A high hiding ink and preparation method thereof

Abstract

The present invention relates to the technical field of inks, and discloses a high hiding ink and a preparation method thereof. The preparation method comprises: reacting caprolactone-modified methacrylate, acetone, triethylamine, chlorinated carbon black, and hydroquinone, adding a terminal hydroxyl hyperbranched polyester to react again, and obtaining a carbon black / hyperbranched polyester composite material; mixing alkenyl fumed silica, butyl acrylate, hydroxyethyl methacrylate, N-hydroxymethyl acrylamide, trimethylolpropane triacrylate, and polyurethane acrylate to obtain an acrylate monomer; mixing carbon black / hyperbranched polyester composite material, acrylate monomer, photoinitiator, defoamer, leveling agent, and acetone, stirring, and obtaining a high hiding ink. The ink has high hiding and insulation properties.

Description

Technical Field

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

[0002] The tempered glass used in electronic products needs to be treated with specific inks for light shielding to achieve the effect of light blocking. In the prior art, the hiding performance of the ink is improved by increasing the proportion of carbon black in the ink or increasing the number of times the ink is printed. However, when the amount of carbon black is too much, the carbon black particles are easy to agglomerate, and the ink will produce light transmission. In addition, carbon black is conductive, and excessive carbon black in the ink will reduce the resistance value of the ink film layer, affecting the safety of electronic products; and increasing the number of times the ink is printed will increase the thickness of the ink film layer, and the defective rate of the product will also increase.

[0003] Prior art, such as Chinese patent application CN114656837A, discloses a high hiding and high insulation black ink and a preparation method thereof. By adding carbon black, barium sulfate, epoxy-modified polysiloxane, dispersant, defoamer, and leveling agent to acrylic resin, the obtained black ink has high hiding power and high insulation, and is better suitable for the light-shielding layer of reinforced glass of electronic products. However, since the carbon black particles are not surface treated, the carbon black has the defect of insufficient dispersibility in the ink, and the hiding and insulation properties need to be improved. Summary of the invention

[0004] 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, wherein the ink has high hiding power and insulation.

[0005] In order to achieve the above object, the technical solution adopted by the present invention is as follows:

[0006] A method for preparing a high hiding ink comprises the following steps:

[0007] Step 1: preparing carbon black / hyperbranched polyester composite material and acrylate monomer;

[0008] Wherein, the carbon black / hyperbranched polyester composite material is prepared by the following steps:

[0009] Step (1), mixing carbon black with aqueous nitric acid solution, ultrasonically dispersing, stirring for reaction, filtering, washing, and drying after the reaction is completed to obtain carboxylated carbon black; mixing carboxylated carbon black with thionyl chloride, ultrasonically dispersing, and reacting, after the reaction is completed, rotary evaporating to remove excess thionyl chloride to obtain acyl chloride carbon black;

[0010] Step (2), mixing caprolactone-modified methacrylate, acetone, and triethylamine, adding acyl chloride carbon black and hydroquinone, reacting, and after the reaction is completed, continuing the reaction, adding terminal hydroxyl hyperbranched polyester, and reacting again, and after the reaction is completed, removing the solvent acetone by rotary evaporation to obtain a carbon black / hyperbranched polyester composite material;

[0011] Wherein, the acrylate monomer is prepared by the following steps:

[0012] Step (1), mixing fumed silica with ethyl acetate, ultrasonically dispersing, adding 3-(2,3-epoxypropoxy)propyltrimethoxysilane and water, reacting, filtering, washing, and drying after the reaction to obtain epoxy fumed silica;

[0013] Mix epoxy fumed silica, maleic acid mono-2-(methacryloyloxy)ethyl ester and acetone, react, cool to room temperature after the reaction, filter, wash with acetone, and dry to obtain alkenyl fumed silica;

[0014] Step (2), mixing alkenyl fumed silica, butyl acrylate, hydroxyethyl methacrylate, N-methylol acrylamide, trimethylolpropane triacrylate, and polyurethane acrylate to obtain an acrylate monomer;

[0015] Step 2: Mix the carbon black / hyperbranched polyester composite material, acrylate monomer, photoinitiator, defoamer, leveling agent and acetone, and stir to obtain a high hiding ink.

[0016] Preferably, when preparing the carbon black / hyperbranched polyester composite material, in step (1): the mass ratio of carbon black to aqueous nitric acid solution is 1:14-16, and the aqueous nitric acid solution is a 65wt% aqueous nitric acid solution; when preparing carboxylated carbon black, the reaction conditions are: stirring and reacting for 24-28h at a temperature of 90-100°C in a nitrogen atmosphere; the mass ratio of carboxylated carbon black to thionyl chloride is 1:8-10; when preparing acyl chloride carbon black, the reaction conditions are: reacting for 18-24h at a temperature of 55-65°C in a nitrogen atmosphere.

[0017] Preferably, when preparing the carbon black / hyperbranched polyester composite material, in step (2): the mass ratio of caprolactone-modified methacrylate, chlorinated carbon black, terminal hydroxyl hyperbranched polyester, acetone, triethylamine, and hydroquinone is 5-5.5:12-14:22-24:50-60:3-3.5:0.01; the reaction conditions are: react at a temperature of -5-0°C for 1-2h; the continued reaction conditions are: continue to react at a temperature of 25-30°C for 3-4h; and the re-reaction conditions are: react again at a temperature of 25-30°C for 2-3h.

[0018] Preferably, when preparing the acrylate monomer, in step (1), the mass ratio of fumed silica, ethyl acetate, 3-(2,3-epoxypropoxy)propyltrimethoxysilane and water is 3.5-4:180-200:35-40:1; when preparing epoxy fumed silica, the reaction conditions are: reacting at a temperature of 60-70°C for 10-12h.

[0019] Preferably, when preparing epoxy fumed silica, the washing agent used in the washing operation includes ethyl acetate.

[0020] Preferably, when preparing the acrylic acid ester monomer, in step (1), the mass ratio of epoxy fumed silica, maleic acid mono-2-(methacryloyloxy)ethyl ester and acetone is 1:25-30:30-40; when preparing alkenyl fumed silica, the reaction conditions are: reacting in a nitrogen atmosphere at a temperature of 80-90° C. for 8-10 hours.

[0021] Preferably, in the case of olefinic fumed silica, the washing agent used in the washing operation comprises acetone.

[0022] Preferably, when preparing the acrylate monomer, in step (2), the mass ratio of alkenyl fumed silica, butyl acrylate, hydroxyethyl methacrylate, N-hydroxymethyl acrylamide, trimethylolpropane triacrylate and polyurethane acrylate is 2-3:25-30:5-8:5-8:10-15:35-40.

[0023] Preferably, in the step 2: the mass ratio of the carbon black / hyperbranched polyester composite material, the acrylate monomer, the photoinitiator, the defoaming agent, the leveling agent and the acetone is 90-100:40:5-6:0.8-1:0.8-1:25-30, and the photoinitiator is a mixture of photoinitiator ITX and photoinitiator 1173 in a mass ratio of 1:1.

[0024] Preferably, a high hiding ink is prepared by the method for preparing the high hiding ink as described above.

[0025] Compared with the prior art, the present invention has the following beneficial effects:

[0026] In the ink prepared by the present invention, carbon black is surface modified to prepare a carbon black / hyperbranched polyester composite material, which is then mixed with an acrylate monomer, a photoinitiator, an additive, and a solvent to increase the dispersibility of the carbon black in the ink while reducing the conductive property of the carbon black, thereby improving the hiding power of the ink.

[0027] The invention prepares carboxylated carbon black by a nitric acid oxidation method, activates the carboxyl groups on the surface of the carboxylated carbon black by thionyl chloride, and converts them into acyl chloride groups. The obtained acyl chloride carbon black reacts with the hydroxyl groups of caprolactone-modified methacrylate, and the remaining acyl chloride groups after the reaction continue to react with the terminal hydroxyl groups of terminal hydroxyl hyperbranched polyester to obtain a carbon black / hyperbranched polyester composite material. The caprolactone-modified methacrylate is a macromolecular monomer formed by polymerization of hydroxyethyl methacrylate and caprolactone monomer, and can improve the mechanical properties of ink such as flexibility. Since the caprolactone-modified methacrylate has an active group carbon-carbon double bond, it can participate in a photocuring reaction after being grafted on the surface of the carbon black. The terminal hydroxyl hyperbranched polyester is a hyperbranched polymer, has good solubility, excellent film-forming property, weather resistance and mechanical property, can be added to the ink as an active polymer to improve the comprehensive property of the ink, and has a large number of active functional group hydroxyl groups, which can react and graft with the acyl chloride groups of the acyl chloride carbon black, and can be used as a surface modifier to improve the dispersion of carbon black in the ink, hinder the contact between carbon black particles, and reduce the conductive property of the carbon black.

[0028] The present invention uses an epoxy silane coupling agent to perform surface modification on fumed silica, and the obtained epoxy fumed silica undergoes a ring-opening reaction with maleic acid mono-2-(methacryloyloxy)ethyl ester to obtain alkenyl fumed silica; alkenyl fumed silica, butyl acrylate, hydroxyethyl methacrylate, N-hydroxymethyl acrylamide, trimethylolpropane triacrylate, and polyurethane acrylate are mixed to obtain an acrylate monomer; wherein the fumed silica has a highly efficient matting effect, and the surface of the fumed silica is modified to graft carbon-carbon double bonds so that the fumed silica can participate in a photocuring reaction, thereby improving the dispersibility and compatibility of the fumed silica in an ink matrix and improving the covering effect of the ink;

[0029] After the carbon black / hyperbranched polyester composite material is mixed with an acrylate monomer, the polymer can be polymerized under the condition of a photoinitiator to form a polymer. In addition, due to the interaction between the carbon black / hyperbranched polyester composite material and the hydroxyl group in the acrylate monomer, the dispersibility of the carbon black in the ink matrix is ​​further improved, the conductivity is reduced, and the covering ability of the ink is synergistically improved with the fumed silica in the acrylate monomer, so that the prepared ink has high covering property. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 It is a process flow chart of preparing high hiding ink in the present invention;

[0031] Figure 2 It is a line graph of the OD values ​​of Examples 1-5 and Comparative Examples 1-2 in the comprehensive performance test of the present invention. DETAILED DESCRIPTION

[0032] 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.

[0033] Example 1

[0034] This embodiment discloses a method for preparing a high hiding ink, comprising the following steps:

[0035] Step 1: preparing carbon black / hyperbranched polyester composite material and acrylate monomer;

[0036] Wherein, the carbon black / hyperbranched polyester composite material is prepared by the following steps:

[0037] Step (1), mixing carbon black with a 65wt% nitric acid aqueous solution in a mass ratio of 1:14, ultrasonically dispersing for 20 minutes, stirring and reacting for 28 hours at 90°C in a nitrogen atmosphere, filtering after the reaction, taking the filter cake, washing with deionized water until the washing liquid is neutral, and drying at 50°C for 16 hours to obtain carboxylated carbon black;

[0038] The carboxylated carbon black and thionyl chloride were mixed in a mass ratio of 1:8, ultrasonically dispersed for 15 minutes, reacted at 55°C for 24 hours in a nitrogen atmosphere, and after the reaction, the excess thionyl chloride was removed by rotary evaporation at 50°C to obtain acyl chloride carbon black;

[0039] Step (2), caprolactone-modified methacrylate, acetone, and triethylamine are mixed and stirred for 20 minutes, acyl chloride carbon black and hydroquinone are added, and the reaction is carried out at a temperature of -5°C for 2 hours. After the reaction is completed, the reaction is continued at a temperature of 25°C for 4 hours. After the reaction is completed, the terminal hydroxyl hyperbranched polyester is added, and the reaction is carried out at a temperature of 25°C for 3 hours. After the reaction is completed, the solvent acetone is removed by rotary evaporation at a temperature of 35°C to obtain a carbon black / hyperbranched polyester composite material;

[0040] Among them, the mass ratio of caprolactone-modified methacrylate, acylated carbon black, terminal hydroxyl hyperbranched polyester, acetone, triethylamine, and hydroquinone is 5:12:22:50:3:0.01;

[0041] Wherein, the acrylate monomer is prepared by the following steps:

[0042] Step (1), mixing fumed silica with ethyl acetate, ultrasonically dispersing for 30 minutes, adding 3-(2,3-epoxypropoxy)propyltrimethoxysilane and water, wherein the mass ratio of fumed silica, ethyl acetate, 3-(2,3-epoxypropoxy)propyltrimethoxysilane and water is 3.5:180:35:1, reacting at 60°C for 12 hours, filtering after the reaction, taking the filter cake, adding ethyl acetate 5 times the mass of the filter cake for washing three times, and drying at 70°C for 12 hours to obtain epoxy fumed silica;

[0043] Epoxy fumed silica, maleic acid mono-2-(methacryloyloxy)ethyl ester and acetone were mixed in a mass ratio of 1:25:30, reacted at 80°C for 10 hours in a nitrogen atmosphere, cooled to room temperature after the reaction, filtered, and the filter cake was taken out, acetone 5 times the mass of the filter cake was added for washing, and dried at 70°C for 24 hours to obtain alkenyl fumed silica;

[0044] Step (2), mixing alkenyl fumed silica, butyl acrylate, hydroxyethyl methacrylate, N-methylol acrylamide, trimethylolpropane triacrylate, and polyurethane acrylate in a mass ratio of 2:30:8:5:10:35 to obtain an acrylate monomer;

[0045] Step 2: Mix the carbon black / hyperbranched polyester composite material, acrylate monomer, photoinitiator, defoamer, leveling agent and acetone in a mass ratio of 90:40:5:0.8:0.8:25 in a light-proof environment, and stir at a speed of 300 r / min for 40 minutes to obtain a high hiding ink;

[0046] The photoinitiator is prepared by mixing photoinitiator ITX and photoinitiator 1173 in a mass ratio of 1:1.

[0047] Example 2

[0048] This embodiment discloses a method for preparing a high hiding ink, comprising the following steps:

[0049] Step 1: preparing carbon black / hyperbranched polyester composite material and acrylate monomer;

[0050] Wherein, the carbon black / hyperbranched polyester composite material is prepared by the following steps:

[0051] Step (1), mixing carbon black with a 65wt% nitric acid aqueous solution in a mass ratio of 1:14, ultrasonically dispersing for 25min, stirring and reacting for 28h at 90°C in a nitrogen atmosphere, filtering after the reaction, taking the filter cake, washing with deionized water until the washing liquid is neutral, and drying at 55°C for 14h to obtain carboxylated carbon black;

[0052] The carboxylated carbon black and thionyl chloride were mixed in a mass ratio of 1:8, ultrasonically dispersed for 15 minutes, reacted at 55°C for 22 hours in a nitrogen atmosphere, and after the reaction, the excess thionyl chloride was removed by rotary evaporation at 55°C to obtain acyl chloride carbon black;

[0053] Step (2), caprolactone-modified methacrylate, acetone, and triethylamine are mixed and stirred for 20 minutes, acyl chloride carbon black and hydroquinone are added, and the reaction is carried out at a temperature of -5°C for 1.5 hours. After the reaction is completed, the reaction is continued at a temperature of 25°C for 3.5 hours. After the reaction is completed, the terminal hydroxyl hyperbranched polyester is added, and the reaction is carried out at a temperature of 25°C for 2.5 hours. After the reaction is completed, the solvent acetone is removed by rotary evaporation at a temperature of 35°C to obtain a carbon black / hyperbranched polyester composite material;

[0054] Among them, the mass ratio of caprolactone-modified methacrylate, chlorinated carbon black, terminal hydroxyl hyperbranched polyester, acetone, triethylamine, and hydroquinone is 5.2:12.5:22.5:53:3.2:0.01;

[0055] Wherein, the acrylate monomer is prepared by the following steps:

[0056] Step (1), mixing fumed silica with ethyl acetate, ultrasonically dispersing for 30 minutes, adding 3-(2,3-epoxypropoxy)propyltrimethoxysilane and water, wherein the mass ratio of fumed silica, ethyl acetate, 3-(2,3-epoxypropoxy)propyltrimethoxysilane and water is 3.6:185:36:1, reacting at 65°C for 11 hours, filtering after the reaction, taking the filter cake, adding ethyl acetate 5 times the mass of the filter cake for washing three times, and drying at 75°C for 11 hours to obtain epoxy fumed silica;

[0057] Epoxy fumed silica, maleic acid mono-2-(methacryloyloxy)ethyl ester and acetone were mixed in a mass ratio of 1:26:33, reacted in a nitrogen atmosphere at 85°C for 9 hours, cooled to room temperature after the reaction, filtered, and the filter cake was taken, 6 times the mass of the filter cake was added with acetone for washing, and dried at 75°C for 22 hours to obtain alkenyl fumed silica;

[0058] Step (2), mixing alkenyl fumed silica, butyl acrylate, hydroxyethyl methacrylate, N-methylol acrylamide, trimethylolpropane triacrylate, and polyurethane acrylate in a mass ratio of 2.3:29:7:6:12:36 to obtain an acrylate monomer;

[0059] Step 2: Mix the carbon black / hyperbranched polyester composite material, acrylate monomer, photoinitiator, defoamer, leveling agent and acetone in a mass ratio of 93:40:5.3:0.8:0.8:26 in a light-proof environment, and stir at a speed of 320 r / min for 40 minutes to obtain a high hiding ink;

[0060] The photoinitiator is prepared by mixing photoinitiator ITX and photoinitiator 1173 in a mass ratio of 1:1.

[0061] Example 3

[0062] This embodiment discloses a method for preparing a high hiding ink, comprising the following steps:

[0063] Step 1: preparing carbon black / hyperbranched polyester composite material and acrylate monomer;

[0064] Wherein, the carbon black / hyperbranched polyester composite material is prepared by the following steps:

[0065] Step (1), mixing carbon black with a 65wt% nitric acid aqueous solution in a mass ratio of 1:15, ultrasonically dispersing for 25min, stirring and reacting for 26h at 95°C in a nitrogen atmosphere, filtering after the reaction, taking the filter cake, washing with deionized water until the washing liquid is neutral, and drying at 55°C for 14h to obtain carboxylated carbon black;

[0066] The carboxylated carbon black and thionyl chloride were mixed in a mass ratio of 1:9, ultrasonically dispersed for 15 minutes, reacted at 60°C for 20 hours in a nitrogen atmosphere, and after the reaction, the excess thionyl chloride was removed by rotary evaporation at 55°C to obtain acyl chloride carbon black;

[0067] Step (2), caprolactone-modified methacrylate, acetone, and triethylamine are mixed and stirred for 25 minutes, acyl chloride carbon black and hydroquinone are added, and the reaction is carried out at a temperature of -2°C for 1.5 hours. After the reaction is completed, the reaction is continued at a temperature of 28°C for 3.5 hours. After the reaction is completed, a terminal hydroxyl hyperbranched polyester is added, and the reaction is carried out at a temperature of 28°C for 2.5 hours. After the reaction is completed, the solvent acetone is removed by rotary evaporation at a temperature of 40°C to obtain a carbon black / hyperbranched polyester composite material;

[0068] Among them, the mass ratio of caprolactone-modified methacrylate, acylated carbon black, terminal hydroxyl hyperbranched polyester, acetone, triethylamine, and hydroquinone is 5.3:13:23:55:3.3:0.01;

[0069] Wherein, the acrylate monomer is prepared by the following steps:

[0070] Step (1), mixing fumed silica with ethyl acetate, ultrasonically dispersing for 40 minutes, adding 3-(2,3-epoxypropoxy)propyltrimethoxysilane and water, wherein the mass ratio of fumed silica, ethyl acetate, 3-(2,3-epoxypropoxy)propyltrimethoxysilane and water is 3.8:190:38:1, reacting at 65°C for 11 hours, filtering after the reaction, taking the filter cake, adding ethyl acetate 6 times the mass of the filter cake for washing three times, and drying at 75°C for 11 hours to obtain epoxy fumed silica;

[0071] Epoxy fumed silica, maleic acid mono-2-(methacryloyloxy)ethyl ester and acetone were mixed in a mass ratio of 1:28:35, reacted at 85°C for 9 hours in a nitrogen atmosphere, cooled to room temperature after the reaction, filtered, and the filter cake was taken out, acetone 6 times the mass of the filter cake was added for washing, and dried at 75°C for 22 hours to obtain alkenyl fumed silica;

[0072] Step (2), mixing alkenyl fumed silica, butyl acrylate, hydroxyethyl methacrylate, N-methylol acrylamide, trimethylolpropane triacrylate, and polyurethane acrylate in a mass ratio of 2.5:28:6:7:13:38 to obtain an acrylate monomer;

[0073] Step 2: Mix the carbon black / hyperbranched polyester composite material, acrylate monomer, photoinitiator, defoamer, leveling agent and acetone in a mass ratio of 95:40:5.5:0.9:0.9:28 in a light-proof environment, and stir at a speed of 350 r / min for 35 minutes to obtain a high hiding ink;

[0074] The photoinitiator is prepared by mixing photoinitiator ITX and photoinitiator 1173 in a mass ratio of 1:1.

[0075] Example 4

[0076] This embodiment discloses a method for preparing a high hiding ink, comprising the following steps:

[0077] Step 1: preparing carbon black / hyperbranched polyester composite material and acrylate monomer;

[0078] Wherein, the carbon black / hyperbranched polyester composite material is prepared by the following steps:

[0079] Step (1), mixing carbon black with a 65wt% nitric acid aqueous solution in a mass ratio of 1:16, ultrasonically dispersing for 30 minutes, stirring and reacting for 24 hours at 100°C in a nitrogen atmosphere, filtering after the reaction, taking the filter cake, washing with deionized water until the washing liquid is neutral, and drying at 55°C for 14 hours to obtain carboxylated carbon black;

[0080] The carboxylated carbon black and thionyl chloride were mixed in a mass ratio of 1:10, ultrasonically dispersed for 15 minutes, reacted at 60°C for 20 hours in a nitrogen atmosphere, and after the reaction, the excess thionyl chloride was removed by rotary evaporation at 55°C to obtain acyl chloride carbon black;

[0081] Step (2), caprolactone-modified methacrylate, acetone, and triethylamine are mixed and stirred for 30 minutes, acyl chloride carbon black and hydroquinone are added, and the reaction is carried out at a temperature of 9° C. for 1 hour. After the reaction is completed, the reaction is continued at a temperature of 30° C. for 3.5 hours. After the reaction is completed, a terminal hydroxyl hyperbranched polyester is added, and the reaction is carried out at a temperature of 30° C. for 2.5 hours. After the reaction is completed, the solvent acetone is removed by rotary evaporation at a temperature of 40° C. to obtain a carbon black / hyperbranched polyester composite material;

[0082] Among them, the mass ratio of caprolactone-modified methacrylate, chlorinated carbon black, terminal hydroxyl hyperbranched polyester, acetone, triethylamine, and hydroquinone is 5.4:13.5:23.5:58:3.4:0.01;

[0083] Wherein, the acrylate monomer is prepared by the following steps:

[0084] Step (1), mixing fumed silica with ethyl acetate, ultrasonically dispersing for 50 minutes, adding 3-(2,3-epoxypropoxy)propyltrimethoxysilane and water, wherein the mass ratio of fumed silica, ethyl acetate, 3-(2,3-epoxypropoxy)propyltrimethoxysilane and water is 3.9:195:39:1, reacting at 65°C for 11 hours, filtering after the reaction, taking the filter cake, adding ethyl acetate 6 times the mass of the filter cake for washing three times, and drying at 75°C for 11 hours to obtain epoxy fumed silica;

[0085] Epoxy fumed silica, maleic acid mono-2-(methacryloyloxy)ethyl ester and acetone were mixed in a mass ratio of 1:29:38, reacted at 90°C for 9 hours in a nitrogen atmosphere, cooled to room temperature after the reaction, filtered, and the filter cake was taken out, acetone 6 times the mass of the filter cake was added for washing, and dried at 75°C for 22 hours to obtain alkenyl fumed silica;

[0086] Step (2), mixing alkenyl fumed silica, butyl acrylate, hydroxyethyl methacrylate, N-methylol acrylamide, trimethylolpropane triacrylate, and polyurethane acrylate in a mass ratio of 2.8:26:5.5:7.5:14:39 to obtain an acrylate monomer;

[0087] Step 2: Mix the carbon black / hyperbranched polyester composite material, acrylate monomer, photoinitiator, defoamer, leveling agent and acetone in a mass ratio of 98:40:5.8:1:1:230 in a light-proof environment, and stir at a speed of 380 r / min for 35 minutes to obtain a high hiding ink;

[0088] The photoinitiator is prepared by mixing photoinitiator ITX and photoinitiator 1173 in a mass ratio of 1:1.

[0089] Example 5

[0090] This embodiment discloses a method for preparing a high hiding ink, comprising the following steps:

[0091] Step 1: preparing carbon black / hyperbranched polyester composite material and acrylate monomer;

[0092] Wherein, the carbon black / hyperbranched polyester composite material is prepared by the following steps:

[0093] Step (1), mixing carbon black with a 65wt% nitric acid aqueous solution in a mass ratio of 1:16, ultrasonically dispersing for 30 minutes, stirring and reacting for 24 hours at 100°C in a nitrogen atmosphere, filtering after the reaction, taking the filter cake, washing with deionized water until the washing liquid is neutral, and drying at 60°C for 12 hours to obtain carboxylated carbon black;

[0094] The carboxylated carbon black and thionyl chloride were mixed in a mass ratio of 1:10, ultrasonically dispersed for 20 minutes, reacted at 65°C for 18 hours in a nitrogen atmosphere, and after the reaction, the excess thionyl chloride was removed by rotary evaporation at 60°C to obtain acyl chloride carbon black;

[0095] Step (2), caprolactone-modified methacrylate, acetone, and triethylamine are mixed and stirred for 30 minutes, acyl chloride carbon black and hydroquinone are added, and the reaction is carried out at a temperature of 0° C. for 1 hour. After the reaction is completed, the reaction is continued at a temperature of 30° C. for 3 hours. After the reaction is completed, a terminal hydroxyl hyperbranched polyester is added, and the reaction is carried out at a temperature of 30° C. for 2 hours. After the reaction is completed, the solvent acetone is removed by rotary evaporation at a temperature of 45° C. to obtain a carbon black / hyperbranched polyester composite material;

[0096] The mass ratio of caprolactone-modified methacrylate, chlorinated carbon black, terminal hydroxyl hyperbranched polyester, acetone, triethylamine, and hydroquinone is 5.5:14:24:60:3.5:0.01;

[0097] Wherein, the acrylate monomer is prepared by the following steps:

[0098] Step (1), mixing fumed silica with ethyl acetate, ultrasonically dispersing for 50 minutes, adding 3-(2,3-epoxypropoxy)propyltrimethoxysilane and water, wherein the mass ratio of fumed silica, ethyl acetate, 3-(2,3-epoxypropoxy)propyltrimethoxysilane and water is 4:200:40:1, reacting at 70°C for 10 hours, filtering after the reaction, taking the filter cake, adding ethyl acetate 8 times the mass of the filter cake for washing three times, and drying at 80°C for 10 hours to obtain epoxy fumed silica;

[0099] Epoxy fumed silica, maleic acid mono-2-(methacryloyloxy)ethyl ester and acetone were mixed in a mass ratio of 1:30:40, reacted at 90°C for 8 hours in a nitrogen atmosphere, cooled to room temperature after the reaction, filtered, and the filter cake was taken out, acetone 8 times the mass of the filter cake was added for washing, and dried at 80°C for 20 hours to obtain alkenyl fumed silica;

[0100] Step (2), mixing alkenyl fumed silica, butyl acrylate, hydroxyethyl methacrylate, N-hydroxymethyl acrylamide, trimethylolpropane triacrylate, and polyurethane acrylate in a mass ratio of 3:25:5:8:15:40 to obtain an acrylate monomer;

[0101] Step 2: Mix the carbon black / hyperbranched polyester composite material, acrylate monomer, photoinitiator, defoamer, leveling agent and acetone in a mass ratio of 100:40:6:1:1:30 in a light-proof environment, and stir at a speed of 400 r / min for 30 minutes to obtain a high hiding ink;

[0102] The photoinitiator is prepared by mixing photoinitiator ITX and photoinitiator 1173 in a mass ratio of 1:1.

[0103] Comparative Example 1

[0104] This comparative example discloses a method for preparing ink, comprising the following steps:

[0105] Step 1: preparing carbon black / hyperbranched polyester composite material and acrylate monomer;

[0106] Wherein, the carbon black / hyperbranched polyester composite material is prepared by the following steps:

[0107] The carbon black and the hydroxyl-terminated hyperbranched polyester are mixed in a mass ratio of 12:27 to obtain a carbon black / hyperbranched polyester composite material;

[0108] Wherein, the acrylate monomer is prepared by the following steps:

[0109] Step (1), mixing fumed silica with ethyl acetate, ultrasonically dispersing for 30 minutes, adding 3-(2,3-epoxypropoxy)propyltrimethoxysilane and water, wherein the mass ratio of fumed silica, ethyl acetate, 3-(2,3-epoxypropoxy)propyltrimethoxysilane and water is 3.5:180:35:1, reacting at 60°C for 12 hours, filtering after the reaction, taking the filter cake, adding ethyl acetate 5 times the mass of the filter cake for washing three times, and drying at 70°C for 12 hours to obtain epoxy fumed silica;

[0110] Epoxy fumed silica, maleic acid mono-2-(methacryloyloxy)ethyl ester and acetone were mixed in a mass ratio of 1:25:30, reacted at 80°C for 10 hours in a nitrogen atmosphere, cooled to room temperature after the reaction, filtered, and the filter cake was taken out, acetone 5 times the mass of the filter cake was added for washing, and dried at 70°C for 24 hours to obtain alkenyl fumed silica;

[0111] Step (2), mixing alkenyl fumed silica, butyl acrylate, hydroxyethyl methacrylate, N-methylol acrylamide, trimethylolpropane triacrylate, and polyurethane acrylate in a mass ratio of 2:30:8:5:10:35 to obtain an acrylate monomer;

[0112] Step 2: Mix the carbon black / hyperbranched polyester composite material, acrylate monomer, photoinitiator, defoamer, leveling agent and acetone in a mass ratio of 90:40:5:0.8:0.8:25 in a light-proof environment, and stir at a speed of 300 r / min for 40 minutes to obtain ink;

[0113] The photoinitiator is prepared by mixing photoinitiator ITX and photoinitiator 1173 in a mass ratio of 1:1.

[0114] Comparative Example 2

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

[0116] Step 1: preparing carbon black / hyperbranched polyester composite material and acrylate monomer;

[0117] Wherein, the carbon black / hyperbranched polyester composite material is prepared by the following steps:

[0118] Step (1), mixing carbon black with a 65wt% nitric acid aqueous solution in a mass ratio of 1:14, ultrasonically dispersing for 20 minutes, stirring and reacting for 28 hours at 90°C in a nitrogen atmosphere, filtering after the reaction, taking the filter cake, washing with deionized water until the washing liquid is neutral, and drying at 50°C for 16 hours to obtain carboxylated carbon black;

[0119] The carboxylated carbon black and thionyl chloride were mixed in a mass ratio of 1:8, ultrasonically dispersed for 15 minutes, reacted at 55°C for 24 hours in a nitrogen atmosphere, and after the reaction, the excess thionyl chloride was removed by rotary evaporation at 50°C to obtain acyl chloride carbon black;

[0120] Step (2), caprolactone-modified methacrylate, acetone, and triethylamine are mixed and stirred for 20 minutes, acyl chloride carbon black and hydroquinone are added, and the reaction is carried out at a temperature of -5°C for 2 hours. After the reaction is completed, the reaction is continued at a temperature of 25°C for 4 hours. After the reaction is completed, the terminal hydroxyl hyperbranched polyester is added, and the reaction is carried out at a temperature of 25°C for 3 hours. After the reaction is completed, the solvent acetone is removed by rotary evaporation at a temperature of 35°C to obtain a carbon black / hyperbranched polyester composite material;

[0121] Among them, the mass ratio of caprolactone-modified methacrylate, acylated carbon black, terminal hydroxyl hyperbranched polyester, acetone, triethylamine, and hydroquinone is 5:12:22:50:3:0.01;

[0122] Wherein, the acrylate monomer is prepared by the following steps:

[0123] Fumed silica, butyl acrylate, hydroxyethyl methacrylate, N-methylol acrylamide, trimethylolpropane triacrylate, and polyurethane acrylate are mixed in a mass ratio of 2:30:8:5:10:35 to obtain an acrylate monomer;

[0124] Step 2: Mix the carbon black / hyperbranched polyester composite material, acrylate monomer, photoinitiator, defoamer, leveling agent and acetone in a mass ratio of 90:40:5:0.8:0.8:25 in a light-proof environment, and stir at a speed of 300 r / min for 40 minutes to obtain ink;

[0125] The photoinitiator is prepared by mixing photoinitiator ITX and photoinitiator 1173 in a mass ratio of 1:1.

[0126] In the above embodiments and comparative examples: carbon black is from Tianjin Xinglongtai Chemical Products Technology Co., Ltd., model high pigment carbon black, particle size 9-17nm; thionyl chloride is from Shanghai Aladdin Biochemical Technology Co., Ltd., CAS No.: 7719-09-7; caprolactone modified methacrylate is from Hunan Juren New Materials Co., Ltd., model PCL-HAM3, Mw = 358g / mol, hydroxyl value 157mgKOH / g; terminal hydroxyl hyperbranched polyester is from Swedish Perstorp, model Boltorn H20; fumed silica comes from Shandong Wanhua Tianhe New Materials Co., Ltd., model fumed white carbon black TH-6380; 3-(2,3-epoxypropoxy)propyltrimethoxysilane comes from Shanghai Aladdin Biochemical Technology Co., Ltd., model KH560, CAS number: 2530-83-8; mono-2-(methacryloyloxy)ethyl maleate comes from Sigma-Aldrich, CAS number: 51978-15-5; polyurethane acrylate comes from Hubei Langbowan Biomedicine Co., Ltd., model PUA901; defoamer comes from BASF, model EfkaPB2001; leveling agent comes from Dow Corning, model DC-57; photoinitiator ITX comes from Guangdong Wengjiang Chemical Reagent Co., Ltd., CAS number: 5495-84-1; photoinitiator 1173 comes from Nanjing Milan Chemical Co., Ltd., CAS number: 7374-98-5.

[0127] Test example

[0128] Comprehensive performance tests were conducted on Examples 1-5 and Comparative Examples 1-2. Specific test results are shown in Table 1:

[0129] Table 1

[0130]

[0131] Among the indicators in Table 1, the light-shielding property is represented by the OD value, and the insulation resistance performance is represented by the insulation resistance value. The specific test operation is: the ink prepared in Examples 1-5 and Comparative Examples 1-2 is coated on the surface of a glass sheet, and cured for 20 seconds at 130°C under UV-LED ultraviolet light. The thickness of the black ink film layer formed after the curing is 4 μm. The OD value of the black ink film layer is tested by an optical density meter, and the insulation resistance value of the black ink film layer is tested by an insulation tester. The spacing between the test leads is 10 mm.

[0132] It can be seen from the test results in Table 1 that the high hiding ink prepared by the present invention has high hiding and insulation properties.

[0133] The present invention obtains a carbon black / hyperbranched polyester composite material by surface modification of carbon black, wherein caprolactone-modified methacrylate is a macromolecular monomer formed by polymerization of hydroxyethyl methacrylate and caprolactone monomer, which can improve the mechanical properties of ink such as flexibility, and because it has an active group carbon-carbon double bond, it can participate in a photocuring reaction after being grafted on the surface of carbon black; terminal hydroxyl hyperbranched polyester is a hyperbranched polymer with good solubility, excellent film-forming properties, weather resistance and mechanical properties, and can be added to ink as an active polymer to improve the comprehensive properties of the ink. At the same time, it has a large number of active functional groups hydroxyl groups, which can react and graft with the acyl chloride groups of acyl chloride carbon black, and act as a surface modifier to improve the dispersion of carbon black in ink, hinder the contact between carbon black particles, and reduce the conductive properties of carbon black. In comparative example 1, the carbon black is not surface modified, the dispersibility in the ink is reduced, and the ink particles are easy to contact each other, so the light-shielding and insulation resistance properties of comparative example 1 are not as good as those of the embodiment;

[0134] The present invention obtains alkenyl fumed silica by surface modification of fumed silica; alkenyl fumed silica, butyl acrylate, hydroxyethyl methacrylate, N-hydroxymethyl acrylamide, trimethylolpropane triacrylate, and polyurethane acrylate are mixed to obtain acrylate monomers; wherein, fumed silica has a high-efficiency matting effect, and its surface is modified to graft carbon-carbon double bonds so that it can participate in the photocuring reaction, thereby improving the dispersibility and compatibility of fumed silica in the ink matrix and improving the covering effect of the ink. In comparative example 2, the fumed silica is not surface modified, and its dispersibility in the ink decreases, so the light-shielding property of comparative example 1 is not as good as that of the embodiment.

[0135] 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 hiding ink, characterized in that: The following steps are involved: Step 1: preparing carbon black / hyperbranched polyester composite material and acrylate monomer; Wherein, the carbon black / hyperbranched polyester composite material is prepared by the following steps: The caprolactone-modified methacrylate, acetone and triethylamine are mixed and stirred, and acyl chloride carbon black and hydroquinone are added to react. The reaction conditions are: react at a temperature of -5-0°C for 1-2 hours. After the reaction is completed, continue to react at a temperature of 25-30°C for 3-4 hours; after the reaction is completed, add the terminal hydroxyl hyperbranched polyester and react again. The reaction conditions are: react again at a temperature of 25-30°C for 2-3 hours; after the reaction is completed, the solvent acetone is removed by rotary evaporation to obtain a carbon black / hyperbranched polyester composite material; Wherein, the acrylate monomer is prepared by the following steps: Step (1), mixing epoxy fumed silica, maleic acid mono-2-(methacryloyloxy)ethyl ester and acetone, reacting, cooling to room temperature after the reaction, filtering, washing with acetone, and drying to obtain alkenyl fumed silica; Step (2), mixing alkenyl fumed silica, butyl acrylate, hydroxyethyl methacrylate, N-hydroxymethyl acrylamide, trimethylolpropane triacrylate, and polyurethane acrylate to obtain an acrylate monomer; Step 2: Mix the carbon black / hyperbranched polyester composite material, acrylate monomer, photoinitiator, defoamer, leveling agent and acetone, and stir to obtain a high hiding ink.

2. The method for preparing a high hiding ink according to claim 1, characterized in that: In the step 1, when preparing the carbon black / hyperbranched polyester composite material, the chlorinated carbon black comprises the following steps: The carbon black is mixed with a nitric acid aqueous solution, ultrasonically dispersed, stirred for reaction, filtered, washed, and dried after the reaction is completed to obtain carboxylated carbon black; the carboxylated carbon black is mixed with thionyl chloride, ultrasonically dispersed, reacted, and after the reaction is completed, the excess thionyl chloride is removed by rotary evaporation to obtain acyl chloride carbon black; Among them, the mass ratio of carbon black to nitric acid aqueous solution is 1:14-16, and the nitric acid aqueous solution is 65wt% nitric acid aqueous solution; when preparing carboxylated carbon black, the reaction conditions are: stirring and reacting for 24-28h in a nitrogen atmosphere at a temperature of 90-100°C; the mass ratio of carboxylated carbon black to thionyl chloride is 1:8-10; when preparing acyl chloride carbon black, the reaction conditions are: reacting for 18-24h in a nitrogen atmosphere at a temperature of 55-65°C.

3. The method for preparing a high hiding ink according to claim 1, characterized in that: In the step 1, when preparing the carbon black / hyperbranched polyester composite material, the mass ratio of caprolactone-modified methacrylate, chlorinated carbon black, terminal hydroxyl hyperbranched polyester, acetone, triethylamine, and hydroquinone is 5-5.5:12-14:22-24:50-60:3-3.5:0.

01.

4. The method for preparing a high hiding ink according to claim 1, characterized in that: In the step 1, when preparing the acrylate monomer, the epoxy fumed silica is prepared by the following steps: The fumed silica is mixed with ethyl acetate, and ultrasonically dispersed, and 3-(2,3-epoxypropoxy)propyltrimethoxysilane and water are added to react. After the reaction is completed, the mixture is filtered, washed, and dried to obtain epoxy fumed silica; Among them, the mass ratio of gas-phase silica, ethyl acetate, 3-(2,3-epoxypropoxy)propyltrimethoxysilane and water is 3.5-4:180-200:35-40:1; the reaction conditions are: react at a temperature of 60-70°C for 10-12h.

5. The method for preparing a high hiding ink according to claim 1, characterized in that: In the step 1, when preparing the acrylic acid ester monomer, in step (1), the mass ratio of epoxy fumed silica, maleic acid mono-2-(methacryloyloxy)ethyl ester and acetone is 1:25-30:30-40; the reaction conditions are: reacting in a nitrogen atmosphere at a temperature of 80-90° C. for 8-10 hours.

6. The method for preparing a high hiding ink according to claim 1, characterized in that: In the step 1, when preparing the acrylic acid ester monomer, in step (2): the mass ratio of alkenyl fumed silica, butyl acrylate, hydroxyethyl methacrylate, N-hydroxymethyl acrylamide, trimethylolpropane triacrylate, and polyurethane acrylate is 2-3:25-30:5-8:5-8:10-15:35-40.

7. The method for preparing a high hiding ink according to claim 1, characterized in that: In the step 2, the mass ratio of the carbon black / hyperbranched polyester composite material, the acrylate monomer, the photoinitiator, the defoaming agent, the leveling agent and the acetone is 90-100:40:5-6:0.8-1:0.8-1:25-30.

8. The method for preparing a high hiding ink according to claim 1, characterized in that: In the step 2: the photoinitiator is prepared by mixing photoinitiator ITX and photoinitiator 1173 in a mass ratio of 1:

1.

9. A high hiding ink prepared by the method for preparing a high hiding ink according to any one of claims 1 to 8.

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