A kind of high adhesion weather-resistant ink and preparation method thereof

Abstract

The invention relates to the technical field of inks, and discloses a high-adhesion weather-resistant ink and a preparation method thereof. The preparation method comprises: reacting modified polyethylene glycol, triethylene glycol, epoxy resin, triethylamine, p-hydroxyanisole, and itaconic acid / isopropanol mixed solution to obtain epoxy itaconate; mixing epoxy itaconate with functionalized carbon black for reaction, neutralizing, and obtaining modified epoxy itaconate; and mixing modified epoxy itaconate, additives, ferrosoferric oxide, silicon dioxide, an organosilicon photoinitiator, and isopropanol to obtain high-adhesion weather-resistant ink.

Description

Technical Field

[0001] The invention relates to the technical field of inks, and in particular to a high-adhesion weather-resistant ink and a preparation method thereof. Background Art

[0002] Ink is a uniform emulsion prepared by evenly dispersing and mixing pigments that present colors, binders that act as pigment carriers, solvents that disperse pigments and binders, and related additives through mechanical stirring, shearing, or ball milling. It is an important type of printing or coating material and is widely used in printing, decoration, circuit board and other industries.

[0003] Traditional inks take a long time to dry after printing, resulting in reduced printing quality. UV curing inks are widely used environmentally friendly inks and are reactive inks. They can be cured in a short time under ultraviolet light and are more suitable for mass printing. At the same time, UV curing inks are green and environmentally friendly, have fast curing rates, low energy consumption, good film-forming properties, and high hardness, and can be used in car center consoles. However, UV curing inks will age under long-term exposure to ultraviolet rays, affecting the mechanical properties of the inks, such as adhesion, and thus affecting the service life of the inks.

[0004] Epoxy acrylate (EA) is obtained by ring-opening reaction of epoxy resin with acrylic acid under the action of catalyst. It has the advantages of fast curing speed, strong chemical corrosion resistance, high hardness, good adhesion and is widely used, but it also has the disadvantages of large viscosity, large brittleness and poor flexibility. Prior art such as Chinese patent application CN102358810A discloses a kind of environmentally friendly packaging printing water-based gravure ink and its preparation method. By adding other auxiliary agents to epoxy acrylate composite emulsion, the obtained ink printing effect is better, glossiness is high, adhesion is strong, and chemical resistance is strong. However, since epoxy acrylate has the disadvantages of large viscosity, large brittleness, insufficient flexibility, and the obtained ink weather resistance is limited, the application of ink is limited. Summary of the invention

[0005] The purpose of the present invention is to overcome the deficiencies of the prior art and provide a high-adhesion weather-resistant ink and a preparation method thereof. The ink has high adhesion and weather resistance and good mechanical properties.

[0006] In order to achieve the above object, the technical solution adopted by the present invention is as follows:

[0007] A method for preparing a high-adhesion weather-resistant ink comprises the following steps:

[0008] Step 1, preparing functionalized carbon black and organosilicon photoinitiator;

[0009] The preparation of functionalized carbon black comprises the following steps:

[0010] Step (1), mixing carbon black with water, ultrasonically dispersing to obtain a carbon black dispersion, introducing ozone into the carbon black dispersion for oxidation, adding an alkaline regulator to adjust the pH value after the oxidation, continuing the oxidation, adding an acidic regulator to adjust the pH value after the oxidation, centrifuging, filtering, washing, and drying to obtain carboxylated carbon black;

[0011] Step (2), dissolving p-aminophenol and acetone, adding carboxylated carbon black and dicyclohexylcarbodiimide, performing ultrasonic dispersion, reacting, filtering, washing, and drying after the reaction is completed to obtain amidated carbon black;

[0012] Step (3), mixing the amidated carbon black with acetone, ultrasonically dispersing, adding isophorone diisocyanate and dibutyltin dilaurate, reacting, filtering and washing after the reaction is completed to obtain functionalized carbon black;

[0013] The preparation of organosilicon photoinitiator includes the following steps:

[0014] 1,3,5,7-tetramethylcyclotetrasiloxane, 4-propyleneoxy-2-hydroxybenzophenone and isopropanol are mixed, chloroplatinic acid is added, and the mixture is reacted. After the reaction is completed, the solvent isopropanol is removed by rotary evaporation to obtain an organosilicon photoinitiator;

[0015] Step 2: Mix polyethylene glycol and nano titanium dioxide, stir and disperse to obtain modified polyethylene glycol; mix modified polyethylene glycol, triethylene glycol, epoxy resin, triethylamine and p-hydroxyanisole, react, add itaconic acid / isopropanol mixed solution after the reaction is completed, continue to react, remove the solvent isopropanol by rotary evaporation after the reaction is completed, and obtain epoxy itaconate; mix epoxy itaconate and functionalized carbon black, react, neutralize after the reaction is completed, and obtain modified epoxy itaconate;

[0016] Step 3: Mix and stir the modified epoxy itaconate, additives, ferrosoferric oxide, silicon dioxide, organosilicon photoinitiator and isopropyl alcohol to obtain a high-adhesion weather-resistant ink.

[0017] Preferably, when preparing the functionalized carbon black, in step (1): the mass ratio of carbon black to water is 1:20-30; the flow rate of ozone is 2.5-3 L / min, and the oxidation conditions are: oxidation at room temperature for 1-2 h; the continued oxidation conditions are: oxidation at a pH value of 13-14 and continued oxidation at room temperature for 7-8 h; the pH value after adjustment with an acidic regulator is 3-4.

[0018] Preferably, the alkaline regulator comprises a saturated sodium hydroxide aqueous solution; and the acidic regulator comprises concentrated hydrochloric acid.

[0019] Preferably, when preparing the functionalized carbon black, in step (2): the mass ratio of p-aminophenol, carboxylated carbon black, dicyclohexylcarbodiimide and acetone is 20-30:5-7:2-4:500-550; and the reaction conditions are: reacting at a temperature of 70-80°C for 10-12h.

[0020] Preferably, when preparing the functionalized carbon black, in step (3): the mass ratio of amidated carbon black, isophorone diisocyanate, dibutyltin dilaurate, and acetone is 5:100-130:0.6-0.7:300-400; and the reaction conditions are: reacting at a temperature of 50-60°C for 3-5h.

[0021] Preferably, when preparing the organosilicon photoinitiator, the mass ratio of 1,3,5,7-tetramethylcyclotetrasiloxane, 4-propyleneoxy-2-hydroxybenzophenone, isopropanol and chloroplatinic acid is 24-26:32-35:10-20:0.05-0.06; the reaction conditions are: reacting in a nitrogen atmosphere at a temperature of 85-95° C. for 4-6 hours.

[0022] Preferably, in step 2: the mass ratio of polyethylene glycol to nano-titanium dioxide is 1:20; and the stirring and dispersing conditions are: stirring and dispersing at a speed of 2500-3500 r / min for 20-30 min.

[0023] Preferably, in the step 2: the mass ratio of modified polyethylene glycol, triethylene glycol, epoxy resin, triethylamine, p-hydroxyanisole, and itaconic acid / isopropanol mixed solution is 30-35:5-10:400-430:1.5-3:0.2-0.3:250-270; when preparing epoxy itaconate, the reaction conditions are: react at 90-95°C for 3-4h; the continued reaction conditions are: continue to react at 100-110°C for 4-6h; the mass ratio of epoxy itaconate to functionalized carbon black is 100:20-30; when preparing modified epoxy itaconate, the reaction conditions are: react at 40-50°C for 3-4h; the pH value after neutralization is 7-7.5.

[0024] Preferably, the itaconic acid / isopropanol mixed solution is prepared by mixing itaconic acid and isopropanol in a mass ratio of 1:10; and the neutralizing agent used in the neutralization operation includes triethanolamine.

[0025] Preferably, in the step three: the mass ratio of modified epoxy itaconate, additive, ferrosoferric oxide, silicon dioxide, silicone photoinitiator and isopropanol is 100:15-20:35-40:0.5-1:6-8:20-30; the additive is prepared by mixing 2-hydroxyethyl methacrylate phosphate, 4-methacrylamide-2,2,6,6-tetramethylpiperidine, trimethylolpropane triacrylate and polyurethane acrylate in a mass ratio of 2-3:4-5:10-15:8-10.

[0026] Preferably, a high adhesion weather-resistant ink is prepared by the method for preparing the high adhesion weather-resistant ink as described above.

[0027] Compared with the prior art, the present invention has the following beneficial effects:

[0028] The present invention obtains carboxylated carbon black by oxidizing carbon black with ozone, and obtains amidated carbon black having phenolic hydroxyl groups by subjecting the carboxyl group of the carboxylated carbon black to an amidation reaction with the amino group of p-aminophenol, and reacts the amidated carbon black with isophorone diisocyanate to obtain functionalized carbon black having isocyanate groups. The surface treatment improves the dispersibility of the carbon black, and the carbon black is not easy to agglomerate in the ink matrix. At the same time, the functionalized carbon black surface has highly reactive isocyanate groups, which can react with the ink matrix material, and further improve the dispersibility of the carbon black in the ink.

[0029] The photocurable epoxy resin has the advantages of good weather resistance and high hardness. The epoxy itaconate prepared by the ring-opening reaction between itaconic acid and the epoxy resin has a photosensitive active group and can be photocured. When preparing the epoxy itaconate, the in-situ polymerization method is used to make triethylene glycol and polyethylene glycol adsorbed on the nano titanium dioxide react with the epoxy resin to react to open the ring. After the reaction, the remaining epoxy groups of the epoxy resin continue to react with itaconic acid to react to open the ring, so as to obtain the epoxy itaconate with carbon-carbon double bond termination and carboxyl and hydroxyl groups on the side groups. Nano titanium dioxide with anti-ultraviolet aging performance is introduced to improve the weather resistance of the epoxy itaconate. At the same time, triethylene glycol and polyethylene glycol are both alcohols with good flexibility. They react with the epoxy resin to react to open the ring and copolymerize in the main chain of the epoxy itaconate, so as to improve the mechanical properties of the ink. Epoxy itaconate is mixed with functionalized carbon black, and the carbon black is grafted onto the epoxy itaconate through the reaction of epoxy itaconate with the isocyanate group on the surface of the functionalized carbon black, thereby further improving the dispersibility and stability of the carbon black. The obtained modified epoxy itaconate has better stability. In addition, since the modified epoxy itaconate has multiple active groups such as carboxyl and hydroxyl groups, the adhesion of the ink is also improved.

[0030] The invention adopts 1,3,5,7-tetramethylcyclotetrasiloxane and 4-propyleneoxy-2-hydroxybenzophenone to undergo a silylation reaction, and a photoinitiator is grafted onto organic silicon to obtain an organic silicon photoinitiator, which is mixed with modified epoxy itaconate, 2-hydroxyethyl methacrylate phosphate, 4-methacrylamide-2,2,6,6-tetramethylpiperidine, trimethylolpropane triacrylate, and polyurethane acrylate as additives, and then mixed with modified epoxy itaconate, ferrosoferric oxide, silicon dioxide, the organic silicon photoinitiator, and isopropyl alcohol to obtain a weather-resistant ink with high adhesion. Among them, the silicone structure in the silicone photoinitiator can increase the adhesion and water resistance of the ink; 2-hydroxyethyl methacrylate phosphate and 4-methacrylamide-2,2,6,6-tetramethylpiperidine both contain carbon-carbon double bond structures, which can participate in the photocuring reaction of the ink and cross-link with the matrix resin. 2-Hydroxyethyl methacrylate phosphate can be used as an adhesion promoter to further improve the adhesion of the ink, and 4-methacrylamide-2,2,6,6-tetramethylpiperidine can be used as a light stabilizer to further improve the weather resistance of the ink; polyurethane acrylate improves the comprehensive performance of the ink; through the synergistic effect of each component, the obtained ink has high adhesion and weather resistance, and good mechanical properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 This is a process flow chart for preparing high-adhesion weather-resistant ink in the present invention;

[0032] Figure 2 It is a schematic diagram of the reaction for preparing functionalized carbon black in the present invention. DETAILED DESCRIPTION

[0033] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0034] Example 1

[0035] This embodiment discloses a method for preparing a high-adhesion weather-resistant ink, comprising the following steps:

[0036] Step 1, preparing functionalized carbon black and organosilicon photoinitiator;

[0037] The preparation of functionalized carbon black comprises the following steps:

[0038] Step (1), mixing carbon black and water in a mass ratio of 1:20, ultrasonically dispersing for 10 minutes to obtain a carbon black dispersion, introducing ozone at a flow rate of 2.5 L / min into the carbon black dispersion, oxidizing at room temperature for 2 hours, adding a saturated sodium hydroxide aqueous solution after the oxidation is completed to adjust the pH value to 13, continuing to oxidize at room temperature for 7 hours, adding concentrated hydrochloric acid after the oxidation is completed to adjust the pH value to 3, centrifuging, filtering, taking a filter cake, adding water 5 times the mass of the filter cake for washing, and drying at 90° C. for 8 hours to obtain carboxylated carbon black;

[0039] Step (2), dissolving p-aminophenol and acetone, adding carboxylated carbon black and dicyclohexylcarbodiimide, ultrasonically dispersing for 10 min, reacting at 70° C. for 12 h, filtering after the reaction, taking the filter cake, adding acetone 5 times the mass of the filter cake to wash three times, and drying at 60° C. for 14 h to obtain amidated carbon black;

[0040] Among them, the mass ratio of p-aminophenol, carboxylated carbon black, dicyclohexylcarbodiimide and acetone is 20:5:2:500;

[0041] Step (3), mixing the amidated carbon black with acetone, ultrasonically dispersing for 20 minutes, adding isophorone diisocyanate and dibutyltin dilaurate, reacting at 50° C. for 5 hours, filtering after the reaction, taking the filter cake, adding acetone 5 times the mass of the filter cake and washing three times to obtain functionalized carbon black;

[0042] Among them, the mass ratio of amidated carbon black, isophorone diisocyanate, dibutyltin dilaurate, and acetone is 5:100:0.6:300;

[0043] The preparation of organosilicon photoinitiator includes the following steps:

[0044] 1,3,5,7-tetramethylcyclotetrasiloxane, 4-propyleneoxy-2-hydroxybenzophenone and isopropanol were mixed, chloroplatinic acid was added, and the mixture was reacted at 85°C for 6 hours in a nitrogen atmosphere. After the reaction was completed, the solvent isopropanol was removed by rotary evaporation at 65°C to obtain an organosilicon photoinitiator;

[0045] Among them, the mass ratio of 1,3,5,7-tetramethylcyclotetrasiloxane, 4-propyleneoxy-2-hydroxybenzophenone, isopropanol, and chloroplatinic acid is 24:32:10:0.05;

[0046] Step 2: Mix polyethylene glycol and nano-titanium dioxide in a mass ratio of 1:20, stir and disperse at a speed of 2500r / min for 30min to obtain modified polyethylene glycol; mix modified polyethylene glycol, triethylene glycol, epoxy resin, triethylamine, and p-hydroxyanisole, react at 90°C for 4h, add itaconic acid / isopropanol mixed solution after the reaction, continue to react at 100°C for 6h, and remove the solvent isopropanol by rotary evaporation at 65°C to obtain epoxy itaconate; mix epoxy itaconate and functionalized carbon black in a mass ratio of 100:20, react at 40°C for 4h, and add triethanolamine to neutralize to a pH of 7 after the reaction to obtain modified epoxy itaconate;

[0047] The mass ratio of modified polyethylene glycol, triethylene glycol, epoxy resin, triethylamine, p-hydroxyanisole, and itaconic acid / isopropanol mixed solution is 30:10:400:1.5:0.2:250; the itaconic acid / isopropanol mixed solution is prepared by mixing itaconic acid and isopropanol in a mass ratio of 1:10;

[0048] Step 3: Mix the modified epoxy itaconate, additives, ferrosilicate, silicon dioxide, silicone photoinitiator, and isopropyl alcohol in a mass ratio of 100:15:35:0.5:6:20 in a light-proof environment, and stir at a speed of 500 r / min for 1 hour to obtain a high-adhesion weather-resistant ink;

[0049] The additive is prepared by mixing 2-hydroxyethyl methacrylate phosphate, 4-methacrylamide-2,2,6,6-tetramethylpiperidine, trimethylolpropane triacrylate, and polyurethane acrylate in a mass ratio of 2:4:10:8.

[0050] Example 2

[0051] This embodiment discloses a method for preparing a high-adhesion weather-resistant ink, comprising the following steps:

[0052] Step 1, preparing functionalized carbon black and organosilicon photoinitiator;

[0053] The preparation of functionalized carbon black comprises the following steps:

[0054] Step (1), mixing carbon black and water in a mass ratio of 1:22, ultrasonically dispersing for 15 minutes to obtain a carbon black dispersion, introducing ozone at a flow rate of 2.6 L / min into the carbon black dispersion, oxidizing at room temperature for 2 hours, adding a saturated sodium hydroxide aqueous solution after the oxidation is completed to adjust the pH value to 13.5, continuing to oxidize at room temperature for 7 hours, after the oxidation is completed, adding concentrated hydrochloric acid to adjust the pH value to 3.5, centrifuging, filtering, taking a filter cake, adding water 6 times the mass of the filter cake for washing, and drying at 95° C. for 7 hours to obtain carboxylated carbon black;

[0055] Step (2), dissolving p-aminophenol and acetone, adding carboxylated carbon black and dicyclohexylcarbodiimide, ultrasonically dispersing for 15 minutes, reacting at 75° C. for 11 hours, filtering after the reaction, taking the filter cake, adding acetone 6 times the mass of the filter cake to wash three times, and drying at 65° C. for 12 hours to obtain amidated carbon black;

[0056] Among them, the mass ratio of p-aminophenol, carboxylated carbon black, dicyclohexylcarbodiimide and acetone is 22:5.5:2.5:515;

[0057] Step (3), mixing the amidated carbon black with acetone, ultrasonically dispersing for 25 minutes, adding isophorone diisocyanate and dibutyltin dilaurate, reacting at 55° C. for 4 hours, filtering after the reaction, taking the filter cake, adding acetone 6 times the mass of the filter cake and washing three times to obtain functionalized carbon black;

[0058] Among them, the mass ratio of amidated carbon black, isophorone diisocyanate, dibutyltin dilaurate, and acetone is 5:110:0.6:330;

[0059] The preparation of organosilicon photoinitiator includes the following steps:

[0060] 1,3,5,7-tetramethylcyclotetrasiloxane, 4-propyleneoxy-2-hydroxybenzophenone and isopropanol were mixed, chloroplatinic acid was added, and the mixture was reacted at 90°C for 5 hours in a nitrogen atmosphere. After the reaction was completed, the solvent isopropanol was removed by rotary evaporation at 70°C to obtain an organosilicon photoinitiator;

[0061] Among them, the mass ratio of 1,3,5,7-tetramethylcyclotetrasiloxane, 4-propyleneoxy-2-hydroxybenzophenone, isopropanol, and chloroplatinic acid is 24.5:33:13:0.05;

[0062] Step 2: Mix polyethylene glycol and nano-titanium dioxide in a mass ratio of 1:20, stir and disperse at a speed of 2800r / min for 25min to obtain modified polyethylene glycol; mix modified polyethylene glycol, triethylene glycol, epoxy resin, triethylamine, and p-hydroxyanisole, react at 90°C for 4h, add itaconic acid / isopropanol mixed solution after the reaction, continue to react at 102°C for 5.5h, and after the reaction, remove the solvent isopropanol by rotary evaporation at 70°C to obtain epoxy itaconate; mix epoxy itaconate and functionalized carbon black in a mass ratio of 100:23, react at 45°C for 3.5h, and after the reaction, add triethanolamine to neutralize to a pH of 7 to obtain modified epoxy itaconate;

[0063] The mass ratio of modified polyethylene glycol, triethylene glycol, epoxy resin, triethylamine, p-hydroxyanisole, and itaconic acid / isopropanol mixed solution is 32:8:410:2:0.2:255; the itaconic acid / isopropanol mixed solution is prepared by mixing itaconic acid and isopropanol in a mass ratio of 1:10;

[0064] Step 3, the modified epoxy itaconate, additives, ferrosilicate, silicon dioxide, silicone photoinitiator, and isopropyl alcohol are mixed in a mass ratio of 100:16:36:0.6:6.5:22 in a light-proof environment, and stirred at a speed of 520 r / min for 1 hour to obtain a high-adhesion weather-resistant ink;

[0065] The additive is prepared by mixing 2-hydroxyethyl methacrylate phosphate, 4-methacrylamide-2,2,6,6-tetramethylpiperidine, trimethylolpropane triacrylate, and polyurethane acrylate in a mass ratio of 2.2:4.2:11:8.5.

[0066] Example 3

[0067] This embodiment discloses a method for preparing a high-adhesion weather-resistant ink, comprising the following steps:

[0068] Step 1, preparing functionalized carbon black and organosilicon photoinitiator;

[0069] The preparation of functionalized carbon black comprises the following steps:

[0070] Step (1), mixing carbon black and water in a mass ratio of 1:25, ultrasonically dispersing for 15 minutes to obtain a carbon black dispersion, introducing ozone at a flow rate of 2.8 L / min into the carbon black dispersion, oxidizing at room temperature for 1.5 hours, adding a saturated sodium hydroxide aqueous solution after the oxidation is completed to adjust the pH value to 13.5, continuing to oxidize at room temperature for 7.5 hours, adding concentrated hydrochloric acid after the oxidation is completed to adjust the pH value to 3.5, centrifuging, filtering, taking a filter cake, adding water 6 times the mass of the filter cake for washing, and drying at 95° C. for 7 hours to obtain carboxylated carbon black;

[0071] Step (2), dissolving p-aminophenol and acetone, adding carboxylated carbon black and dicyclohexylcarbodiimide, ultrasonically dispersing for 15 minutes, reacting at 75° C. for 11 hours, filtering after the reaction, taking the filter cake, adding acetone 6 times the mass of the filter cake to wash three times, and drying at 65° C. for 12 hours to obtain amidated carbon black;

[0072] Among them, the mass ratio of p-aminophenol, carboxylated carbon black, dicyclohexylcarbodiimide and acetone is 25:6:3:530;

[0073] Step (3), mixing the amidated carbon black with acetone, ultrasonically dispersing for 25 minutes, adding isophorone diisocyanate and dibutyltin dilaurate, reacting at 55° C. for 4 hours, filtering after the reaction, taking the filter cake, adding acetone 6 times the mass of the filter cake and washing three times to obtain functionalized carbon black;

[0074] Among them, the mass ratio of amidated carbon black, isophorone diisocyanate, dibutyltin dilaurate, and acetone is 5:115:0.65:350;

[0075] The preparation of organosilicon photoinitiator includes the following steps:

[0076] 1,3,5,7-tetramethylcyclotetrasiloxane, 4-propyleneoxy-2-hydroxybenzophenone and isopropanol were mixed, chloroplatinic acid was added, and the mixture was reacted at 90°C for 5 hours in a nitrogen atmosphere. After the reaction was completed, the solvent isopropanol was removed by rotary evaporation at 70°C to obtain an organosilicon photoinitiator;

[0077] Among them, the mass ratio of 1,3,5,7-tetramethylcyclotetrasiloxane, 4-propyleneoxy-2-hydroxybenzophenone, isopropanol, and chloroplatinic acid is 25:33.5:15:0.05;

[0078] Step 2: Mix polyethylene glycol and nano-titanium dioxide in a mass ratio of 1:20, stir and disperse at a speed of 3000r / min for 25min to obtain modified polyethylene glycol; mix modified polyethylene glycol, triethylene glycol, epoxy resin, triethylamine, and p-hydroxyanisole, react at 92°C for 3.5h, add itaconic acid / isopropanol mixed solution after the reaction, continue to react at 105°C for 5h, and after the reaction, remove the solvent isopropanol by rotary evaporation at 70°C to obtain epoxy itaconate; mix epoxy itaconate and functionalized carbon black in a mass ratio of 100:25, react at 45°C for 3.5h, and after the reaction, add triethanolamine to neutralize to a pH value of 7.2 to obtain modified epoxy itaconate;

[0079] The mass ratio of modified polyethylene glycol, triethylene glycol, epoxy resin, triethylamine, p-hydroxyanisole, and itaconic acid / isopropanol mixed solution is 33:7:415:2.5:0.2:260; the itaconic acid / isopropanol mixed solution is prepared by mixing itaconic acid and isopropanol in a mass ratio of 1:10;

[0080] Step 3, the modified epoxy itaconate, additives, ferrosilicate, silicon dioxide, silicone photoinitiator, and isopropyl alcohol are mixed in a mass ratio of 100:18:38:0.8:7:25 in a light-proof environment, and stirred at a speed of 550 r / min for 0.8 h to obtain a high-adhesion weather-resistant ink;

[0081] The additive is prepared by mixing 2-hydroxyethyl methacrylate phosphate, 4-methacrylamide-2,2,6,6-tetramethylpiperidine, trimethylolpropane triacrylate, and polyurethane acrylate in a mass ratio of 2.5:4.5:12:9.

[0082] Example 4

[0083] This embodiment discloses a method for preparing a high-adhesion weather-resistant ink, comprising the following steps:

[0084] Step 1, preparing functionalized carbon black and organosilicon photoinitiator;

[0085] The preparation of functionalized carbon black comprises the following steps:

[0086] Step (1), mixing carbon black and water in a mass ratio of 1:28, ultrasonically dispersing for 20 minutes to obtain a carbon black dispersion, introducing ozone at a flow rate of 3L / min into the carbon black dispersion, oxidizing at room temperature for 1.5 hours, adding a saturated sodium hydroxide aqueous solution after the oxidation is completed to adjust the pH value to 14, continuing to oxidize at room temperature for 7.5 hours, adding concentrated hydrochloric acid after the oxidation is completed to adjust the pH value to 4, centrifuging, filtering, taking a filter cake, adding water 6 times the mass of the filter cake for washing, and drying at 95°C for 7 hours to obtain carboxylated carbon black;

[0087] Step (2), dissolving p-aminophenol and acetone, adding carboxylated carbon black and dicyclohexylcarbodiimide, ultrasonically dispersing for 15 minutes, reacting at 75° C. for 11 hours, filtering after the reaction, taking the filter cake, adding acetone 6 times the mass of the filter cake to wash three times, and drying at 65° C. for 12 hours to obtain amidated carbon black;

[0088] Among them, the mass ratio of p-aminophenol, carboxylated carbon black, dicyclohexylcarbodiimide and acetone is 28:6.5:3.5:540;

[0089] Step (3), mixing the amidated carbon black with acetone, ultrasonically dispersing for 25 minutes, adding isophorone diisocyanate and dibutyltin dilaurate, reacting at 55° C. for 4 hours, filtering after the reaction, taking the filter cake, adding acetone 6 times the mass of the filter cake and washing three times to obtain functionalized carbon black;

[0090] Among them, the mass ratio of amidated carbon black, isophorone diisocyanate, dibutyltin dilaurate, and acetone is 5:120:0.7:380;

[0091] The preparation of organosilicon photoinitiator includes the following steps:

[0092] 1,3,5,7-tetramethylcyclotetrasiloxane, 4-propyleneoxy-2-hydroxybenzophenone and isopropanol were mixed, chloroplatinic acid was added, and the mixture was reacted at 90°C for 5 hours in a nitrogen atmosphere. After the reaction was completed, the solvent isopropanol was removed by rotary evaporation at 70°C to obtain an organosilicon photoinitiator;

[0093] Among them, the mass ratio of 1,3,5,7-tetramethylcyclotetrasiloxane, 4-propyleneoxy-2-hydroxybenzophenone, isopropanol, and chloroplatinic acid is 25.5:34:18:0.06;

[0094] Step 2: Mix polyethylene glycol and nano-titanium dioxide in a mass ratio of 1:20, stir and disperse at a speed of 3300r / min for 25min to obtain modified polyethylene glycol; mix modified polyethylene glycol, triethylene glycol, epoxy resin, triethylamine, and p-hydroxyanisole, react at 94°C for 3h, add itaconic acid / isopropanol mixed solution after the reaction, continue to react at 108°C for 4.5h, and after the reaction, remove the solvent isopropanol by rotary evaporation at 70°C to obtain epoxy itaconate; mix epoxy itaconate and functionalized carbon black in a mass ratio of 100:28, react at 45°C for 3.5h, and after the reaction, add triethanolamine to neutralize to a pH value of 7.4 to obtain modified epoxy itaconate;

[0095] The mass ratio of modified polyethylene glycol, triethylene glycol, epoxy resin, triethylamine, p-hydroxyanisole, and itaconic acid / isopropanol mixed solution is 34:6:420:2.8:0.3:265; the itaconic acid / isopropanol mixed solution is prepared by mixing itaconic acid and isopropanol in a mass ratio of 1:10;

[0096] Step 3: Mix the modified epoxy itaconate, additives, ferrosilicate, silicon dioxide, silicone photoinitiator and isopropyl alcohol in a mass ratio of 100:19:39:0.9:7.5:28 in a light-proof environment, stir at a speed of 580 r / min for 0.6 h, and obtain a high-adhesion weather-resistant ink.

[0097] The additive is prepared by mixing 2-hydroxyethyl methacrylate phosphate, 4-methacrylamide-2,2,6,6-tetramethylpiperidine, trimethylolpropane triacrylate, and polyurethane acrylate in a mass ratio of 2.8:4.8:14:9.5.

[0098] Example 5

[0099] This embodiment discloses a method for preparing a high-adhesion weather-resistant ink, comprising the following steps:

[0100] Step 1, preparing functionalized carbon black and organosilicon photoinitiator;

[0101] The preparation of functionalized carbon black comprises the following steps:

[0102] Step (1), mixing carbon black and water in a mass ratio of 1:30, ultrasonically dispersing for 20 minutes to obtain a carbon black dispersion, introducing ozone at a flow rate of 3L / min into the carbon black dispersion, oxidizing at room temperature for 1 hour, adding a saturated sodium hydroxide aqueous solution after the oxidation is completed to adjust the pH value to 14, continuing to oxidize at room temperature for 8 hours, adding concentrated hydrochloric acid after the oxidation is completed to adjust the pH value to 4, centrifuging, filtering, taking a filter cake, adding water 8 times the mass of the filter cake for washing, and drying at 100°C for 6 hours to obtain carboxylated carbon black;

[0103] Step (2), dissolving p-aminophenol and acetone, adding carboxylated carbon black and dicyclohexylcarbodiimide, ultrasonically dispersing for 20 minutes, reacting at 80° C. for 10 hours, filtering after the reaction, taking the filter cake, adding acetone 8 times the mass of the filter cake to wash three times, and drying at 70° C. for 10 hours to obtain amidated carbon black;

[0104] Among them, the mass ratio of p-aminophenol, carboxylated carbon black, dicyclohexylcarbodiimide and acetone is 30:7:4:550;

[0105] Step (3), mixing the amidated carbon black with acetone, ultrasonically dispersing for 30 minutes, adding isophorone diisocyanate and dibutyltin dilaurate, reacting at 60° C. for 3 hours, filtering after the reaction, taking the filter cake, adding acetone 8 times the mass of the filter cake and washing three times to obtain functionalized carbon black;

[0106] Among them, the mass ratio of amidated carbon black, isophorone diisocyanate, dibutyltin dilaurate, and acetone is 5:130:0.7:400;

[0107] The preparation of organosilicon photoinitiator includes the following steps:

[0108] 1,3,5,7-tetramethylcyclotetrasiloxane, 4-propyleneoxy-2-hydroxybenzophenone and isopropanol were mixed, chloroplatinic acid was added, and the mixture was reacted at 95°C for 4 hours in a nitrogen atmosphere. After the reaction was completed, the solvent isopropanol was removed by rotary evaporation at 75°C to obtain an organosilicon photoinitiator;

[0109] Among them, the mass ratio of 1,3,5,7-tetramethylcyclotetrasiloxane, 4-propyleneoxy-2-hydroxybenzophenone, isopropanol, and chloroplatinic acid is 26:35:20:0.06;

[0110] Step 2: Mix polyethylene glycol and nano-titanium dioxide in a mass ratio of 1:20, stir and disperse at a speed of 3500r / min for 20min to obtain modified polyethylene glycol; mix modified polyethylene glycol, triethylene glycol, epoxy resin, triethylamine, and p-hydroxyanisole, react at 95°C for 3h, add itaconic acid / isopropanol mixed solution after the reaction, continue to react at 110°C for 4h, and after the reaction, remove the solvent isopropanol by rotary evaporation at 75°C to obtain epoxy itaconate; mix epoxy itaconate and functionalized carbon black in a mass ratio of 100:30, react at 50°C for 3h, and after the reaction, add triethanolamine to neutralize to a pH value of 7.5 to obtain modified epoxy itaconate;

[0111] The mass ratio of modified polyethylene glycol, triethylene glycol, epoxy resin, triethylamine, p-hydroxyanisole, and itaconic acid / isopropanol mixed solution is 35:5:430:3:0.3:270; the itaconic acid / isopropanol mixed solution is prepared by mixing itaconic acid and isopropanol in a mass ratio of 1:10;

[0112] Step 3: Mix the modified epoxy itaconate, additives, ferrosilicate, silicon dioxide, silicone photoinitiator, and isopropyl alcohol in a mass ratio of 100:20:40:1:8:30 in a light-proof environment, and stir at a speed of 600 r / min for 0.5 h to obtain a high-adhesion weather-resistant ink;

[0113] The additive is prepared by mixing 2-hydroxyethyl methacrylate phosphate, 4-methacrylamide-2,2,6,6-tetramethylpiperidine, trimethylolpropane triacrylate, and polyurethane acrylate in a mass ratio of 3:5:15:10.

[0114] Comparative Example 1

[0115] This comparative example discloses a method for preparing ink, comprising the following steps:

[0116] Step 1, polyethylene glycol and nano titanium dioxide are mixed in a mass ratio of 1:20, and stirred and dispersed at a speed of 2500r / min for 30min to obtain modified polyethylene glycol; modified polyethylene glycol, triethylene glycol, epoxy resin, triethylamine, and p-hydroxyanisole are mixed, and reacted at 90°C for 4h. After the reaction is completed, itaconic acid / isopropanol mixed solution is added, and the reaction is continued at 100°C for 6h. After the reaction is completed, the solvent isopropanol is removed by rotary evaporation at 65°C to obtain epoxy itaconate; epoxy itaconate and carbon black are mixed in a mass ratio of 100:20, and triethanolamine is added to neutralize to a pH value of 7 to obtain modified epoxy itaconate;

[0117] The mass ratio of modified polyethylene glycol, triethylene glycol, epoxy resin, triethylamine, p-hydroxyanisole, and itaconic acid / isopropanol mixed solution is 30:10:400:1.5:0.2:250; the itaconic acid / isopropanol mixed solution is prepared by mixing itaconic acid and isopropanol in a mass ratio of 1:10;

[0118] Step 2: 1,3,5,7-tetramethylcyclotetrasiloxane, 4-propyleneoxy-2-hydroxybenzophenone and isopropanol are mixed, chloroplatinic acid is added, and the mixture is reacted at 85° C. for 6 h in a nitrogen atmosphere. After the reaction is completed, the solvent isopropanol is removed by rotary evaporation at 65° C. to obtain an organosilicon photoinitiator;

[0119] Among them, the mass ratio of 1,3,5,7-tetramethylcyclotetrasiloxane, 4-propyleneoxy-2-hydroxybenzophenone, isopropanol, and chloroplatinic acid is 24:32:10:0.05;

[0120] Step 3, the modified epoxy itaconate, additives, ferrosilicate, silicon dioxide, silicone photoinitiator, and isopropyl alcohol are mixed in a mass ratio of 100:15:35:0.5:6:20 in a light-proof environment, and stirred at a speed of 500 r / min for 1 hour to obtain ink;

[0121] The additive is prepared by mixing 2-hydroxyethyl methacrylate phosphate, 4-methacrylamide-2,2,6,6-tetramethylpiperidine, trimethylolpropane triacrylate, and polyurethane acrylate in a mass ratio of 2:4:10:8.

[0122] Comparative Example 2

[0123] This comparative example discloses a method for preparing ink, comprising the following steps:

[0124] Step 1, carbon black and water are mixed at a mass ratio of 1:20, and ultrasonically dispersed for 10 minutes to obtain a carbon black dispersion, ozone with a flow rate of 2.5L / min is introduced into the carbon black dispersion, and oxidation is carried out at room temperature for 2 hours. After the oxidation is completed, a saturated sodium hydroxide aqueous solution is added to adjust the pH value to 13, and the oxidation is continued at room temperature for 7 hours. After the oxidation is completed, concentrated hydrochloric acid is added to adjust the pH value to 3, centrifuged, filtered, and the filter cake is taken, and water 5 times the mass of the filter cake is added for washing, and dried at 90°C for 8 hours to obtain carboxylated carbon black;

[0125] The p-aminophenol and acetone were mixed and dissolved, carboxylated carbon black and dicyclohexylcarbodiimide were added, ultrasonic dispersion was performed for 10 minutes, the mixture was reacted at 70°C for 12 hours, and after the reaction, the mixture was filtered, the filter cake was taken, acetone of 5 times the mass of the filter cake was added for washing three times, and the mixture was dried at 60°C for 14 hours to obtain amidated carbon black;

[0126] Among them, the mass ratio of p-aminophenol, carboxylated carbon black, dicyclohexylcarbodiimide and acetone is 20:5:2:500;

[0127] The amidated carbon black was mixed with acetone, and ultrasonically dispersed for 20 minutes. Isophorone diisocyanate and dibutyltin dilaurate were added, and the mixture was reacted at 50°C for 5 hours. After the reaction was completed, the mixture was filtered, and the filter cake was taken and washed three times with acetone 5 times the mass of the filter cake to obtain functionalized carbon black.

[0128] Among them, the mass ratio of amidated carbon black, isophorone diisocyanate, dibutyltin dilaurate, and acetone is 5:100:0.6:300;

[0129] Step 2: Mix polyethylene glycol and nano-titanium dioxide in a mass ratio of 1:20, stir and disperse at a speed of 2500r / min for 30min to obtain modified polyethylene glycol; mix modified polyethylene glycol, triethylene glycol, epoxy resin, triethylamine, and p-hydroxyanisole, react at 90°C for 4h, add itaconic acid / isopropanol mixed solution after the reaction, continue to react at 100°C for 6h, and remove the solvent isopropanol by rotary evaporation at 65°C to obtain epoxy itaconate; mix epoxy itaconate and functionalized carbon black in a mass ratio of 100:20, react at 40°C for 4h, and add triethanolamine to neutralize to a pH of 7 after the reaction to obtain modified epoxy itaconate;

[0130] The mass ratio of modified polyethylene glycol, triethylene glycol, epoxy resin, triethylamine, p-hydroxyanisole, and itaconic acid / isopropanol mixed solution is 30:10:400:1.5:0.2:250; the itaconic acid / isopropanol mixed solution is prepared by mixing itaconic acid and isopropanol in a mass ratio of 1:10;

[0131] Step 3, the modified epoxy itaconate, additives, ferrosoferric oxide, silicon dioxide, 4-propyleneoxy-2-hydroxybenzophenone, and isopropanol are mixed in a mass ratio of 100:15:35:0.5:6:20 in a light-proof environment, and stirred at a speed of 500 r / min for 1 hour to obtain ink;

[0132] The additive is prepared by mixing 4-methylacrylamide-2,2,6,6-tetramethylpiperidine, trimethylolpropane triacrylate and polyurethane acrylate in a mass ratio of 4:10:8.

[0133] Comparative Example 3

[0134] This comparative example discloses a method for preparing ink, comprising the following steps:

[0135] Step 1, preparing functionalized carbon black and organosilicon photoinitiator;

[0136] The preparation of functionalized carbon black comprises the following steps:

[0137] Step (1), mixing carbon black and water in a mass ratio of 1:20, ultrasonically dispersing for 10 minutes to obtain a carbon black dispersion, introducing ozone at a flow rate of 2.5 L / min into the carbon black dispersion, oxidizing at room temperature for 2 hours, adding a saturated sodium hydroxide aqueous solution after the oxidation is completed to adjust the pH value to 13, continuing to oxidize at room temperature for 7 hours, adding concentrated hydrochloric acid after the oxidation is completed to adjust the pH value to 3, centrifuging, filtering, taking a filter cake, adding water 5 times the mass of the filter cake for washing, and drying at 90° C. for 8 hours to obtain carboxylated carbon black;

[0138] Step (2), dissolving p-aminophenol and acetone, adding carboxylated carbon black and dicyclohexylcarbodiimide, ultrasonically dispersing for 10 min, reacting at 70° C. for 12 h, filtering after the reaction, taking the filter cake, adding acetone 5 times the mass of the filter cake to wash three times, and drying at 60° C. for 14 h to obtain amidated carbon black;

[0139] Among them, the mass ratio of p-aminophenol, carboxylated carbon black, dicyclohexylcarbodiimide and acetone is 20:5:2:500;

[0140] Step (3), mixing the amidated carbon black with acetone, ultrasonically dispersing for 20 minutes, adding isophorone diisocyanate and dibutyltin dilaurate, reacting at 50° C. for 5 hours, filtering after the reaction, taking the filter cake, adding acetone 5 times the mass of the filter cake and washing three times to obtain functionalized carbon black;

[0141] Among them, the mass ratio of amidated carbon black, isophorone diisocyanate, dibutyltin dilaurate, and acetone is 5:100:0.6:300;

[0142] The preparation of organosilicon photoinitiator includes the following steps:

[0143] 1,3,5,7-tetramethylcyclotetrasiloxane, 4-propyleneoxy-2-hydroxybenzophenone and isopropanol were mixed, chloroplatinic acid was added, and the mixture was reacted at 85°C for 6 hours in a nitrogen atmosphere. After the reaction was completed, the solvent isopropanol was removed by rotary evaporation at 65°C to obtain an organosilicon photoinitiator;

[0144] Among them, the mass ratio of 1,3,5,7-tetramethylcyclotetrasiloxane, 4-propyleneoxy-2-hydroxybenzophenone, isopropanol, and chloroplatinic acid is 24:32:10:0.05;

[0145] Step 2: Mix polyethylene glycol, triethylene glycol, epoxy resin, triethylamine and p-hydroxyanisole, react at 90°C for 4 hours, add itaconic acid / isopropanol mixed solution after the reaction, continue to react at 100°C for 6 hours, remove the solvent isopropanol by rotary evaporation at 65°C to obtain epoxy itaconate; mix epoxy itaconate with functionalized carbon black in a mass ratio of 100:20, react at 40°C for 4 hours, add triethanolamine to neutralize to pH 7 after the reaction, and obtain modified epoxy itaconate;

[0146] Wherein, the mass ratio of polyethylene glycol, triethylene glycol, epoxy resin, triethylamine, p-hydroxyanisole, and itaconic acid / isopropanol mixed solution is 30:10:400:1.5:0.2:250; the itaconic acid / isopropanol mixed solution is prepared by mixing itaconic acid and isopropanol in a mass ratio of 1:10;

[0147] Step 3, the modified epoxy itaconate, additives, ferrosilicate, silicon dioxide, silicone photoinitiator, and isopropyl alcohol are mixed in a mass ratio of 100:15:35:0.5:6:20 in a light-proof environment, and stirred at a speed of 500 r / min for 1 hour to obtain ink;

[0148] The additive is prepared by mixing 2-hydroxyethyl methacrylate phosphate, trimethylolpropane triacrylate and polyurethane acrylate in a mass ratio of 2:10:8.

[0149] In the above embodiments and comparative examples: carbon black is from Shanghai Baiyan Industrial Co., Ltd., model carbon black CB611, CAS number: 1333-86-4; sodium hydroxide is from Wuxi Jingke Chemical Co., Ltd., CAS number: 1310-73-2; concentrated hydrochloric acid is from Sigma-Aldrich, model 38wt% hydrogen chloride aqueous solution; p-aminophenol is from Shandong Guohua Chemical Co., Ltd., CAS number: 123-30-8; acetone is from Shandong Wenshao Chemical Co., Ltd., CAS number: 67-64-1; dicyclohexylcarbodiimide is from AlfaAesar, CAS number: 538-75-0; isophorone diisocyanate is from Shanghai Aladdin Biochemical Technology Co., Ltd., CAS number :4098-71-9; dibutyltin dilaurate comes from Maoming Xiongda Chemical Co., Ltd., CAS No.: 77-58-7; 1,3,5,7-tetramethylcyclotetrasiloxane comes from Wuhan Kemik Biopharmaceutical Technology Co., Ltd., CAS No.: 2370-88-9; 4-propyleneoxy-2-hydroxybenzophenone comes from Guangdong Wengjiang Chemical Reagent Co., Ltd., CAS No.: 2549-87-3; isopropanol comes from Wuxi Jingke Chemical Co., Ltd., CAS No.: 67-63-0; chloroplatinic acid comes from Shandong New Kinetic Energy Chemical Co., Ltd., CAS No.: 16941-12-1; polyethylene glycol comes from Shandong Baihua Chemical Co., Ltd., model PEG-400, CAS No.: 25322-68-3; Nano titanium dioxide comes from Hangzhou Hengge Nanotechnology Co., Ltd., with an average particle size of 30 nm and CAS number: 13463-67-7; triethylene glycol comes from Shandong Xiya Chemical Co., Ltd., with CAS number: 112-27-6; epoxy resin comes from Baling Petrochemical Company, model epoxy resin E-51; triethylamine comes from Shanghai Aladdin Biochemical Technology Co., Ltd., with CAS number: 121-44-8; p-Hydroxyanisole comes from Maoming Xiongda Chemical Co., Ltd., with CAS number: 150-76-5; itaconic acid comes from Guangdong Wengjiang Chemical Reagent Co., Ltd., with CAS number: 97-65-4; triethanolamine comes from Chengdu Kelong Chemical Co., Ltd., with CAS number: 102-71-6; 2-Hydroxyethyl Methacrylate Ester phosphate was from Shanghai Aladdin Biochemical Technology Co., Ltd., CAS number: 52628-03-2; 4-methacrylamido-2,2,6,6-tetramethylpiperidine was from Shanghai MacLean Biochemical Technology Co., Ltd., CAS number: 31582-46-4; trimethylolpropane triacrylate was from Guangdong Wengjiang Chemical Reagent Co., Ltd., CAS number: 15625-89-5; polyurethane acrylate was from Hubei Langbowan Biomedicine Co., Ltd., model PUA901; ferroferric oxide was from Shanghai MacLean Biochemical Technology Co., Ltd., product name nano ferroferric oxide, product number I903421, particle size 50nm; silicon dioxide was from Hangzhou Hengge Nanotechnology Co., Ltd., with an average particle size of 30nm.

[0150] Test example

[0151] Comprehensive performance tests were conducted on Examples 1-5 and Comparative Examples 1-3. Specific test results are shown in Table 1:

[0152] Table 1

[0153]

[0154]

[0155] The tests of the various indicators in Table 1 are respectively based on the following standards: adhesion is measured with reference to GB / T13217.7-2023 "Ink Adhesion Test Method"; hardness is measured with reference to GB / T6739-2006 "Determination of Film Hardness by Pencil Method for Paints and Varnishes"; viscosity change rate is measured with reference to QB / T5489-2020 "Test Method for Storage Stability of Inkjet Inks"; the specific test method for weather resistance is as follows: the inks prepared in Examples 1-5 and Comparative Examples 1-3 are respectively printed on the surface of a glass plate, with an ink film thickness of 3 μm, and cured for 20 seconds under UV-LED ultraviolet light to obtain samples 1-8, and samples 1-8 are tested for weather resistance using a QUV ultraviolet accelerated aging tester, wherein the number of cycles is 25, and each cycle includes an irradiation intensity of 0.89 W / m 2 , irradiate with UV light at 60°C for 4 hours, and let it stand to room temperature after the cycle.

[0156] It can be seen from the test results in Table 1 that the high-adhesion weather-resistant ink prepared by the present invention has high adhesion and weather resistance, good storage stability and excellent mechanical properties.

[0157] The present invention obtains carboxylated carbon black by oxidizing carbon black, and obtains amidated carbon black having phenolic hydroxyl groups by reacting the carboxyl group of the carboxylated carbon black with the amino group of p-aminophenol, and reacts the amidated carbon black with isophorone diisocyanate to obtain functionalized carbon black having isocyanate groups. The surface treatment improves the dispersibility of carbon black, and it is not easy to agglomerate in the ink matrix. At the same time, the surface of the functionalized carbon black has highly reactive isocyanate groups, which can react with epoxy itaconate, the ink matrix material, so that the carbon black is grafted on the epoxy itaconate, further improving the dispersibility of carbon black in the ink and the stability of the ink. In Comparative Example 1, the carbon black has no surface modification, and its dispersibility in the matrix material becomes poor, and it is easy to agglomerate and stratify, thereby reducing the stability of the ink, so the viscosity change rate of Comparative Example 1 is higher than that of the embodiment.

[0158] The present invention grafts the photoinitiator onto the organosilicon by a hydrosilylation reaction between 1,3,5,7-tetramethylcyclotetrasiloxane and 4-propyleneoxy-2-hydroxybenzophenone. The organosilicon structure in the obtained organosilicon photoinitiator can increase the adhesion of the ink; 2-hydroxyethyl methacrylate phosphate contains a carbon-carbon double bond structure, which can participate in the photocuring reaction of the ink and cross-link with the matrix resin, and further improve the adhesion of the ink as an adhesion promoter. In Comparative Example 2, the photoinitiator is not grafted with organosilicon, and 2-hydroxyethyl methacrylate phosphate is not added to the ink, so the adhesion of Comparative Example 2 is lower than that of the embodiment.

[0159] The present invention uses an in-situ polymerization method to make triethylene glycol, polyethylene glycol adsorbed on nano titanium dioxide and epoxy resin undergo a ring-opening reaction, introduces nano titanium dioxide with anti-ultraviolet aging performance, improves the weather resistance of epoxy itaconate, and adds 4-methyl acrylamide-2,2,6,6-tetramethyl piperidine containing a carbon-carbon double bond structure, which can participate in the photocuring reaction of the ink and cross-link with the matrix resin, and further improve the weather resistance of the ink as a light stabilizer. In Comparative Example 3, nano titanium dioxide is not added to the polyethylene glycol, and 4-methyl acrylamide-2,2,6,6-tetramethyl piperidine is not added to the ink, so the weather resistance of Sample 8 prepared by Comparative Example 3 is not as good as that of the embodiment.

[0160] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a high-adhesion weather-resistant ink, characterized in that: The following steps are involved: Step 1, preparing functionalized carbon black and organosilicon photoinitiator; Wherein, the preparation of functionalized carbon black comprises the following steps: Step (1), dissolving p-aminophenol and acetone, adding carboxylated carbon black and dicyclohexylcarbodiimide, performing ultrasonic dispersion, reacting, filtering, washing, and drying after the reaction is completed to obtain amidated carbon black; The mass ratio of p-aminophenol, carboxylated carbon black, dicyclohexylcarbodiimide and acetone is 20-30:5-7:2-4:500-550; the reaction conditions are: reacting at 70-80°C for 10-12h; Step (2), mixing the amidated carbon black with acetone, ultrasonically dispersing, adding isophorone diisocyanate and dibutyltin dilaurate, reacting, filtering and washing after the reaction is completed to obtain functionalized carbon black; The mass ratio of amidated carbon black, isophorone diisocyanate, dibutyltin dilaurate and acetone is 5:100-130:0.6-0.7:300-400; the reaction conditions are: reacting at a temperature of 50-60°C for 3-5h; The preparation of organosilicon photoinitiator includes the following steps: 1,3,5,7-tetramethylcyclotetrasiloxane, 4-propyleneoxy-2-hydroxybenzophenone and isopropanol are mixed, chloroplatinic acid is added, and the mixture is reacted. After the reaction is completed, the solvent isopropanol is removed by rotary evaporation to obtain an organosilicon photoinitiator; The mass ratio of 1,3,5,7-tetramethylcyclotetrasiloxane, 4-propyleneoxy-2-hydroxybenzophenone, isopropanol and chloroplatinic acid is 24-26:32-35:10-20:0.05-0.06; the reaction conditions are: reacting in a nitrogen atmosphere at a temperature of 85-95° C. for 4-6 hours; Step 2: Mix polyethylene glycol and nano titanium dioxide, stir and disperse to obtain modified polyethylene glycol; mix modified polyethylene glycol, triethylene glycol, epoxy resin, triethylamine and p-hydroxyanisole, react, add itaconic acid / isopropanol mixed solution after the reaction is completed, continue to react, remove the solvent isopropanol by rotary evaporation after the reaction is completed, and obtain epoxy itaconate; mix epoxy itaconate and functionalized carbon black, react, neutralize after the reaction is completed, and obtain modified epoxy itaconate; Wherein, when preparing epoxy itaconate, the mass ratio of modified polyethylene glycol, triethylene glycol, epoxy resin, triethylamine, p-hydroxyanisole, itaconic acid / isopropanol mixed solution is 30-35:5-10:400-430:1.5-3:0.2-0.3:250-270, and the reaction conditions are: react at 90-95°C for 3-4h; and the continued reaction conditions are: continue to react at 100-110°C for 4-6h; When preparing modified epoxy itaconate, the mass ratio of epoxy itaconate to functionalized carbon black is 100:20-30; the reaction conditions are: reacting at 40-50°C for 3-4h; the pH value after neutralization is 7-7.5; Step 3, mixing and stirring the modified epoxy itaconate, additives, ferrosoferric oxide, silicon dioxide, organosilicon photoinitiator and isopropyl alcohol to obtain a high-adhesion weather-resistant ink; The additive is prepared by mixing 2-hydroxyethyl methacrylate phosphate, 4-methacrylamide-2,2,6,6-tetramethylpiperidine, trimethylolpropane triacrylate and polyurethane acrylate in a mass ratio of 2-3:4-5:10-15:8-10.

2. The method for preparing a high-adhesion weather-resistant ink according to claim 1, characterized in that: In the preparation of the functionalized carbon black, the carboxylation carbon black in step (1) comprises the following steps: The carbon black is mixed with water, and ultrasonically dispersed to obtain a carbon black dispersion liquid. Ozone is introduced into the carbon black dispersion liquid for oxidation. After the oxidation is completed, an alkaline regulator is added to adjust the pH value. The oxidation is continued. After the oxidation is completed, an acidic regulator is added to adjust the pH value. The mixture is centrifuged, filtered, washed, and dried to obtain carboxylated carbon black. Among them, the mass ratio of carbon black to water is 1:20-30; the flow rate of ozone is 2.5-3L / min, the oxidation conditions are: oxidation at room temperature for 1-2h; the continued oxidation conditions are: oxidation at a pH value of 13-14 and continued oxidation at room temperature for 7-8h; the pH value after adjustment by the acidic regulator is 3-4.

3. The method for preparing a high-adhesion weather-resistant ink according to claim 1, characterized in that: In the step 2, the mass ratio of polyethylene glycol to nano-titanium dioxide is 1:20; the stirring and dispersing conditions are: stirring and dispersing at a speed of 2500-3500 r / min for 20-30 min.

4. The method for preparing a high-adhesion weather-resistant ink according to claim 1, characterized in that: In the step three, the mass ratio of modified epoxy itaconate, additive, ferrosoferric oxide, silicon dioxide, organosilicon photoinitiator and isopropanol is 100:15-20:35-40:0.5-1:6-8:20-30.

5. A high-adhesion weather-resistant ink prepared by the method for preparing a high-adhesion weather-resistant ink as described in any one of claims 1 to 4.

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