A UV waterproof ink and its preparation method

Abstract

This invention discloses a UV waterproof ink and its preparation method, belonging to the field of UV waterproof ink technology. The invention uses the esterification product of linoleic acid and linoleyl alcohol as the A-phase component of the ink, and simultaneously uses terminal mercapto polyethylene glycol as the B-phase component. The thiol-ene click reaction is utilized to accelerate the film-forming speed of the ink under ultraviolet light. The polyethylene glycol backbone introduced into the structure is integrated into the three-dimensional network formed after ink curing during the UV curing process, improving the ink viscosity and enhancing the adhesion between the ink and the printing medium. Furthermore, a self-made antioxidant is formed by rosmarinic acid and mercaptoethylamine under ultraviolet light irradiation and added to the ink to efficiently capture oxygen, protect other components in the ink, and extend the ink's lifespan. The UV waterproof ink prepared by this invention has a high UV curing rate and strong waterproof, temperature-resistant, and antioxidant properties.

Description

Technical Field

[0001] This invention relates to the field of UV waterproof ink technology, specifically to a UV waterproof ink and its preparation method. Background Technology

[0002] With the continuous advancement of printing technology and the rapid development of the printing industry, the performance requirements for printing inks are constantly increasing. Traditional inks have limitations in terms of drying speed, resistance to oxidation and aging, and adhesion. Furthermore, they may generate harmful substances such as volatile organic compounds (VOCs) during production and use, causing environmental pollution. This is especially true in printing fields requiring rapid drying and waterproofing, such as advertising, decoration, 3C products, signage, reproduction, and industrial applications, where traditional inks often fail to meet the requirements. As the market demand for high-quality printed materials continues to grow, and with ongoing technological innovation, the research and application of UV waterproof inks have also developed rapidly. The development of new monomers, resins, and additives, along with continuous improvements to photoinitiators, has led to continuous improvements in the performance of UV waterproof inks and an expansion of their application range. People are also paying increasing attention to the environmental performance of printing inks. UV waterproof inks utilize ultraviolet curing technology, with no VOC emissions during the curing process, meeting environmental requirements and thus gaining favor from governments and enterprises. Therefore, developing new inks with rapid curing, waterproofing, and anti-oxidation properties has become an important demand in the printing industry. Summary of the Invention

[0003] The purpose of this invention is to provide a UV waterproof ink to solve the problems existing in the prior art.

[0004] To solve the above-mentioned technical problems, the present invention provides the following technical solution: a UV waterproof ink, wherein the UV waterproof ink comprises an A phase component and a B phase component, wherein the A phase component comprises a linoleic acid linoleyl alcohol compound, pigment, mercaptopolysiloxane, and a self-made antioxidant, and the B phase component comprises terminal mercaptopolyethylene glycol, a photoinitiator, glycerol, trimethylaluminum, and a self-made antioxidant.

[0005] Furthermore, the self-made antioxidant is prepared by reacting rosmarinic acid and mercaptoethylamine under ultraviolet light irradiation with a photoinitiator.

[0006] Furthermore, the pigment is one or more of carbon black, iron oxide red, iron oxide yellow, phthalocyanine blue, phthalocyanine green, scarlet, lightfast yellow, and permanent violet, the molecular weight of the mercapto polysiloxane is 400-800, and the molecular weight of the terminal mercapto polyethylene glycol is 2000-3000.

[0007] Furthermore, the photoinitiator is one or more of benzophenone, thioxanone, camphorquinone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and 2,2-dimethoxy-2-phenylacetophenone.

[0008] Furthermore, a method for preparing a UV waterproof ink includes the following preparation steps:

[0009] (1) Dissolve rosmarinic acid, mercaptoethylamine and photoinitiator in anhydrous ethanol. Stir at 40-60℃, UV wavelength of 250-360nm and stirring rate of 200-400r / min for 2-4 hours under nitrogen atmosphere. Transfer to drying oven and dry at 50-60℃ for 2-4 hours to obtain self-made antioxidant.

[0010] (2) Linoleic acid, linoleyl alcohol, and sulfuric acid with a mass fraction of 60% were added to anhydrous ethanol. The mixture was stirred at 300-600 r / min for 4-8 h in an oil bath at 40-50 °C under a nitrogen atmosphere. After cooling to room temperature, the solvent was removed by rotary evaporation to obtain a crude product. The crude product was redissolved in tetrahydrofuran to prepare a solution C containing 50-60 wt% crude product. Solution C was then added to n-hexane at a rate of 0.5-1 drops / s, with a volume ratio of n-hexane to solution C of 3:1. The mixture was allowed to stand for 10-18 h to recrystallize at the interface between n-hexane and tetrahydrofuran to obtain crystals. The upper solvent was then discarded, the mixture was dried by vacuum pump, and then dissolved in tetrahydrofuran. This crystallization process was repeated 5-8 times to finally obtain the alcohol ester compound.

[0011] (3) Add alcohol ester compound, pigment, mercapto polysiloxane and self-made antioxidant to anhydrous ethanol, stir at 50-80℃ and 100-300r / min for 3-6h to obtain ink phase A component;

[0012] (4) Add polyethylene glycol containing terminal mercapto groups, photoinitiator, glycerol, trimethylaluminum and self-made antioxidant to anhydrous ethanol, stir at 50-80℃ and 100-300r / min for 3-6h to obtain ink phase B component.

[0013] Furthermore, in step (1), by weight, there are 30-60 parts of rosmarinic acid, 20-40 parts of mercaptoethylamine, 1-5 parts of photoinitiator, and 50-60 parts of anhydrous ethanol.

[0014] Furthermore, in step (2), by weight, there are 20-30 parts of linoleic acid, 15-25 parts of linoleyl alcohol, 20-30 parts of sulfuric acid, and 50-60 parts of anhydrous ethanol.

[0015] Furthermore, in step (3), by weight, there are 30-40 parts of alcohol ester compound, 10-20 parts of pigment, 5-10 parts of mercaptopolysiloxane, 20-30 parts of self-made antioxidant, and 50-60 parts of anhydrous ethanol.

[0016] Furthermore, in step (4), by weight, there are 25-45 parts of terminal thiol polyethylene glycol, 2-8 parts of photoinitiator, 10-20 parts of glycerol, 1-5 parts of trimethylaluminum, 20-30 parts of self-made antioxidant, and 50-60 parts of anhydrous ethanol.

[0017] Furthermore, when using the ink, 50 parts of ink phase A and 50 parts of ink phase B are mixed and stirred evenly. After printing, it is cured for 0.5 to 2 seconds under ultraviolet light with a wavelength of 350 to 400 nm.

[0018] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0019] The UV waterproof ink prepared by this invention achieves high-speed UV curing and enhances the ink's waterproof, temperature-resistant, and antioxidant properties.

[0020] First, the esterification product of linoleic acid and linoleyl alcohol is used as the A-phase component of the ink, introducing more double bonds into the ink. During the ink curing process, this provides sufficient double-bonded functional groups for the thiol ene polymerization reaction, increasing the concentration of double-bonded functional groups in the system and accelerating the UV curing rate of the ink. Simultaneously, the introduction of a large number of alkyl groups into the ink gives the cured ink high hydrophobicity, effectively blocking water molecules from entering the ink after film formation and providing effective waterproofing. Meanwhile, terminal thiol polyethylene glycol is used as the B-phase component of the ink, providing two thiol groups for the thiol ene polymerization reaction during UV curing, achieving high-efficiency UV curing performance. The polyethylene glycol backbone introduced into the structure is integrated into the three-dimensional network formed after ink curing during UV curing, effectively improving the ink viscosity and enhancing the adhesion between the ink and the printing medium, resulting in clearer prints and more saturated colors. Furthermore, the ether bonds in the polyethylene glycol backbone have high thermal stability, further improving the ink's high-temperature resistance.

[0021] Secondly, rosmarinic acid and mercaptoethylamine are reacted under ultraviolet light to introduce amino groups into rosmarinic acid, forming a self-made antioxidant. When added to the ink, the phenolic hydroxyl and amino groups in the antioxidant structure can efficiently capture oxygen when oxygen in the air attacks the ink, forming a stable compound that protects other components in the ink from oxygen erosion and extends the ink's lifespan. The benzene ring in the structure provides a stable structure for the antioxidant, extending its service life. During the ink curing process, the carboxyl groups in the structure can react with the functional groups between the printing media, allowing the antioxidant to bind to the printing media through chemical bonds, enhancing its adhesion and ensuring that the cured ink maintains high-efficiency antioxidant performance. Detailed Implementation

[0022] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0023] To more clearly illustrate the method provided by the present invention, the following embodiments are provided in detail. The test methods for various indicators of the UV waterproof ink produced in the following embodiments are as follows:

[0024] Ink viscosity: The viscosity of the UV waterproof inks prepared in Examples 1-3 and Comparative Examples 1-5 was tested according to GB / T 13217.4-2008;

[0025] Curing time: A quantitative amount of UV waterproof ink was rolled onto a substrate and irradiated with UV light at a wavelength of 380 nm. The curing time of the UV waterproof inks prepared in Examples 1-3 and Comparative Examples 1-5 was tested by the finger dry method to characterize complete curing.

[0026] Ink flexibility properties: Referring to GB / T1731.93, the flexibility properties of the UV waterproof inks prepared in Examples 1-3 and Comparative Examples 1-5 were determined by testing them using a QTX.1 type film elasticity tester.

[0027] Pencil hardness of coating: Referring to GB6739.86, the pencil hardness of the UV waterproof inks prepared in Examples 1-3 and Comparative Examples 1-5 was determined by testing the coating with a QHQ type pencil scratch hardness tester.

[0028] Ink adhesion: The adhesion of the coating film was determined by testing the UV waterproof inks prepared in Examples 1-3 and Comparative Examples 1-5 using the cross-cut test method, in accordance with GB9256-88.

[0029] Waterproofing: A quantitative amount of UV waterproof ink was rolled onto a substrate, irradiated with ultraviolet light at a wavelength of 380 nm, and cured into a film. After immersion in warm water at 40°C for 240 h, the appearance changes of the UV waterproof inks prepared in Examples 1-3 and Comparative Examples 1-5 were observed.

[0030] Example 1

[0031] (1) Take 30 parts of rosmarinic acid, 20 parts of mercaptoethylamine and 1 part of benzophenone and dissolve them in 50 parts of anhydrous ethanol. Stir for 4 hours at 50°C, 320nm wavelength and 350r / min under nitrogen atmosphere. Transfer to drying oven and dry at 50°C for 3 hours to obtain the self-made antioxidant.

[0032] (2) Add 20 parts of linoleic acid, 15 parts of linoleyl alcohol, and 20 parts of sulfuric acid with a mass fraction of 60% to 50 parts of anhydrous ethanol. Stir at 400 r / min for 6 h in an oil bath at 50 °C under a nitrogen atmosphere. Cool to room temperature and remove the solvent by rotary evaporation to obtain crude product. Redissolve the crude product with tetrahydrofuran to prepare a solution C with the crude product accounting for 60 wt%. Add solution C to n-hexane at a rate of 1 drop / s. The volume ratio of n-hexane to solution C is 3:1. Let stand for 15 h to recrystallize at the interface of n-hexane and tetrahydrofuran. Finally, crystals are obtained. Then, the upper solvent is poured off, the solution is dried by vacuum pump, and then dissolved in tetrahydrofuran. Repeat the crystallization process 6 times to finally obtain the alcohol ester compound.

[0033] (3) Add 30 parts of alcohol ester compound, 10 parts of pigment, 5 parts of mercaptopolysiloxane with a molecular weight of 600 and 20 parts of self-made antioxidant to 50 parts of anhydrous ethanol, stir at 60°C and 200 r / min for 5 h to obtain ink phase A component.

[0034] (4) Add 25 parts of 2000-molecular-weight end-thiol polyethylene glycol, 2 parts of benzophenone, 10 parts of glycerol, 1 part of trimethylaluminum, and 20 parts of self-made antioxidant to 50-60 parts of anhydrous ethanol, stir at 60°C and 250 r / min for 6 h to obtain the B phase component of ink.

[0035] Example 2

[0036] (1) Take 45 parts of rosmarinic acid, 30 parts of mercaptoethylamine and 3 parts of benzophenone and dissolve them in 55 parts of anhydrous ethanol. Stir for 4 hours at 50°C, 320nm wavelength and 350r / min under nitrogen atmosphere. Transfer to drying oven and dry at 50°C for 3 hours to obtain the self-made antioxidant.

[0037] (2) Add 25 parts of linoleic acid, 20 parts of linoleyl alcohol, and 25 parts of sulfuric acid with a mass fraction of 60% to 55 parts of anhydrous ethanol. Stir at 400 r / min for 6 h in an oil bath at 50 °C under a nitrogen atmosphere. Cool to room temperature and remove the solvent by rotary evaporation to obtain crude product. Redissolve the crude product with tetrahydrofuran to prepare a solution C with the crude product accounting for 60 wt%. Add solution C to n-hexane at a rate of 1 drop / s. The volume ratio of n-hexane to solution C is 3:1. Let stand for 15 h to recrystallize at the interface of n-hexane and tetrahydrofuran. Finally, crystals are obtained. Then, the upper solvent is poured off, the solution is dried by vacuum pump, and then dissolved in tetrahydrofuran. Repeat the crystallization process 6 times to finally obtain the alcohol ester compound.

[0038] (3) Add 35 parts of alcohol ester compound, 15 parts of pigment, 8 parts of mercaptopolysiloxane with a molecular weight of 600 and 25 parts of self-made antioxidant to 55 parts of anhydrous ethanol, stir at 60°C and 200 r / min for 5 h to obtain ink phase A component.

[0039] (4) Add 35 parts of 2000-molecular-weight end-thiol polyethylene glycol, 5 parts of benzophenone, 15 parts of glycerol, 3 parts of trimethylaluminum, and 25 parts of self-made antioxidant to 55 parts of anhydrous ethanol, and stir at 60°C and 250 r / min for 6 h to obtain the B phase component of ink.

[0040] Example 3

[0041] (1) Dissolve 60 parts of rosmarinic acid, 40 parts of mercaptoethylamine and 5 parts of benzophenone in 60 parts of anhydrous ethanol. Stir for 4 hours at 50°C, 320nm wavelength and 350r / min under a nitrogen atmosphere. Transfer to a drying oven and dry at 50°C for 3 hours to obtain the self-made antioxidant.

[0042] (2) Add 30 parts of linoleic acid, 25 parts of linoleyl alcohol, and 30 parts of sulfuric acid with a mass fraction of 60% to 60 parts of anhydrous ethanol. Stir at 400 r / min for 6 h in an oil bath at 50 °C under a nitrogen atmosphere. Cool to room temperature and remove the solvent by rotary evaporation to obtain crude product. Redissolve the crude product with tetrahydrofuran to prepare a solution C with the crude product accounting for 60 wt%. Add solution C to n-hexane at a rate of 1 drop / s. The volume ratio of n-hexane to solution C is 3:1. Let stand for 15 h to recrystallize at the interface of n-hexane and tetrahydrofuran. Finally, crystals are obtained. Then, the upper solvent is poured off, the solution is dried by vacuum pump, and then dissolved in tetrahydrofuran. Repeat the crystallization process 6 times to finally obtain the alcohol ester compound.

[0043] (3) Add 40 parts of alcohol ester compound, 20 parts of pigment, 10 parts of mercaptopolysiloxane with a molecular weight of 600 and 30 parts of self-made antioxidant to 60 parts of anhydrous ethanol, stir at 60°C and 200 r / min for 5 h to obtain ink phase A component.

[0044] (4) Add 45 parts of 2000-molecular-weight end-thiol polyethylene glycol, 8 parts of benzophenone, 20 parts of glycerol, 5 parts of trimethylaluminum, and 30 parts of self-made antioxidant to 60 parts of anhydrous ethanol, and stir at 60°C and 250 r / min for 6 h to obtain the B phase component of ink.

[0045] Comparative Example 1

[0046] (1) Add 25 parts of linoleic acid, 20 parts of linoleyl alcohol, and 25 parts of sulfuric acid with a mass fraction of 60% to 55 parts of anhydrous ethanol. Stir at 400 r / min for 6 h in an oil bath at 50 °C under a nitrogen atmosphere. Cool to room temperature and then remove the solvent by rotary evaporation to obtain crude product. Redissolve the crude product with tetrahydrofuran to prepare a solution C with the crude product accounting for 60 wt%. Add solution C to n-hexane at a rate of 1 drop / s. The volume ratio of n-hexane to solution C is 3:1. Let stand for 15 h to recrystallize at the interface of n-hexane and tetrahydrofuran. Finally, crystals are obtained. Then, the upper solvent is poured off, the solution is dried by vacuum pump, and then dissolved in tetrahydrofuran. Repeat the crystallization process 6 times to finally obtain the alcohol ester compound.

[0047] (2) Add 35 parts of alcohol ester compound, 15 parts of pigment, 8 parts of mercaptopolysiloxane with a molecular weight of 600 and 25 parts of mercaptoethylamine to 55 parts of anhydrous ethanol, stir at 60°C and 200 r / min for 5 h to obtain ink phase A component.

[0048] (3) Add 35 parts of terminal thiol polyethylene glycol with a molecular weight of 2000, 5 parts of benzophenone, 15 parts of glycerol, 3 parts of trimethylaluminum, and 25 parts of mercaptoethylamine to 55 parts of anhydrous ethanol, and stir at 60°C and 250 r / min for 6 h to obtain the B phase component of ink.

[0049] Comparative Example 2

[0050] (1) Add 25 parts of linoleic acid, 20 parts of linoleyl alcohol, and 25 parts of sulfuric acid with a mass fraction of 60% to 55 parts of anhydrous ethanol. Stir at 400 r / min for 6 h in an oil bath at 50 °C under a nitrogen atmosphere. Cool to room temperature and then remove the solvent by rotary evaporation to obtain crude product. Redissolve the crude product with tetrahydrofuran to prepare a solution C with the crude product accounting for 60 wt%. Add solution C to n-hexane at a rate of 1 drop / s. The volume ratio of n-hexane to solution C is 3:1. Let stand for 15 h to recrystallize at the interface of n-hexane and tetrahydrofuran. Finally, crystals are obtained. Then, the upper solvent is poured off, the solution is dried by vacuum pump, and then dissolved in tetrahydrofuran. Repeat the crystallization process 6 times to finally obtain the alcohol ester compound.

[0051] (2) Add 35 parts of alcohol ester compound, 15 parts of pigment, 8 parts of mercaptopolysiloxane with a molecular weight of 600 and 25 parts of rosmarinic acid to 55 parts of anhydrous ethanol, stir at 60°C and 200 r / min for 5 h to obtain ink phase A component.

[0052] (3) Add 35 parts of 2000-molecular-weight end-thiol polyethylene glycol, 5 parts of benzophenone, 15 parts of glycerol, 3 parts of trimethylaluminum, and 25 parts of rosmarinic acid to 55 parts of anhydrous ethanol, and stir at 60°C and 250 r / min for 6 h to obtain the B phase component of ink.

[0053] Comparative Example 3

[0054] (1) Take 45 parts of rosmarinic acid, 30 parts of mercaptoethylamine and 3 parts of benzophenone and dissolve them in 55 parts of anhydrous ethanol. Stir for 4 hours at 50°C, 320nm wavelength and 350r / min under nitrogen atmosphere. Transfer to drying oven and dry at 50°C for 3 hours to obtain the self-made antioxidant.

[0055] (2) Add 15 parts of pigment, 8 parts of mercaptopolysiloxane with a molecular weight of 600 and 25 parts of self-made antioxidant to 55 parts of anhydrous ethanol, stir at 60°C and 200 r / min for 5 h to obtain ink phase A component.

[0056] (3) Add 35 parts of terminal thiol polyethylene glycol with a molecular weight of 2000, 5 parts of benzophenone, 15 parts of glycerol, 3 parts of trimethylaluminum, and 25 parts of self-made antioxidant to 55 parts of anhydrous ethanol, and stir at 60°C and 250 r / min for 6 h to obtain the B phase component of ink.

[0057] Comparative Example 4

[0058] (1) Take 45 parts of rosmarinic acid, 30 parts of mercaptoethylamine and 3 parts of benzophenone and dissolve them in 55 parts of anhydrous ethanol. Stir for 4 hours at 50°C, 320nm wavelength and 350r / min under nitrogen atmosphere. Transfer to drying oven and dry at 50°C for 3 hours to obtain the self-made antioxidant.

[0059] (2) Add 25 parts of linoleic acid, 20 parts of linoleyl alcohol, and 25 parts of sulfuric acid with a mass fraction of 60% to 55 parts of anhydrous ethanol. Stir at 400 r / min for 6 h in an oil bath at 50 °C under a nitrogen atmosphere. Cool to room temperature and remove the solvent by rotary evaporation to obtain crude product. Redissolve the crude product with tetrahydrofuran to prepare a solution C with the crude product accounting for 60 wt%. Add solution C to n-hexane at a rate of 1 drop / s. The volume ratio of n-hexane to solution C is 3:1. Let stand for 15 h to recrystallize at the interface of n-hexane and tetrahydrofuran. Finally, crystals are obtained. Then, the upper solvent is poured off, the solution is dried by vacuum pump, and then dissolved in tetrahydrofuran. Repeat the crystallization process 6 times to finally obtain the alcohol ester compound.

[0060] (3) Add 35 parts of alcohol ester compound, 15 parts of pigment, 8 parts of mercaptopolysiloxane with a molecular weight of 600 and 25 parts of self-made antioxidant to 55 parts of anhydrous ethanol, stir at 60°C and 200 r / min for 5 h to obtain ink phase A component.

[0061] (4) Add 5 parts benzophenone, 15 parts glycerol, 3 parts trimethylaluminum and 25 parts self-made antioxidant to 55 parts anhydrous ethanol, stir at 60°C and 250 r / min for 6 h to obtain ink phase B component.

[0062] Comparative Example 5

[0063] (1) Take 45 parts of rosmarinic acid, 30 parts of mercaptoethylamine and 3 parts of benzophenone and dissolve them in 55 parts of anhydrous ethanol. Stir for 4 hours at 50°C, 320nm wavelength and 350r / min under nitrogen atmosphere. Transfer to drying oven and dry at 50°C for 3 hours to obtain the self-made antioxidant.

[0064] (2) Add 25 parts of linoleic acid, 20 parts of linoleyl alcohol, and 25 parts of sulfuric acid with a mass fraction of 60% to 55 parts of anhydrous ethanol. Stir at 400 r / min for 6 h in an oil bath at 50 °C under a nitrogen atmosphere. Cool to room temperature and remove the solvent by rotary evaporation to obtain crude product. Redissolve the crude product with tetrahydrofuran to prepare a solution C with the crude product accounting for 60 wt%. Add solution C to n-hexane at a rate of 1 drop / s. The volume ratio of n-hexane to solution C is 3:1. Let stand for 15 h to recrystallize at the interface of n-hexane and tetrahydrofuran. Finally, crystals are obtained. Then, the upper solvent is poured off, the solution is dried by vacuum pump, and then dissolved in tetrahydrofuran. Repeat the crystallization process 6 times to finally obtain the alcohol ester compound.

[0065] (3) Add 35 parts of alcohol ester compound, 15 parts of pigment, 8 parts of mercaptopolysiloxane with a molecular weight of 600, 50 parts of self-made antioxidant, 35 parts of terminal mercaptopolyethylene glycol with a molecular weight of 2000, 5 parts of benzophenone, 15 parts of glycerol, and 3 parts of trimethylaluminum to 55 parts of anhydrous ethanol, and stir at 60°C and 200 r / min for 5 h to obtain ink.

[0066] Example of effect

[0067] Table 1 below shows the performance analysis results of the UV waterproof inks used in Examples 1 to 3 and Comparative Examples 1 to 5 of the present invention.

[0068] Table 1. Performance test results of UV waterproof inks prepared in Examples 1 to 3 and Comparative Examples 1 to 5

[0069]

[0070] The results in Table 1 show that the UV waterproof ink prepared by this invention has a fast curing rate, good adhesion, excellent flexibility, and high pencil hardness after curing. It retains its original state even after being soaked in water for 240 hours, demonstrating high water resistance. Comparing the results of Example 2 and Comparative Example 5, it was found that storing the two ink phases together affects the quality of the ink. Comparing the results of Example 2 and Comparative Examples 3-4, it was found that the use of alcohol ester compounds improved the waterproof effect of the UV waterproof ink, thus enhancing its waterproof performance.

[0071] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from its spirit or essential characteristics. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, all variations falling within the meaning and scope of equivalents of the claims are intended to be included within the present invention. No markings in the claims should be construed as limiting the scope of the claims.

Claims

1. A method for preparing a UV waterproof ink, characterized in that, The preparation steps include the following: (1) Dissolve rosmarinic acid, mercaptoethylamine and photoinitiator in anhydrous ethanol. Stir at 40-60℃, UV wavelength of 250-360nm and stirring rate of 200-400r / min for 2-4h under nitrogen atmosphere. Transfer to drying oven and dry at 50-60℃ for 2-4h to obtain self-made antioxidant. (2) Linoleic acid, linoleyl alcohol, and sulfuric acid with a mass fraction of 60% are added to anhydrous ethanol. The mixture is stirred at 300-600 r / min for 4-8 h in an oil bath at 40-50 °C under a nitrogen atmosphere. After cooling to room temperature, the solvent is removed by rotary evaporation to obtain a crude product. The crude product is redissolved in tetrahydrofuran to prepare a solution C with a crude product content of 50-60 wt%. Solution C is then added to n-hexane at a rate of 0.5-1 drops / s, with a volume ratio of n-hexane to solution C of 3:

1. The mixture is allowed to stand for 10-18 h to recrystallize at the interface between n-hexane and tetrahydrofuran to obtain crystals. The upper solvent is then discarded, the mixture is dried by vacuum pump, and then dissolved in tetrahydrofuran. This crystallization process is repeated 5-8 times to finally obtain the alcohol ester compound. (3) Add alcohol ester compound, pigment, mercaptopolysiloxane and self-made antioxidant to anhydrous ethanol, stir at 50~80℃ and 100~300r / min for 3~6h to obtain ink phase A component; (4) Add polyethylene glycol containing terminal mercapto groups, photoinitiator, glycerol, trimethylaluminum and self-made antioxidant to anhydrous ethanol, stir at 50~80℃ and 100~300r / min for 3~6h to obtain ink phase B component.

2. The method for preparing a UV waterproof ink according to claim 1, characterized in that, In step (1), by weight, there are 30-60 parts of rosmarinic acid, 20-40 parts of mercaptoethylamine, 1-5 parts of photoinitiator, and 50-60 parts of anhydrous ethanol.

3. The method for preparing a UV waterproof ink according to claim 1, characterized in that, In step (2), by weight, there are 20-30 parts of linoleic acid, 15-25 parts of linoleyl alcohol, 20-30 parts of sulfuric acid, and 50-60 parts of anhydrous ethanol.

4. The method for preparing a UV waterproof ink according to claim 1, characterized in that, In step (3), by weight, there are 30-40 parts of alcohol ester compound, 10-20 parts of pigment, 5-10 parts of mercaptopolysiloxane, 20-30 parts of self-made antioxidant, and 50-60 parts of anhydrous ethanol.

5. The method for preparing a UV waterproof ink according to claim 1, characterized in that, In step (4), by weight, there are 25-45 parts of terminal thiol polyethylene glycol, 2-8 parts of photoinitiator, 10-20 parts of glycerol, 1-5 parts of trimethylaluminum, 20-30 parts of self-made antioxidant, and 50-60 parts of anhydrous ethanol.

6. The method for preparing a UV waterproof ink according to claim 1, characterized in that, When using the ink, mix 50 parts of ink phase A and 50 parts of ink phase B, stir well, print, and then cure for 0.5 to 2 seconds under ultraviolet light with a wavelength of 350 to 400 nm.

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