Water-based liquid laser ink and preparation method thereof

Abstract

The invention relates to the technical field of ink, and provides water-based liquid laser ink and a preparation method thereof.The water-based liquid laser ink is prepared from, by weight, 40-60 parts of acrylic resin, 1-4 parts of amino acrylate, 3-7 parts of ethoxylated trimethylolpropane triacrylate, 2-6 parts of photoinitiator and 10-15 parts of nano calcium carbonate. The ink is prepared from the following raw materials in parts by weight: 3-6 parts of black slurry, 4-10 parts of a composite antioxidant, 0.5-1.5 parts of a thickening agent, 0.1-0.5 part of a shrinkage-proof agent, 0.3-1 part of a dispersing agent and 20-40 parts of deionized water. The water-based liquid laser ink provided by the invention not only has good corrosion resistance and wear resistance, but also has excellent oxidation resistance.

Description

Technical Field

[0001] The present invention relates to the technical field of inks, and particularly to an aqueous liquid laser ink and a preparation method thereof. Background Art

[0002] Laser ink is a kind of ink with special optical effects, which is widely used in high-end packaging, anti-counterfeiting labels, security printing and other fields. Its unique optical properties give it significant advantages in visual effects and security, and it has gradually become one of the important development directions in the printing industry. However, with the gradual enhancement of people's environmental awareness, traditional solvent-based inks are gradually restricted due to the presence of volatile organic compounds (VOCs). In order to develop an environmentally friendly alternative, aqueous liquid laser ink has emerged under this background.

[0003] Aqueous liquid photosensitive laser oil has excellent photosensitivity under laser exposure, can achieve a resolution of micrometers or even nanometers, meets the requirements of high-precision lithography, and uses water as a solvent, greatly reducing the use of organic solvents, meeting the requirements of green environmental protection, reducing the emission of volatile organic compounds (VOC), and compared with traditional organic solvent photoresists, the raw material cost of aqueous photoresists is lower, and it is easy to obtain, the preparation process is simple, suitable for large-scale production. In addition, it also has a wide range of application prospects, not only limited to semiconductor lithography, but also can be applied to multiple fields such as 3D printing, micro-nano manufacturing, etc.

[0004] Aqueous liquid laser ink often selects water-soluble resins such as acrylic resins as the main component. Acrylic resins not only have good solubility, but also can crosslink quickly under laser irradiation, and acrylic resins also have good corrosion resistance and wear resistance. However, acrylic resins still have the defect of being easily oxidized by environmental factors such as light, heat, ultraviolet rays, etc., which will lead to a decrease in the service life of aqueous liquid laser ink.

[0005] Patent CN 104031470B discloses an aqueous laser anti-counterfeiting ink, whose main resin components are aqueous polyurethane and aqueous acrylic resins, and with the cooperation of wetting and dispersing agents, defoamers, alcohol and deionized water, this aqueous laser anti-counterfeiting ink is prepared, which has good adhesion fastness, water resistance, oil resistance, etc. after printing, protects the laser anti-counterfeiting pattern, and can print different effects on the same laser pattern. However, the laser ink prepared in this application does not consider the problem of poor antioxidant performance of aqueous polyurethane and aqueous acrylic resins, resulting in the ink may not be able to be stored and used for a long time.

[0006] Therefore, there is an urgent need in the market for an aqueous liquid laser ink that not only has good corrosion resistance and wear resistance, but also has excellent antioxidant performance. Summary of the Invention

[0007] In view of the problems existing in the prior art, the present invention uses acrylic resin as the main component of the water-based liquid laser ink, adds aminoacrylate and ethoxylated trimethylolpropane triacrylate, and designs and synthesizes a composite antioxidant composed of hindered phenol antioxidants and phosphite antioxidants. In combination with components such as nano calcium carbonate and photoinitiator, a water-based liquid laser ink is synthesized, which has good corrosion resistance, wear resistance and excellent antioxidant performance.

[0008] In order to achieve the above object, the technical solution adopted by the present invention is as follows:

[0009] On the one hand, the present invention provides a water-based liquid laser ink. By weight, the water-based liquid laser ink comprises the following raw materials: 40-60 parts of acrylic resin, 1-4 parts of aminoacrylate, 3-7 parts of ethoxylated trimethylolpropane triacrylate, 2-6 parts of photoinitiator, 10-15 parts of nano calcium carbonate, 3-6 parts of black paste, 4-10 parts of composite antioxidant, 0.5-1.5 parts of thickener, 0.1-0.5 parts of anti-cratering agent, 0.3-1 part of dispersant, and 20-40 parts of deionized water.

[0010] Among them, the thickener is carboxymethyl cellulose or carboxyethyl cellulose; the anti-cratering agent is a polyether silicone anti-cratering agent.

[0011] Preferably, the thickener is carboxymethyl cellulose.

[0012] By adding aminoacrylate and ethoxylated trimethylolpropane triacrylate and using them in combination with acrylic resin, the applicant can form a cross-linked structure during the curing process of the laser ink, thereby improving the hardness and corrosion resistance of the coating.

[0013] In some embodiments of the present invention, the photoinitiator is photoinitiator 907 or photoinitiator ITX.

[0014] In some embodiments of the present invention, the average particle size of the nano calcium carbonate is 35-50 nm.

[0015] Preferably, the average particle size of the nano calcium carbonate is 40 nm.

[0016] By selecting nano calcium carbonate within this particle size range as the filler, the applicant enables the nano calcium carbonate to maintain a high specific surface area and effectively reduce the agglomeration phenomenon. Furthermore, it has good dispersibility in the acrylic resin system, thereby significantly improving the corrosion resistance and wear resistance of the laser ink.

[0017] In some embodiments of the present invention, the composite antioxidant is a mixture of hindered phenol antioxidants and phosphite antioxidants.

[0018] Preferably, the mass ratio of the hindered phenol antioxidant to the phosphite antioxidant is 1:(0.4 - 0.8).

[0019] More preferably, the mass ratio of the hindered phenol antioxidant to the phosphite antioxidant is 1:0.65.

[0020] In some embodiments of the present invention, the preparation method of the hindered phenol antioxidant comprises the following steps:

[0021] (1) Place 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid in a reaction vessel, add chloroform, and under an inert atmosphere, add thionyl chloride. Heat to 45 - 55 °C and stir for 4 - 6 h. Then perform vacuum distillation to obtain a product for later use;

[0022] (2) Mix the product of step (1) with anhydrous acetonitrile and stir to obtain a solution for later use. Add 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone to anhydrous acetonitrile. Add the solution under the condition of -5 to 2 °C. Under an inert atmosphere, add a triethylamine acetonitrile solution, control the pH = 9 - 10, stir, heat to 55 - 65 °C, stir for 23 - 25 h, perform vacuum distillation, and perform post-treatment to obtain the hindered phenol antioxidant.

[0023] In some embodiments of the present invention, in step (1), the molar ratio of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid to thionyl chloride is 1:(1.4 - 2.5).

[0024] Preferably, in step (1), the molar ratio of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid to thionyl chloride is 1:2.

[0025] In some embodiments of the present invention, the molar ratio of 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone to 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid is 1:(8 - 11).

[0026] Preferably, the molar ratio of 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone to 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid is 1:10.

[0027] In some embodiments of the present invention, the phosphite antioxidant is tetra(2,4-di-tert-butylphenyl) 4,4'-biphenyldiphosphite.

[0028] Acrylic resin has good application prospects in the field of waterborne laser inks due to its advantages of good transparency, gloss, adhesion, abrasion resistance, and high environmental friendliness. However, acrylic resin is relatively susceptible to environmental factors such as light and heat, which can cause it to turn yellow and age, resulting in poor durability of the laser ink. Therefore, antioxidants are often added to improve its anti-aging performance. Among them, hindered phenol antioxidants have received extensive attention due to their low toxicity and good compatibility. However, most of the industrial hindered phenol antioxidants are small molecules, and there are still problems such as poor migration resistance and thermal stability.

[0029] The applicant uses a combination of phosphite antioxidants and hindered phenol antioxidants as a composite antioxidant. Based on the complementarity of their antioxidant mechanisms, the two have a synergistic antioxidant effect. In addition, the applicant selects a specific type of phosphite antioxidant, tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenyldiphosphite. Compared with conventional phosphite antioxidants, it has a higher molecular weight, better migration resistance, and good compatibility with the polymer matrix. In addition, the P-C bond in the structure of tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenyldiphosphite gives it good high-temperature resistance, which can effectively solve the problems of poor migration resistance and thermal stability of hindered phenol antioxidants. Further, the applicant designed and synthesized a hindered phenol antioxidant. First, the proportion was controlled to allow 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid and thionyl chloride to fully undergo amidation condensation reaction (to obtain the product). Then, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone with two molecules of hydroxyl and two molecules of amino was selected as the bridging substance, and the proportion was controlled to allow 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone to react with the product and control the molar excess of the product, so that the prepared hindered phenol antioxidant has multiple hindered phenol units and a relatively high molecular weight, effectively solving the problems of poor thermal stability and easy migration of traditional hindered phenol antioxidants, which result in their antioxidant performance not reaching the ideal effect. In addition, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone as the bridging substance has a rigid structure and is not prone to hydrolysis reaction, which can effectively inhibit the occurrence of material aging.

[0030] In addition, the applicant unexpectedly found that the introduction of this hindered phenol antioxidant can improve the overall stability and abrasion resistance of the laser ink to a certain extent. It is speculated that the reason may be that in the aqueous liquid environment, there is a certain electrostatic and hydrogen bond interaction between the -NH- bond in the structure of the hindered phenol antioxidant and the carboxyl group of the thickener carboxymethyl cellulose, thereby improving the overall stability and abrasion resistance of the aqueous liquid laser ink.

[0031] In some embodiments of the present invention, the dispersant is a polycarboxylate dispersant.

[0032] On the other hand, the present invention also provides a method for preparing the aqueous liquid laser ink described in the above technical solution, comprising the following steps:

[0033] Mix acrylic resin, aminoacrylate, ethoxylated trimethylolpropane triacrylate, photoinitiator, nano calcium carbonate, black paste, compound antioxidant, thickener, anti-cratering agent, dispersant and deionized water, and stir for 40 - 60 min to obtain the aqueous liquid laser ink.

[0034] Compared with the prior art, the present invention has the following beneficial effects:

[0035] (1) In the present invention, acrylic resin is used as the main component of the aqueous liquid laser ink, aminoacrylate and ethoxylated trimethylolpropane triacrylate are added, and a compound antioxidant composed of a hindered phenol antioxidant and a phosphite antioxidant is designed and synthesized. In combination with components such as nano calcium carbonate and photoinitiator, an aqueous liquid laser ink is synthesized. Through the synergistic effect between the components, it has the characteristics of good corrosion resistance, wear resistance and excellent antioxidant performance, and can be widely applied to the field of ink technology.

[0036] (2) The present invention uses nano calcium carbonate with a specific particle size as a filler, which has good dispersibility in the acrylic resin system, and further improves the corrosion resistance and wear resistance of the laser ink.

[0037] (3) The present invention uses 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, thionyl chloride and 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone as the main raw materials to design and synthesize a hindered phenol antioxidant, which has good thermal stability and migration resistance and thus high antioxidant properties. Further, the hindered phenol antioxidant and the phosphite antioxidant tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenyldiphosphite are compounded and used as a compound antioxidant. Through the synergistic connection between the components, the two have a good synergistic antioxidant effect. Specific Embodiments

[0038] The present invention will be described below in conjunction with specific embodiments. It should be noted that the following examples are examples of the present invention, only for illustrating the present invention, and not for limiting the present invention. Other combinations and various improvements within the concept of the present invention can be made without departing from the gist or scope of the present invention.

[0039] In the following examples and comparative examples, except for the hindered phenol antioxidants, the other compound monomers and related reagents used can be purchased from the market. Among them, the acrylic resin model is ACR-S4857, purchased from Huashi (Guangdong) New Materials Technology Co., Ltd.; two types of nano calcium carbonate with average particle sizes of 40 nm and 20 nm are selected; the black slurry is purchased from Dongguan Caishiming Coating Technology Co., Ltd.; the thickener is carboxymethyl cellulose, model CLHG-005, purchased from Langfang Changlin Cellulose Co., Ltd.; the polyether silicone anti-cratering agent model is Wet270, purchased from Yinhuang (Shanghai) Industrial Co., Ltd.; the dispersant is a polycarboxylate dispersant, model Dispex CX 4320AM, purchased from Shanghai Zhenlishi Network Technology Co., Ltd.

[0040] Preparation Example 1

[0041] The synthesis method of the hindered phenol antioxidant A includes the following steps:

[0042] (1) Place 0.04 mol of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid in a reaction vessel, add 100 ml of chloroform, under a nitrogen atmosphere, add 0.08 mol of thionyl chloride, heat up to 50 °C, stir for 5 h, and perform vacuum distillation to obtain the product for standby;

[0043] (2) Mix the product of step (1) with 150 ml of anhydrous acetonitrile and stir for 30 min to obtain a solution for standby. Add 0.004 mol of 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone to 40 ml of anhydrous acetonitrile, add the solution under the condition of 0 °C, under a nitrogen atmosphere, add 0.2 mol / L triethylamine acetonitrile solution, control pH = 9.5, stir for 12 h, heat up to 60 °C, stir for 24 h, perform vacuum distillation, and perform post-treatment (add the solid obtained by vacuum distillation to 100 ml of dichloromethane, stir for 20 min, wash three times with 5 wt% NaHCO3 aqueous solution and 0.5 mol / L HCl aqueous solution respectively, then wash twice with saturated NaCl solution, add to 100 ml of anhydrous ethanol after vacuum distillation, stir for 20 min, add 1 mol / L NaOH aqueous solution, filter, wash the solid with deionized water until neutral, and dry at 60 °C for 12 h), and the hindered phenol antioxidant A is obtained.

[0044] Preparation Example 2

[0045] For the hindered phenol antioxidant B, the specific implementation method is the same as that of the hindered phenol antioxidant A, the difference is that: in step (1), the molar amount of thionyl chloride is replaced by 0.05 mol.

[0046] Preparation Example 3

[0047] The hindered phenol antioxidant C has the same specific implementation as the hindered phenol antioxidant A, except that: in step (2), the molar amount of 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone is replaced with 0.006 mol.

[0048] Example 1

[0049] A water-based liquid laser ink, by weight, the water-based liquid laser ink comprises the following raw materials: 50 parts of acrylic resin, 2.5 parts of amino acrylate, 5 parts of ethoxylated trimethylolpropane triacrylate, 4 parts of photoinitiator 907, 13 parts of nano calcium carbonate, 4.5 parts of black paste, 7 parts of compound antioxidant, 1 part of carboxymethyl cellulose, 0.3 part of anti-cratering agent, 0.6 part of dispersant, 30 parts of deionized water.

[0050] Among them, the compound antioxidant is a mixture of hindered phenol antioxidant A and tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenyldiphosphite, and the mass ratio is 1:0.65.

[0051] The average particle size of the nano calcium carbonate is 40 nm.

[0052] The preparation method of the water-based liquid laser ink in this example comprises the following steps:

[0053] Mix acrylic resin, amino acrylate, ethoxylated trimethylolpropane triacrylate, photoinitiator 907, nano calcium carbonate, black paste, compound antioxidant, carboxymethyl cellulose, anti-cratering agent, dispersant and deionized water, and stir for 50 min to obtain the water-based liquid laser ink.

[0054] Example 2

[0055] A water-based liquid laser ink, by weight, the water-based liquid laser ink comprises the following raw materials: 40 parts of acrylic resin, 1 part of amino acrylate, 3 parts of ethoxylated trimethylolpropane triacrylate, 2 parts of photoinitiator ITX, 10 parts of nano calcium carbonate, 3 parts of black paste, 4 parts of compound antioxidant, 0.5 part of carboxymethyl cellulose, 0.1 part of anti-cratering agent, 0.3 part of dispersant, 20 parts of deionized water.

[0056] Among them, the compound antioxidant is a mixture of hindered phenol antioxidant A and tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenyldiphosphite, and the mass ratio is 1:0.4.

[0057] The average particle size of the nano calcium carbonate is 40 nm.

[0058] The preparation method of the water-based liquid laser ink in this example comprises the following steps:

[0059] Mix acrylic resin, aminoacrylate, ethoxylated trimethylolpropane triacrylate, photoinitiator ITX, nano calcium carbonate, black paste, compound antioxidant, carboxymethyl cellulose, anti-cratering agent, dispersant and deionized water, and stir for 40 min to obtain the waterborne liquid laser ink.

[0060] Example 3

[0061] A waterborne liquid laser ink, by weight, the waterborne liquid laser ink comprises the following raw materials: 60 parts of acrylic resin, 4 parts of aminoacrylate, 7 parts of ethoxylated trimethylolpropane triacrylate, 6 parts of photoinitiator ITX, 15 parts of nano calcium carbonate, 6 parts of black paste, 10 parts of compound antioxidant, 1.5 parts of carboxymethyl cellulose, 0.5 part of anti-cratering agent, 1 part of dispersant, 40 parts of deionized water.

[0062] Among them, the compound antioxidant is a mixture of hindered phenol antioxidant A and tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenyldiphosphite, and the mass ratio is 1:0.8.

[0063] The average particle size of the nano calcium carbonate is 40 nm.

[0064] The preparation method of the waterborne liquid laser ink in this example comprises the following steps:

[0065] Mix acrylic resin, aminoacrylate, ethoxylated trimethylolpropane triacrylate, photoinitiator ITX, nano calcium carbonate, black paste, compound antioxidant, carboxymethyl cellulose, anti-cratering agent, dispersant and deionized water, and stir for 60 min to obtain the waterborne liquid laser ink.

[0066] Example 4

[0067] This example provides a waterborne liquid laser ink and its preparation method. The specific implementation manner is the same as that of Example 1, except that the average particle size of the nano calcium carbonate is 20 nm.

[0068] Example 5

[0069] This example provides a waterborne liquid laser ink and its preparation method. The specific implementation manner is the same as that of Example 1, except that the mass ratio of hindered phenol antioxidant A and tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenyldiphosphite in the compound antioxidant is 1:0.2.

[0070] Example 6

[0071] This embodiment provides an aqueous liquid laser ink and a preparation method thereof. The specific implementation manner is the same as that of Embodiment 1, except that the mass ratio of the hindered phenol antioxidant A and tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenyldiphosphite in the compound antioxidant is 1:1.

[0072] Example 7

[0073] This embodiment provides an aqueous liquid laser ink and a preparation method thereof. The specific implementation manner is the same as that of Embodiment 1, except that the hindered phenol antioxidant A is replaced by an equal amount of the hindered phenol antioxidant B.

[0074] Example 8

[0075] This embodiment provides an aqueous liquid laser ink and a preparation method thereof. The specific implementation manner is the same as that of Embodiment 1, except that the hindered phenol antioxidant A is replaced by an equal amount of the hindered phenol antioxidant C.

[0076] Example 9

[0077] This embodiment provides an aqueous liquid laser ink and a preparation method thereof. The specific implementation manner is the same as that of Embodiment 1, except that the hindered phenol antioxidant A is replaced by an equal amount of antioxidant 1076.

[0078] Comparative Example 1

[0079] This comparative example provides an aqueous liquid laser ink and a preparation method thereof. The specific implementation manner is the same as that of Embodiment 1, except that the compound antioxidant is replaced by an equal amount of the hindered phenol antioxidant A.

[0080] Comparative Example 2

[0081] This comparative example provides an aqueous liquid laser ink and a preparation method thereof. The specific implementation manner is the same as that of Embodiment 1, except that the compound antioxidant is replaced by an equal amount of tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenyldiphosphite.

[0082] Performance Test

[0083] The corrosion resistance, abrasion resistance and antioxidant properties of the aqueous liquid laser inks of the above Embodiments 1-9 and Comparative Examples 1-2 were tested, and the test results are shown in Table 1.

[0084] The aqueous liquid laser ink was coated on the tinplate to a thickness of 10 ± 2 μm. After forming, ultraviolet light was irradiated for 20 min under a light intensity of 40 mW / cm 2 to obtain a coated layer for standby.

[0085] (1) Corrosion Resistance

[0086] Put the coating into an aqueous solution of 95 wt% sulfuric acid at 120 mL / L and 55 °C for 2 h, and observe whether corrosion occurs on the coating surface. If there is no peeling on the coating surface, the corrosion resistance is "excellent"; if there is slight peeling on the coating surface, the corrosion resistance is "good"; if there is large-scale peeling on the coating surface, the corrosion resistance is "poor".

[0087] (2) Abrasion resistance

[0088] Refer to the standard GB / T 1768-1979 "Method for Determining the Abrasion Resistance of Paint Films" to test the abrasion resistance of the coating, and measure the mass of the coating worn per unit area under the conditions of 750 g and 500 r.

[0089] (3) Oxidation resistance

[0090] The oxidation resistance is judged by the degree of yellowing. Prepare the paint without adding black paste according to the methods of Examples 1-9 and Comparative Examples 1-2, and then prepare the coating according to the methods in the above performance tests. First, place the coating at 150 °C and let it stand for 24 h, and then irradiate it with a carbon rod lamp type solar climate tester for 30 hours. Then, use a colorimeter to measure the degree of yellowing of the coating, and use the yellowing value (Y I ) to represent. The larger the yellowing value, the worse the oxidation resistance.

[0091] Table 1

[0092]

[0093] As can be seen from the data in Table 1, the aqueous liquid laser inks in Examples 1-3 of the present invention as a whole have good corrosion resistance, wear resistance and oxidation resistance. Among them, in Example 4, the average particle size of nano calcium carbonate was changed, resulting in a decrease in its dispersibility in the ink, and further resulting in a decrease in corrosion resistance and wear resistance, with little effect on oxidation resistance; in Examples 5-6, the ratio between the hindered phenol antioxidant A and tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenylyl diphosphite in the composite antioxidant was changed, weakening the antioxidant synergistic effect between the two, and further resulting in a decrease in the oxidation resistance of the ink; in Examples 7-8, the ratio between 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid and thionyl chloride and the addition amount of the bridging substance 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone in the synthesis process of the hindered phenol antioxidant A were changed, resulting in a decrease in the molecular weight, the proportion of hindered phenol units and the thermal stability of the obtained hindered phenol antioxidant, and further resulting in a significant decrease in the oxidation resistance of the ink, and to a certain extent affecting the interaction between the hindered phenol antioxidant and the thickener, and further resulting in a slightly worse wear resistance of the ink; in Example 9 and Comparative Examples 1-2, antioxidant 1076 was used to replace the hindered phenol antioxidant A in equal amounts and the hindered phenol antioxidant and tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenylyl diphosphite were used to replace the composite antioxidant in equal amounts respectively, both resulting in poor oxidation resistance performance of the ink, and the wear resistance in Example 9 and Comparative Example 2 also became worse to a certain extent.

[0094] The above embodiments are only for illustrating the technical concept and features of the present invention, and the purpose is to enable those who are familiar with this technology to understand the content of the present invention and implement it, and it cannot be used to limit the protection scope of the present invention. All equivalent changes or modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.

Claims

1. A water-based liquid laser ink, characterized in that: The aqueous liquid laser ink comprises the following raw materials in parts by weight: 40-60 parts of acrylic resin, 1-4 parts of amino acrylate, 3-7 parts of ethoxylated trimethylolpropane triacrylate, 2-6 parts of photoinitiator, 10-15 parts of nano calcium carbonate, 3-6 parts of black slurry, 4-10 parts of composite antioxidant, 0.5-1.5 parts of thickener, 0.1-0.5 parts of anti-crater agent, 0.3-1 parts of dispersant, and 20-40 parts of deionized water.

2. The aqueous liquid laser ink according to claim 1, characterized in that: The photoinitiator is photoinitiator 907 or photoinitiator ITX.

3. The aqueous liquid laser ink according to claim 1, characterized in that: The average particle size of the nano calcium carbonate is 35-50nm.

4. The aqueous liquid laser ink according to claim 1, characterized in that: The composite antioxidant is a mixture of hindered phenol antioxidants and phosphite antioxidants.

5. The aqueous liquid laser ink according to claim 1, characterized in that: The preparation method of the hindered phenol antioxidant comprises the following steps: (1) 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid is placed in a reaction vessel, chloroform is added, and under an inert atmosphere, thionyl chloride is added, the temperature is raised to 45-55° C., stirred for 4-6 hours, and distilled under reduced pressure to obtain a product for later use; (2) The product of step (1) is mixed with anhydrous acetonitrile, stirred to obtain a solution for use, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone is added to anhydrous acetonitrile, the solution is added at -5 to 2°C, triethylamine acetonitrile solution is added under an inert atmosphere, pH is controlled to 9-10, stirred, heated to 55-65°C, stirred for 23-25h, distilled under reduced pressure, and post-treated to obtain a hindered phenol antioxidant.

6. The aqueous liquid laser ink according to claim 5, characterized in that: In the step (1), the molar ratio of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid to thionyl chloride is 1:(1.4-2.5).

7. The aqueous liquid laser ink according to claim 5, characterized in that: The molar ratio of the 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone to 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid is 1:(8-11).

8. The aqueous liquid laser ink according to claim 4, characterized in that: The phosphite antioxidant is tetrakis(2,4-di-tert-butylphenyl)4,4'-biphenyl diphosphite.

9. The aqueous liquid laser ink according to claim 1, characterized in that: The dispersant is a polycarboxylate dispersant.

10. A method for preparing the aqueous liquid laser ink according to any one of claims 1 to 9, characterized in that: The following steps are involved: Acrylic resin, aminoacrylate, ethoxylated trimethylolpropane triacrylate, photoinitiator, nano calcium carbonate, black slurry, composite antioxidant, thickener, anti-crater agent, dispersant and deionized water are mixed and stirred for 40-60 minutes to obtain water-based liquid laser ink.

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