Cross-linked polymer micro-wax powder for ink and preparation method thereof

Abstract

The application relates to the field of inks, and discloses a crosslinked polymer micro-wax powder for inks and a preparation method thereof. The ink introduces a wax monomer into an epoxy acrylate, and a core-shell polymer emulsion is prepared by using a soap-free core-shell emulsion polymerization method, wherein the modified wax monomer is a core, a polymer formed by butyl acrylate, acrylic acid, a functionalized silane coupling agent and a comonomer is a shell, and the crosslinked polymer micro-wax powder for inks is prepared by using a spray drying process. The functionalized silane coupling agent is prepared by reacting a modified silane coupling agent obtained by reacting vinyl trimethoxysilane and tetramethyldisiloxane with eugenol, and then is reacted with isocyanatoethyl methacrylate. The comonomer is prepared by reacting eugenol, cardanol and 1,4-p-dichlorobenzyl, and the obtained product has the antibacterial property, water resistance and adhesion of the shell monomer and the mechanical property, heat resistance and antibacterial property of the core monomer.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of inks, and particularly relates to a cross-linked polymer micro-wax powder for inks and a preparation method thereof. BACKGROUND

[0002] In the technical field of inks, natural and synthetic wax additives play an important role in the performance quality of products, helping the surface properties of the final coating product, improved coating integrity and surface appearance, and helping the downstream processing of the coating product and prolonging the service life thereof. The natural wax is composed of long-chain fatty acid esters, has a low softening point, and the high-temperature coating is easy to fail, and the gloss is uneven; the low-molecular synthetic wax has a low molecular weight, a low melting point, a low hardness, poor high-temperature resistance, and poor compatibility with resins, and is easy to have a mist shadow when the addition amount is slightly high, and cannot meet the requirements in the high-performance requirements and functionalization requirements; the polytetrafluoroethylene wax has a high melting point, good high-temperature resistance and wear resistance, and is suitable for high-end industrial paint, but has a high price and is difficult to disperse; and the traditional wax cannot meet the multifunctional requirements of slip, scratch resistance, wear resistance, and touch feeling, thereby limiting the application range of the coating, and in addition, the waterborne polyurethane is used as a connecting material resin in the existing water-based ink, the waterborne polyurethane is widely used due to its good film-forming property, flexibility and chemical stability, but the wear resistance, antibacterial property and scratch resistance of the waterborne polyurethane are slightly poor, and due to the fact that the waterborne polyurethane contains a large number of hydrophilic groups, the water resistance and heat resistance of the waterborne polyurethane need to be further improved. SUMMARY

[0003] To solve the problems mentioned in the background, the purpose of the present application is to provide a cross-linked polymer micro-wax powder for inks and a preparation method thereof, the obtained cross-linked polymer micro-wax powder not only has excellent antibacterial property, water resistance, adhesion and film-forming property of the shell monomer, but also has mechanical property, heat resistance, antibacterial property and weather resistance of the core monomer, and comprehensively has the slip and lubricity of the wax monomer and the functionality of the core-shell polymer emulsion.

[0004] The purpose of the present application can be achieved by the following technical solutions.

[0005] A preparation method of a cross-linked polymer micro-wax powder for inks, comprising the following steps:

[0006] A, the epoxy resin and styrene are taken in a reactor, the wax monomer and hydroquinone are added after being uniformly stirred, and the mixture is placed in an oil bath pot at 105-115 DEG C and stirred for 8-12 min, then the acrylic acid and triethylamine are uniformly mixed and added dropwise into the reactor within 30-40 min, after the dropwise addition is completed, the mixture is kept at a constant temperature for 2-2.5 h, and a modified wax monomer is prepared;

[0007] B, take the emulsifier SE-10N dissolved in deionized water two parts, placed at 60~65℃ under respectively drop modified wax monomer and butyl acrylate pre-emulsification, respectively, the core pre-emulsion and shell pre-emulsion, then the core pre-emulsion temperature is reduced to 40~45℃, nitrogen is imported, add acrylic acid, functional silane coupling agent, comonomer and acrylamide continue to react 0.5~1h, then add initiator sodium bisulfite and ammonium persulfate, the shell pre-emulsion is dropped into the core pre-emulsion in 1.5~2h, after the end of drop, placed at 65~70℃ continue to react 2~2.5h, the core-shell polymer emulsion is prepared;

[0008] C, take the core-shell polymer emulsion adding defoamer continue to stir uniform, the dispersion liquid obtained at room temperature and normal pressure after filtration is carried out spray drying, the crosslinked polymer micro wax powder for ink is prepared;

[0009] The functional silane coupling agent is prepared by using vinyl trimethoxysilane and tetramethyldisiloxane to carry out silicon hydrogen addition reaction, then the modified silane coupling agent prepared and eugenol continue to carry out silicon hydrogen addition reaction, eugenol modified silane coupling agent is prepared, then nucleophilic addition reaction with isocyanato methyl methacrylate is carried out; The comonomer is prepared by using eugenol and cardanol to carry out substitution reaction with the chlorine atom at both ends of 1,4-p-dichlorobenzene.

[0010] Preferably, the wax monomer is one or more of oxidized polyethylene wax, maleic anhydride grafted polyethylene wax, maleic anhydride grafted polypropylene wax, oxidized Fischer-Tropsch wax.

[0011] Preferably, the mass ratio of epoxy resin, wax monomer and hydroquinone in step A is 50:0.4~0.9:0.08.

[0012] Preferably, the mass ratio of modified wax monomer, butyl acrylate, acrylic acid, functional silane coupling agent, comonomer in step B is 10:18~20:0.8~1:0.5~0.7:3~4.

[0013] Preferably, the process parameters of spray drying in step C are: the inlet air temperature is 155~170℃, the outlet air temperature is 75~90℃, and the atomizer speed is 12000~15000r / min.

[0014] Preferably, the epoxy resin is E44; the defoamer is BYK-011.

[0015] Preferably, the preparation method of functional silane coupling agent in step B comprises the following steps:

[0016] B1, take vinyl trimethoxysilane and tetramethyl disiloxane into a reactor containing toluene, heat to 75~80℃ under nitrogen atmosphere, then add Wilkinson catalyst, constant temperature reaction for 5~6h, after reaction, remove the solvent by rotary evaporation, pour the reaction product into a chromatographic column containing silica gel, use n-hexane and ethyl acetate to prepare eluent, after elution, vacuum rotary evaporation, to prepare modified silane coupling agent;

[0017] B2, take eugenol and cast catalyst into a reactor containing toluene, heat to 55~60℃ under nitrogen atmosphere, then add modified silane coupling agent, stir for 20~24h, after reaction, remove unreacted substances by rotary evaporation, to prepare eugenol modified silane coupling agent;

[0018] B3, take eugenol modified silane coupling agent, isocyanatoethyl methacrylate and dibutyl tin dilaurate into a reactor containing acetone, heat to 45~50℃, stir for 10~12h, after reaction, rotary evaporation, washing, drying, to prepare functional silane coupling agent.

[0019] Preferably, the molar ratio of vinyl trimethoxysilane and tetramethyl disiloxane in step B1 is 1~1.1:1.

[0020] Preferably, the preparation method of the copolymer includes the following steps: take eugenol into a reactor containing N,N-dimethylformamide, heat to 50~60℃ under nitrogen atmosphere, then add sodium hydroxide and 1,4-p-dichlorobenzene, stir for 2~3h, then add cardanol, heat to 75~80℃ and continue to react for 3~4h, after reaction, filter, wash, dry, to prepare copolymer.

[0021] A crosslinked polymer micro-wax powder for ink, prepared by the above-mentioned preparation method.

[0022] The beneficial effects of the present application are:

[0023] The present application utilizes the silicon-hydrogen addition reaction of a molecule of vinyl trimethoxysilane and tetramethyldisiloxane to prepare a modified silane coupling agent, then utilizes the silicon-hydrogen addition reaction of eugenol and the ungrafted silicon-hydrogen bond in the modified silane coupling agent to prepare an eugenol-modified silane coupling agent, and then utilizes the nucleophilic addition reaction of the eugenol-modified silane coupling agent and isocyanatoethyl methacrylate to prepare a functionalized silane coupling agent. The natural antibacterial agent eugenol, high-heat-resistance and water-resistance silicone chain segment and rigid benzene ring are introduced into the structure of the silane coupling agent, which endows the core layer monomer with good water resistance, wear resistance, heat resistance and antibacterial property. In addition, the present application utilizes the substitution reaction of eugenol and cardanol with the chlorine atoms at both ends of 1,4-p-dichlorobenzene to prepare a copolymerization monomer containing a double bond and a hydrophobic alkyl long chain, wherein the eugenol and cardanol both belong to green and environmentally friendly raw materials, and are low in cost and renewable. The copolymerization monomer is introduced into the emulsion polymerization system to endow the shell layer monomer with good antibacterial property, adhesion and water resistance.

[0024] The present application introduces a wax monomer into the epoxy acrylate, and the hydroxyl or carboxyl in the wax monomer and the epoxy group in the epoxy acrylate can form a hydrogen bond, thereby improving the intermolecular interaction and further promoting the occurrence of crosslinking reaction, and a soap-free core-shell emulsion polymerization method is used to prepare a core-shell polymer emulsion, wherein the modified wax monomer is the core, and the polymer formed by butyl acrylate, acrylic acid, functionalized silane coupling agent and copolymerization monomer is the shell, and a spray drying process is used to prepare a crosslinked polymer micro-wax powder for ink. The crosslinked polymer micro-wax powder prepared by the present application combines the slipperiness and lubricity of the wax monomer and the functionality of the polymer emulsion, and the wrapped wax monomer is beneficial to uniform distribution in the ink system, has good compatibility with polar resins (such as water-based systems, epoxy and polyurethane), and is gradually released during printing or drying, thereby continuously providing lubrication and protection. In addition, the crosslinked polymer micro-wax powder obtained by the present application has excellent mechanical properties, antibacterial property, heat resistance, water resistance and adhesion of the shell layer monomer. DETAILED DESCRIPTION

[0025] The technical solutions in the embodiments of the present application will be clearly and completely described below in combination with the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative labor fall within the scope of protection of the present application.

[0026] A preparation method of a functionalized silane coupling agent in Example 1 includes the following steps:

[0027] B1, 3.7 g of vinyl trimethoxysilane and 3.3 g of tetramethyldisiloxane were placed in a reactor containing 50 mL of toluene, heated to 80°C under a nitrogen atmosphere, then 0.005 g of Wilkinson catalyst was added and reacted at constant temperature for 6 h. After the reaction was completed, the solvent was removed by rotary evaporation, and the reaction product was poured into a chromatographic column containing silica gel. An eluent was prepared by mixing 60 mL of n-hexane and 30 mL of ethyl acetate, and the eluent was used to elute the product. After elution, vacuum rotary evaporation was performed to obtain the modified silane coupling agent;

[0028] B2, 3.5 g of eugenol and 0.08 g of Karstedt catalyst were placed in a reactor containing 20 mL of toluene, heated to 60°C under a nitrogen atmosphere, then 6.1 g of modified silane coupling agent was added and stirred for 24 h. After the reaction was completed, the unreacted material was removed by rotary evaporation to obtain the eugenol-modified silane coupling agent.

[0029] B3, 8.8 g of eugenol-modified silane coupling agent, 3.2 g of isocyanatoethyl methacrylate, and one drop of dibutyltin dilaurate were placed in a reactor containing 40 mL of acetone, heated to 45°C, and stirred for 12 h. After the reaction was completed, the unreacted material was removed by rotary evaporation to obtain the functionalized silane coupling agent.

[0030] The preparation method of the copolymer monomer of Example 2 comprises the following steps:

[0031] 2.5 g of eugenol was placed in a reactor containing 50 mL of N,N-dimethylformamide, heated to 55°C under a nitrogen atmosphere, then 1.3 g of sodium hydroxide and 2.7 g of 1,4-p-dichlorobenzene were added and stirred for 2 h. Then 4.8 g of cardanol was added and the temperature was raised to 80°C for further reaction for 3.5 h. After the reaction was completed, the copolymer monomer was prepared by filtration, washing, and drying.

[0032] The preparation method of the cross-linked polymer micro-wax powder for ink of Example 3 comprises the following steps:

[0033] A, 50 g of epoxy resin E44 and 75 g of styrene were placed in a reactor, stirred uniformly, then 0.45 g of oxidized polyethylene wax and 0.08 g of hydroquinone were added and placed in an oil bath at 110°C for stirring reaction for 10 min. Then 16.5 g of acrylic acid and 0.25 g of triethylamine were mixed uniformly and added dropwise into the reactor within 40 min. After the addition was completed, the temperature was kept constant for 2 h to obtain the modified wax monomer.

[0034] B, take 150 mL deionized water to dissolve 3 g emulsifier SE-10N, take 200 mL deionized water to dissolve 4 g emulsifier SE-10N twice, respectively, drop 100 g modified wax monomer and 180 g butyl acrylate at 65 DEG C to carry out pre-emulsification, respectively, obtain core pre-emulsion and shell pre-emulsion, then the temperature of core pre-emulsion is reduced to 45 DEG C, nitrogen is introduced, 10 g acrylic acid, 5 g functionalized silane coupling agent, 40 g copolymer monomer and 3 g acrylamide are added to continuously react for 0.5 h, then 0.8 g initiator sodium bisulfite and 1.2 g ammonium persulfate are added, the shell pre-emulsion is dropped into the core pre-emulsion in 2 h, after the dropping is completed, it is continuously reacted at 65 DEG C for 2 h, a core-shell polymer emulsion is prepared;

[0035] C, take the core-shell polymer emulsion to add defoamer BYK-011 to continue stirring uniformly, the obtained dispersion is filtered at normal temperature and pressure, then is carried out spray drying, the inlet air temperature is 155 DEG C, the outlet air temperature is 78 DEG C, the atomizer rotating speed is 12000 r / min, an ink crosslinked polymer micro-wax powder is prepared.

[0036] Example 4, a preparation method of an ink crosslinked polymer micro-wax powder, comprising the following steps:

[0037] A, take 50 g epoxy resin E44 and 75 g styrene in a reactor, after stirring uniformly, add 0.78 g oxidized polyethylene wax and 0.08 g hydroquinone, place in an oil bath at 110 DEG C to stir and react for 10 min, then mix 16.5 g acrylic acid and 0.25 g triethylamine uniformly, drop into the reactor in 40 min, after the dropping is completed, constant temperature reaction is carried out for 2 h, a modified wax monomer is prepared;

[0038] B, take 150 mL deionized water to dissolve 3 g emulsifier SE-10N, take 200 mL deionized water to dissolve 4 g emulsifier SE-10N twice, respectively, drop 100 g modified wax monomer and 200 g butyl acrylate at 65 DEG C to carry out pre-emulsification, respectively, obtain core pre-emulsion and shell pre-emulsion, then the temperature of core pre-emulsion is reduced to 45 DEG C, nitrogen is introduced, 9 g acrylic acid, 5.5 g functionalized silane coupling agent, 35 g copolymer monomer and 3 g acrylamide are added to continuously react for 0.5 h, then 0.8 g initiator sodium bisulfite and 1.2 g ammonium persulfate are added, the shell pre-emulsion is dropped into the core pre-emulsion in 2 h, after the dropping is completed, it is continuously reacted at 65 DEG C for 2 h, a core-shell polymer emulsion is prepared;

[0039] C, take the core-shell polymer emulsion to add defoamer BYK-011 to continue stirring uniformly, the obtained dispersion is filtered at normal temperature and pressure, then is carried out spray drying, the inlet air temperature is 155 DEG C, the outlet air temperature is 78 DEG C, the atomizer rotating speed is 12000 r / min, an ink crosslinked polymer micro-wax powder is prepared.

[0040] Example 5 A method for preparing a cross-linked polymer micro-wax powder for ink, comprising the following steps:

[0041] A, take 50g epoxy resin E44 and 75g styrene in a reactor, after stirring evenly, add 0.88g oxidized polyethylene wax and 0.08g hydroquinone, place in an oil bath at 110℃ and stir for 10min, then mix 16.5g acrylic acid and 0.25g triethylamine evenly and drop into the reactor within 40min, after the drop is completed, constant temperature reaction for 2h, to prepare a modified wax monomer;

[0042] B, take 150mL deionized water to dissolve 3g emulsifier SE-10N, take 200mL deionized water to dissolve 4g emulsifier SE-10N, place in 65℃ and drop 100g modified wax monomer and 180g butyl acrylate respectively to carry out pre-emulsification, to obtain core pre-emulsion and shell pre-emulsion respectively, then reduce the temperature of the core pre-emulsion to 45℃, introduce nitrogen, add 8g acrylic acid, 6.5g functionalized silane coupling agent, 30g comonomer and 3g acrylamide to continue reaction for 0.5h, then add 0.8g initiator sodium bisulfite and 1.2g ammonium persulfate, drop the shell pre-emulsion into the core pre-emulsion within 2h, after the drop is completed, continue to react at 65℃ for 2h, to prepare a core-shell polymer emulsion;

[0043] C, take the core-shell polymer emulsion, add defoamer BYK-011 and continue to stir evenly, filter the obtained dispersion at normal temperature and pressure, then carry out spray drying, the inlet air temperature is 170℃, the outlet air temperature is 90℃, the atomizer speed is 15000r / min, to prepare a cross-linked polymer micro-wax powder for ink.

[0044] Comparative Example 1 A method for preparing a cross-linked polymer micro-wax powder for ink, comprising the following steps:

[0045] A, take 50g epoxy resin E44 and 75g styrene in a reactor, after stirring evenly, add 0.88g oxidized polyethylene wax and 0.08g hydroquinone, place in an oil bath at 110℃ and stir for 10min, then mix 16.5g acrylic acid and 0.25g triethylamine evenly and drop into the reactor within 40min, after the drop is completed, constant temperature reaction for 2h, to prepare a modified wax monomer;

[0046] B, take 150 mL deionized water to dissolve 3 g emulsifier SE-10N, take 200 mL deionized water to dissolve 4 g emulsifier SE-10N twice, respectively, drop 100 g modified wax monomer and 180 g butyl acrylate at 65 DEG C for pre-emulsification, respectively, to obtain core pre-emulsion and shell pre-emulsion, then the temperature of core pre-emulsion is reduced to 45 DEG C, nitrogen is introduced, 8 g acrylic acid, 6.5 g vinyl trimethoxysilane, 30 g comonomer and 3 g acrylamide are added for continuous reaction for 0.5 h, then 0.8 g initiator sodium bisulfite and 1.2 g ammonium persulfate are added, the shell pre-emulsion is dropped into the core pre-emulsion within 2 h, after the dropping is completed, it is continuously reacted at 65 DEG C for 2 h, to prepare a core-shell polymer emulsion;

[0047] C, take the core-shell polymer emulsion to add defoamer BYK-011 to continue stirring, filter the obtained dispersion at normal temperature and pressure, and then spray dry, the inlet air temperature is 170 DEG C, the outlet air temperature is 90 DEG C, and the atomizer rotating speed is 15000 r / min, to prepare an ink crosslinked polymer micro-wax powder.

[0048] Preparation method of an ink crosslinked polymer micro-wax powder, comprising the following steps:

[0049] A, take 50 g epoxy resin E44 and 75 g styrene in a reactor, stir uniformly, then add 0.88 g oxidized polyethylene wax and 0.08 g hydroquinone, place in an oil bath at 110 DEG C and stir for 10 min, then mix 16.5 g acrylic acid and 0.25 g triethylamine uniformly and drop into the reactor within 40 min, after the dropping is completed, constant temperature reaction for 2 h, to prepare a modified wax monomer;

[0050] B, take 150 mL deionized water to dissolve 3 g emulsifier SE-10N, take 200 mL deionized water to dissolve 4 g emulsifier SE-10N twice, respectively, drop 100 g modified wax monomer and 180 g butyl acrylate at 65 DEG C for pre-emulsification, respectively, to obtain core pre-emulsion and shell pre-emulsion, then the temperature of core pre-emulsion is reduced to 45 DEG C, nitrogen is introduced, 8 g acrylic acid, 6.5 g functionalized silane coupling agent, 30 g methyl methacrylate and 3 g acrylamide are added for continuous reaction for 0.5 h, then 0.8 g initiator sodium bisulfite and 1.2 g ammonium persulfate are added, the shell pre-emulsion is dropped into the core pre-emulsion within 2 h, after the dropping is completed, it is continuously reacted at 65 DEG C for 2 h, to prepare a core-shell polymer emulsion;

[0051] C. The core-shell polymer emulsion was added with defoaming agent BYK-011 and stirred uniformly, and the obtained dispersion was filtered at normal temperature and pressure and then spray dried, with an inlet temperature of 170°C, an outlet temperature of 90°C, and an atomizer rotating speed of 15000 r / min, to prepare the crosslinked polymer micro-wax powder for ink.

[0052] Comparative Example 3 A method for preparing a crosslinked polymer micro-wax powder for ink, comprising the following steps:

[0053] A. 50g of epoxy resin E44 and 75g of styrene were taken into a reactor, stirred uniformly, and then 0.88g of oxidized polyethylene wax and 0.08g of hydroquinone were added, and the mixture was stirred in an oil bath at 110°C for 10min. Then 16.5g of acrylic acid and 0.25g of triethylamine were mixed uniformly and added dropwise into the reactor within 40min. After the dropwise addition was completed, the mixture was reacted at constant temperature for 2h to prepare a modified wax monomer.

[0054] B. 150mL of deionized water was taken to dissolve 3g of emulsifier SE-10N, and 200mL of deionized water was taken to dissolve 4g of emulsifier SE-10N, and the two portions were separately added dropwise into 100g of the modified wax monomer and 180g of butyl acrylate at 65°C to perform pre-emulsification, respectively, to obtain a core pre-emulsion and a shell pre-emulsion. Then the temperature of the core pre-emulsion was lowered to 45°C, nitrogen was introduced, 8g of acrylic acid, 30g of a comonomer, and 3g of acrylamide were added, and the mixture was continuously reacted for 0.5h. Then 0.8g of initiator sodium bisulfite and 1.2g of ammonium persulfate were added, and the shell pre-emulsion was added dropwise into the core pre-emulsion within 2h. After the dropwise addition was completed, the mixture was continuously reacted at 65°C for 2h to prepare a core-shell polymer emulsion.

[0055] C. The core-shell polymer emulsion was added with defoaming agent BYK-011 and stirred uniformly, and the obtained dispersion was filtered at normal temperature and pressure and then spray dried, with an inlet temperature of 170°C, an outlet temperature of 90°C, and an atomizer rotating speed of 15000 r / min, to prepare the crosslinked polymer micro-wax powder for ink.

[0056] Performance detection

[0057] The crosslinked polymer micro-wax powder for ink prepared in Examples 3-5 and Comparative Examples 1-3 was subjected to performance detection.

[0058] (1) Particle size analysis: 0.006g of the sample was added into 6mL of deionized water, ultrasonically dispersed, and the average particle size was tested by dynamic light scattering particle size analyzer. The data results are shown in Table 1.

[0059] (2) Heat resistance detection: The sample was heated at a rate of 10°C / min from 35°C to 700°C under a nitrogen atmosphere, and the initial decomposition temperature was recorded to evaluate the heat resistance. The data results are shown in Table 1.

[0060] (3) Anti-bacterial performance test: the sample was mixed with bacterial suspension (10 6 CFU / mL), 200 μL water-based paint color paste was added respectively, the mixture was uniformly coated on the culture medium, and incubated at 37°C for 48 h, the anti-bacterial effect of the sample was evaluated by the inhibition rate, and the data results were shown in Table 1.

[0061] The water-based polyurethane emulsion, the sample prepared in Examples 3-5 and Comparative Examples 1-3, water-based carbon black paste and sodium carboxymethyl cellulose were mixed to prepare ink, and the following performance tests were carried out:

[0062] (4) Water resistance test: the data results were shown in Table 1 by water contact angle measurement.

[0063] (5) Abrasion resistance test: a 7000-mesh SiC sandpaper was placed on the surface of the ink printed surface, and a 200g weight was pressed on the sandpaper, the sandpaper was uniformly dragged in the horizontal direction for 10 cm, the sample was rotated clockwise by 90°, and then uniformly dragged in the horizontal direction for 10 cm, which was taken as a cycle, and the abrasion cycle was repeated for 30 times. The water contact angle of the ink printed surface after abrasion was measured, and the data results were shown in Table 1.

[0064] (6) Hardness test: according to ASTM D3363-00, the hardness of the ink printed surface was tested by pencil scratch hardness tester, and the data results were shown in Table 1.

[0065] (7) Adhesion test: according to ASTM D3359-97, the adhesion of the ink printed surface was tested by cross-cut knife and 3M tape, and the data results were shown in Table 1.

[0066] Table 1 Performance test results of samples

[0067]

[0068] As can be seen from the data results in Table 1, the crosslinked polymer micro-wax powder for ink prepared in Examples 3-5 has good hardness, adhesion, antibacterial effect, water resistance and wear resistance and heat resistance. In Comparative Example 1, the functional silane coupling agent is replaced with an equal amount of vinyl trimethoxysilane, and in Comparative Example 3, no functional silane coupling agent is added. The measured antibacterial rate, water resistance and wear resistance, hardness and heat resistance of Comparative Examples 1 and 3 are lower than those of Examples 3-5, because the functional coupling agent introduces antibacterial component eugenol, more siloxane bonds and rigid benzene rings. The water resistance and wear resistance and heat resistance of Comparative Example 3 are slightly lower than those of Comparative Example 1, because the vinyl trimethoxysilane introduces a certain number of siloxane bonds. In Comparative Example 2, the comonomer is replaced with an equal amount of methyl methacrylate, and the measured antibacterial rate, water contact angle and adhesion are lower than those of Examples 3-5, indicating that the addition of comonomer can improve the antibacterial effect, water resistance and adhesion of the material.

[0069] In the description of the present specification, the description of the terms "one embodiment", "an example", "a specific example" and the like means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present application. In the present specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0070] The basic principles, main features and advantages of the present application are shown and described above. It should be understood by those skilled in the art that the present application is not limited by the above examples, and the above examples and descriptions in the specification are only illustrative of the principles of the present application. Without departing from the spirit and scope of the present application, various changes and improvements can be made to the present application, and these changes and improvements all fall within the scope of the claimed present application.

Claims

1. A method for preparing cross-linked polymer microwax powder for inks, characterized in that, Includes the following steps: A. Take epoxy resin and styrene into a reactor, stir evenly, add wax monomer and hydroquinone, place in an oil bath at 105~115℃ and stir for 8~12 min. Then, mix acrylic acid and triethylamine evenly and add dropwise to the reactor over 30~40 min. After the addition is complete, keep the temperature constant for 2~2.5 h to prepare the modified wax monomer. B. Take two portions of emulsifier SE-10N dissolved in deionized water, and pre-emulsify them by adding modified wax monomer and butyl acrylate dropwise at 60~65℃ to obtain core pre-emulsion and shell pre-emulsion respectively. Then, lower the temperature of the core pre-emulsion to 40~45℃, introduce nitrogen gas, add acrylic acid, functionalized silane coupling agent, comonomer and acrylamide and continue to react for 0.5~1h. Then add initiator sodium bisulfite and ammonium persulfate, and drop the shell pre-emulsion into the core pre-emulsion within 1.5~2h. After the dropwise addition is completed, continue to react at 65~70℃ for 2~2.5h to prepare core-shell polymer emulsion. C. Take the core-shell polymer emulsion, add defoamer and continue stirring until uniform. Filter the resulting dispersion at room temperature and pressure and then spray dry it to prepare cross-linked polymer microwax powder for ink. The functionalized silane coupling agent is prepared by hydrosilylation reaction of vinyltrimethoxysilane and tetramethyldisiloxane, followed by hydrosilylation reaction of the prepared modified silane coupling agent with eugenol to obtain eugenol-based modified silane coupling agent, which is then prepared by nucleophilic addition reaction with isocyanate methacrylate; the comonomer is prepared by substitution reaction of eugenol and cashew nut shell phenol with the chlorine atoms at both ends of 1,4-dichlorobenzyl, respectively. The wax monomer is one or more of the following: oxidized polyethylene wax, maleic anhydride-grafted polyethylene wax, maleic anhydride-grafted polypropylene wax, and oxidized Fischer-Tropsch wax.

2. The method for preparing cross-linked polymer microwax 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.

3. The method for preparing cross-linked polymer microwax powder for ink according to claim 1, characterized in that, In step B, the mass ratio of 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.

4. The method for preparing cross-linked polymer microwax powder for ink according to claim 1, characterized in that, The process parameters for spray drying in step C are: inlet air temperature of 155~170℃, outlet air temperature of 75~90℃, and atomizer speed of 12000~15000r / min.

5. The method for preparing cross-linked polymer microwax powder for ink according to claim 1, characterized in that, The epoxy resin is E44; the defoamer is BYK-011.

6. The method for preparing cross-linked polymer microwax powder for ink according to claim 1, characterized in that, The preparation method of the functionalized silane coupling agent in step B includes the following steps: B1. Vinyltrimethoxysilane and tetramethyldisiloxane were placed in a reactor containing toluene and heated to 75-80°C under a nitrogen atmosphere. Then, Wilkinson catalyst was added and reacted 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 containing silica gel. An eluent was prepared using n-hexane and ethyl acetate. After elution, the product was subjected to vacuum rotary evaporation to prepare the modified silane coupling agent. B2. Eugenol and cassette catalyst were placed in a reactor containing toluene and heated to 55-60°C under a nitrogen atmosphere. Then, modified silane coupling agent was added and stirred for 20-24 hours. After the reaction was completed, unreacted material was removed by rotary evaporation to prepare eugenol-based modified silane coupling agent. B3. Eugenol-modified silane coupling agent, isocyanate methacrylate and dibutyltin dilaurate are placed in a reactor containing acetone, heated to 45-50℃, and stirred for 10-12 hours. After the reaction is completed, the functionalized silane coupling agent is prepared by rotary evaporation, washing and drying.

7. The method for preparing cross-linked polymer microwax powder for ink according to claim 6, characterized in that, In step B1, the molar ratio of vinyltrimethoxysilane to tetramethyldisiloxane is 1~1.1:

1.

8. The method for preparing cross-linked polymer microwax powder for ink according to claim 1, characterized in that, The preparation method of the comonomer includes the following steps: Eugenol is placed in a reactor containing N,N-dimethylformamide, and the temperature is raised to 50~60℃ under a nitrogen atmosphere. Then sodium hydroxide and 1,4-dichlorobenzyl are added, and the mixture is stirred for 2~3 hours. Subsequently, cashew phenol is added, and the temperature is raised to 75~80℃ to continue the reaction for 3~4 hours. After the reaction is completed, the mixture is filtered, washed, and dried to obtain the comonomer.

9. A cross-linked polymer microwax powder for inks, characterized in that, It is prepared by the preparation method described in any one of claims 1 to 8.

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