core-shell polymer emulsion. C. Add defoamer BYK-011 to the core-shell polymer emulsion and continue stirring evenly. Filter the obtained dispersion at room temperature and pressure and then spray dry it. The inlet air temperature is 165°C, the outlet air temperature is 85°C, and the atomizer speed is 13000 r / min to prepare a cross-linked polymer micro wax powder for ink.

[0021] Example 5 A method for preparing a cross-linked polymer wax powder for ink comprises the following steps: A. Take 50g of epoxy resin E44 and 75g of styrene in a reactor, stir evenly, add 0.88g of oxidized polyethylene wax and 0.08g of hydroquinone, place in an oil bath at 110°C and stir for 10 minutes, then mix 16.5g of acrylic acid and 0.25g of triethylamine evenly and add dropwise to the reactor within 40 minutes. After the addition is completed, react at a constant temperature for 2 hours to prepare a modified wax monomer; B. Dissolve 3g of emulsifier SE-10N in 150mL of deionized water and dissolve 4g of emulsifier SE-10N in 200mL of deionized water. Place 100g of modified wax monomer and 180g of butyl acrylate at 65°C for pre-emulsification to obtain core pre-emulsion and shell pre-emulsion, respectively. Then, reduce the temperature of the core pre-emulsion to 45°C, introduce nitrogen, add 8g of acrylic acid, 6.5g of functionalized silane coupling agent, 30g of comonomer and 3g of acrylamide, and continue to react for 0.5h. Then, add 0.8g of initiator sodium bisulfite and 1.2g of ammonium persulfate, and add the shell pre-emulsion dropwise to the core pre-emulsion within 2h. After the addition is completed, place at 65°C and continue to react for 2h to prepare a core-shell polymer emulsion. C. Add defoamer BYK-011 to the core-shell polymer emulsion and continue stirring evenly. Filter the obtained dispersion at room temperature and pressure and then spray dry it. The inlet air temperature is 170°C, the outlet air temperature is 90°C, and the atomizer speed is 15000 r / min to prepare a cross-linked polymer micro wax powder for ink.

[0022] Comparative Example 1 A method for preparing a cross-linked polymer micro wax powder for ink comprises the following steps: A. Take 50g of epoxy resin E44 and 75g of styrene in a reactor, stir evenly, add 0.88g of oxidized polyethylene wax and 0.08g of hydroquinone, place in an oil bath at 110°C and stir for 10 minutes, then mix 16.5g of acrylic acid and 0.25g of triethylamine evenly and add dropwise to the reactor within 40 minutes. After the addition is completed, react at a constant temperature for 2 hours to prepare a modified wax monomer; B. Dissolve 3g of emulsifier SE-10N in 150mL of deionized water and dissolve 4g of emulsifier SE-10N in 200mL of deionized water. Place 100g of modified wax monomer and 180g of butyl acrylate at 65°C for pre-emulsification to obtain core pre-emulsion and shell pre-emulsion, respectively. Then, reduce the temperature of the core pre-emulsion to 45°C, introduce nitrogen, add 8g of acrylic acid, 6.5g of vinyltrimethoxysilane, 30g of comonomer and 3g of acrylamide, and continue to react for 0.5h. Then, add 0.8g of initiator sodium bisulfite and 1.2g of ammonium persulfate, and add the shell pre-emulsion dropwise to the core pre-emulsion within 2h. After the addition is completed, place at 65°C and continue to react for 2h to prepare a core-shell polymer emulsion. C. Add defoamer BYK-011 to the core-shell polymer emulsion and continue stirring evenly. Filter the obtained dispersion at room temperature and pressure and then spray dry it. The inlet air temperature is 170°C, the outlet air temperature is 90°C, and the atomizer speed is 15000 r / min to prepare a cross-linked polymer micro wax powder for ink.

[0023] Comparative Example 2 A method for preparing a cross-linked polymer micro wax powder for ink comprises the following steps: A. Take 50g of epoxy resin E44 and 75g of styrene in a reactor, stir evenly, add 0.88g of oxidized polyethylene wax and 0.08g of hydroquinone, place in an oil bath at 110°C and stir for 10 minutes, then mix 16.5g of acrylic acid and 0.25g of triethylamine evenly and add dropwise to the reactor within 40 minutes. After the addition is completed, react at a constant temperature for 2 hours to prepare a modified wax monomer; B. Dissolve 3g of emulsifier SE-10N in 150mL of deionized water and dissolve 4g of emulsifier SE-10N in 200mL of deionized water. Place 100g of modified wax monomer and 180g of butyl acrylate at 65°C for pre-emulsification to obtain core pre-emulsion and shell pre-emulsion, respectively. Then, reduce the temperature of the core pre-emulsion to 45°C, introduce nitrogen, add 8g of acrylic acid, 6.5g of functionalized silane coupling agent, 30g of methyl methacrylate and 3g of acrylamide, and continue to react for 0.5h. Then, add 0.8g of initiator sodium bisulfite and 1.2g of ammonium persulfate, and add the shell pre-emulsion dropwise to the core pre-emulsion within 2h. After the addition is completed, place at 65°C and continue to react for 2h to prepare a core-shell polymer emulsion. C. Add defoamer BYK-011 to the core-shell polymer emulsion and continue stirring evenly. Filter the obtained dispersion at room temperature and pressure and then spray dry it. The inlet air temperature is 170°C, the outlet air temperature is 90°C, and the atomizer speed is 15000 r / min to prepare a cross-linked polymer micro wax powder for ink.

[0024] Comparative Example 3 A method for preparing a cross-linked polymer micro wax powder for ink comprises the following steps: A. Take 50g of epoxy resin E44 and 75g of styrene in a reactor, stir evenly, add 0.88g of oxidized polyethylene wax and 0.08g of hydroquinone, place in an oil bath at 110°C and stir for 10 minutes, then mix 16.5g of acrylic acid and 0.25g of triethylamine evenly and add dropwise to the reactor within 40 minutes. After the addition is completed, react at a constant temperature for 2 hours to prepare a modified wax monomer; B. Dissolve 3g of emulsifier SE-10N in 150mL of deionized water and dissolve 4g of emulsifier SE-10N in 200mL of deionized water. Place 100g of modified wax monomer and 180g of butyl acrylate at 65°C for pre-emulsification to obtain core pre-emulsion and shell pre-emulsion, respectively. Then, reduce the temperature of the core pre-emulsion to 45°C, introduce nitrogen, add 8g of acrylic acid, 30g of comonomer and 3g of acrylamide, and continue to react for 0.5h. Then, add 0.8g of initiator sodium bisulfite and 1.2g of ammonium persulfate, and add the shell pre-emulsion dropwise to the core pre-emulsion within 2h. After the addition is completed, place at 65°C and continue to react for 2h to prepare a core-shell polymer emulsion. C. Add defoamer BYK-011 to the core-shell polymer emulsion and continue stirring evenly. Filter the obtained dispersion at room temperature and pressure and then spray dry it. The inlet air temperature is 170°C, the outlet air temperature is 90°C, and the atomizer speed is 15000 r / min to prepare a cross-linked polymer micro wax powder for ink.

[0025] Performance testing The inks prepared in Examples 3-5 and Comparative Examples 1-3 were subjected to performance testing using cross-linked polymer microwax powders: (1) Particle size analysis: 0.006 g of sample was added to 6 mL of deionized water and ultrasonically dispersed. The average particle size was measured using a dynamic light scattering particle size analyzer. The data results are shown in Table 1.

[0026] (2) Heat resistance test: Under nitrogen atmosphere, the sample was heated from 35°C to 700°C at a heating rate of 10°C / min, and the initial decomposition temperature was recorded to evaluate its heat resistance. The data results are shown in Table 1.

[0027] (3) Antibacterial performance test: The sample was mixed with bacterial suspension (10 6 CFU / mL) were mixed, 200 μL of water-based paint paste was added respectively, the mixture was evenly coated on the culture medium, and cultured at 37°C for 48 h. The antibacterial effect of the sample was evaluated by the inhibition rate, and the data results are shown in Table 1.

[0028] The aqueous polyurethane emulsion, the samples prepared in Examples 3-5 and Comparative Examples 1-3, the aqueous carbon black slurry and sodium carboxymethyl cellulose were mixed to prepare ink, and the following performance tests were performed: (4) Water resistance test: The water contact angle test was performed using a water contact angle meter, and the data results are shown in Table 1.

[0029] (5) Abrasion resistance test: Place a 7000 mesh SiC sandpaper on the ink printed surface, and press a 200g weight on the gauze paper. Drag the sandpaper horizontally at a constant speed for 10cm, rotate the sample 90° clockwise, and then drag it horizontally at a constant speed for 10cm. This is one cycle, and the abrasion cycle is repeated 30 times. The water contact angle of the ink printed surface after abrasion is measured, and the data results are shown in Table 1.

[0030] (6) Hardness test: According to ASTM D3363-00, the hardness of the ink printed surface was tested using a pencil scratch hardness tester. The data results are shown in Table 1.

[0031] (7) Adhesion test: According to ASTM D3359-97, the adhesion test of the ink printed surface was carried out using a grid knife and 3M tape. The data results are shown in Table 1.

[0032] Table 1 Sample performance test results As can be seen from the data results in Table 1, the cross-linked polymer micro-wax powder for ink prepared in Examples 3-5 of the present invention has good hardness, adhesion, antibacterial effect, water resistance, wear resistance, and heat resistance. In Comparative Example 1, the functionalized silane coupling agent was replaced with vinyl trimethoxysilane in equal amounts, and no functionalized silane coupling agent was added in Comparative Example 3. The antibacterial rate, water resistance, wear resistance, hardness, and heat resistance of Comparative Examples 1 and 3 were lower than those of Examples 3-5. This is because the functionalized coupling agent introduced the antibacterial component eugenol, a large number of silane bonds, and rigid benzene rings. The water resistance, wear resistance, and heat resistance of Comparative Example 3 were slightly lower than those of Comparative Example 1. This is because vinyl trimethoxysilane introduced a certain number of silane bonds. In Comparative Example 2, the comonomer was replaced with methyl methacrylate in equal amounts. The antibacterial rate, water contact angle, and adhesion were lower than those of Examples 3-5, indicating that the addition of the comonomer can improve the antibacterial effect, water resistance, and adhesion of the material.

[0033] Throughout this specification, references to terms such as "one embodiment," "example," or "specific example" indicate that the specific features, structures, materials, or characteristics described in conjunction with that embodiment or example are included in at least one embodiment or example of the present invention. In this specification, schematic representations of these terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

[0034] The basic principles, main features, and advantages of the present invention are shown and described above. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The above embodiments and descriptions are merely illustrative of the principles of the present invention. Various changes and modifications may be made to the present invention without departing from the spirit and scope of the present invention, and such changes and modifications fall within the scope of the invention as claimed.

Claims

1. A method for preparing cross-linked polymer micro wax powder for ink, characterized in that: The following steps are involved: A. Epoxy resin and styrene are placed in a reactor, stirred evenly, and then wax monomer and hydroquinone are added. The mixture is placed in an oil bath at 105-115°C and stirred for 8-12 minutes. Acrylic acid and triethylamine are then mixed evenly and added dropwise to the reactor within 30-40 minutes. After the addition is completed, the mixture is kept at a constant temperature for 2-2.5 hours to prepare a modified wax monomer. B. Take two parts of the emulsifier SE-10N dissolved in deionized water, place them at 60-65°C, add modified wax monomer and butyl acrylate respectively for pre-emulsification, and obtain core pre-emulsion and shell pre-emulsion, respectively. Then, reduce the temperature of the core pre-emulsion to 40-45°C, introduce nitrogen, add acrylic acid, functionalized silane coupling agent, comonomer and acrylamide, and continue to react for 0.5-1 hour. Then, add initiators sodium bisulfite and ammonium persulfate, and drop the shell pre-emulsion into the core pre-emulsion within 1.5-2 hours. After the addition is completed, place them at 65-70°C and continue to react for 2-2.5 hours to prepare a core-shell polymer emulsion; C. Add a defoamer to the core-shell polymer emulsion and continue stirring until uniform. Filter the resulting dispersion at room temperature and pressure and then spray dry it to prepare a cross-linked polymer microwax powder for ink. The functionalized silane coupling agent is prepared by subjecting vinyltrimethoxysilane and tetramethyldisiloxane to a hydrosilylation reaction, and then subjecting the prepared modified silane coupling agent to a further hydrosilylation reaction with eugenol to prepare a eugenol-modified silane coupling agent, which is then subjected to a nucleophilic addition reaction with isocyanoethyl methacrylate; the comonomer is prepared by subjecting eugenol and cardanol to a substitution reaction with the chlorine atoms at both ends of 1,4-dichlorobenzyl, respectively.

2. The method for preparing the cross-linked polymer micro wax powder for ink according to claim 1, characterized in that: The wax monomer is one or more of oxidized polyethylene wax, maleic anhydride grafted polyethylene wax, maleic anhydride grafted polypropylene wax, and oxidized Fischer-Tropsch wax.

3. The method for preparing cross-linked polymer micro wax powder for ink according to claim 1, characterized in that: In step A, the mass ratio of epoxy resin, wax monomer and hydroquinone is 50:0.4-0.9:0.

08.

4. The method for preparing cross-linked polymer micro wax powder for ink according to claim 1, characterized in that: In the step B, the mass ratio of the modified wax monomer, butyl acrylate, acrylic acid, functionalized silane coupling agent, and comonomer is 10:18-20:0.8-1:0.5-0.7:3-4.

5. The method for preparing cross-linked polymer micro wax powder for ink according to claim 1, characterized in that: The process parameters of the spray drying in step C are: air inlet temperature of 155-170° C., air outlet temperature of 75-90° C., and atomizer speed of 12,000-15,000 r / min.

6. The method for preparing cross-linked polymer wax powder for ink according to claim 1, characterized in that: The epoxy resin is E44; the defoaming agent is BYK-011.

7. The method for preparing cross-linked polymer wax powder for ink according to claim 1, characterized in that: The preparation method of the functionalized silane coupling agent in step B comprises the following steps: B1. Vinyltrimethoxysilane and tetramethyldisiloxane were placed in a reactor filled with toluene, and the temperature was raised to 75-80° C. under a nitrogen atmosphere. Wilkinson catalyst was then added and the reaction was continued at a constant temperature for 5-6 hours. After the reaction was completed, the solvent was removed by rotary evaporation. The reaction product was poured into a chromatography column filled with silica gel, and the eluent was prepared with n-hexane and ethyl acetate. After elution, the column was vacuum-evaporated to prepare a modified silane coupling agent. B2. Place eugenol and Custer's catalyst into a reactor containing toluene, raise the temperature to 55-60° C. under a nitrogen atmosphere, then add a modified silane coupling agent and stir to react for 20-24 hours. After the reaction is complete, remove the unreacted product by rotary evaporation to prepare a eugenol-based modified silane coupling agent; B3. Take eugenol-modified silane coupling agent, isocyanoethyl methacrylate and dibutyltin dilaurate, put them into a reactor filled with acetone, heat to 45-50°C, stir and react for 10-12 hours. After the reaction is completed, carry out rotary evaporation, wash and dry to prepare a functionalized silane coupling agent.

8. The method for preparing cross-linked polymer wax powder for ink according to claim 7, characterized in that: The molar ratio of vinyltrimethoxysilane to tetramethyldisiloxane in step B1 is 1-1.1:

1.

9. The method for preparing cross-linked polymer wax powder for ink according to claim 1, characterized in that: The preparation method of the comonomer comprises the following steps: taking eugenol and placing it in a reactor filled with N,N-dimethylformamide, heating the mixture to 50-60° C. under a nitrogen atmosphere, then adding sodium hydroxide and 1,4-dichlorobenzyl, stirring and reacting for 2-3 hours, then adding cardanol, heating the mixture to 75-80° C. and continuing the reaction for 3-4 hours, and filtering, washing, and drying the mixture after the reaction is completed to prepare the comonomer.

10. A cross-linked polymer wax powder for ink, characterized in that: Prepared by the preparation method according to any one of claims 1 to 9.

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