UV-cured acid-resistant protective ink and preparation method thereof

Abstract

The invention discloses UV-cured acid-resistant protective ink and a preparation method thereof, and belongs to the technical field of glass protective ink. The UV-cured acid-resistant protective ink is prepared from the following raw materials: 50 to 60 parts of carboxylated polyurethane acrylate, 10 to 15 parts of reactive diluent, 4 to 7 parts of photoinitiator, 2 to 4 parts of silane coupling agent, 12 to 18 parts of nano silicon dioxide, 1 to 1.5 parts of defoaming agent and 1 to 1.5 parts of flatting agent. The preparation method comprises the following steps: firstly, reacting 4, 4 '-methylene bis (phenyl isocyanate) with 1, 11-undecanediol, and generating polyurethane by using lactic acid as an end-capping reagent; reacting with glycidyl acrylate to generate polyurethane acrylate, and finally reacting with butanedioic anhydride to obtain the polyurethane acrylate. The UV-cured acid-resistant protective ink prepared by the invention has the advantages of short curing time, smooth surface after curing, favorable acid resistance and quick deinking performance.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of glass protection ink, in particular to a UV-cured acid-resistant protection ink and a preparation method thereof. BACKGROUND

[0002] In the processing of ultra-thin flexible glass (UTG), such as laser cutting, chemical etching, etc., the glass surface needs to be protected to prevent it from being eroded by chemical reagents such as acid. Traditional protection methods usually use acid-resistant protective film or baking ink, but these methods have many shortcomings. Although acid-resistant protective film can provide certain protection, it is prone to problems such as poor adhesion or residual stains; baking ink requires a long curing time and high energy consumption, which does not meet the energy-saving and environmentally friendly production requirements. Therefore, it is of great practical significance to develop a high-performance protection ink suitable for the processing of ultra-thin flexible glass.

[0003] Chinese invention patent with publication number CN114656834A discloses a glass protection ink and a preparation method thereof. The raw material components of the protection ink include, by weight: phenolic resin 30-40 parts, solvent 10-30 parts, and auxiliary agent 0.1-4 parts; wherein the phenolic resin is DCPDN structure. The glass protection ink of the invention example has good acid resistance and film fading resistance, but its curing time is relatively long. SUMMARY

[0004] In view of the shortcomings of the prior art, the purpose of the present application is to provide a UV-cured acid-resistant protection ink and a preparation method thereof.

[0005] To achieve the above-mentioned purpose, the present application realizes the following technical solutions:

[0006] A UV-cured acid-resistant protection ink, comprising the following raw materials by weight:

[0007] 50-60 parts of carboxylated polyurethane acrylate, 10-15 parts of active diluent, 4-7 parts of photoinitiator, 2-4 parts of silane coupling agent, 12-18 parts of nano-silicon dioxide, 1-1.5 parts of defoaming agent, and 1-1.5 parts of leveling agent;

[0008] The carboxylated polyurethane acrylate is prepared by the following method:

[0009] S1: 4,4'-methylenebis (isocyanate phenyl) and 1,11-undecanediol are reacted, and lactic acid is used as a capping agent to generate polyurethane; the reaction equation is as follows:

[0010]

[0011] S2: the polyurethane reacts with glycidyl acrylate to form a polyurethane acrylate; the reaction equation is shown as follows:

[0012]

[0013] S3: the polyurethane acrylate reacts with succinic anhydride to form a carboxylated polyurethane acrylate; the reaction equation is shown as follows:

[0014]

[0015] In step S1, the feeding molar ratio of the 4,4'-methylenebis(phenyl isocyanate) to 1,11-undecanediol is (1.1-1.2):1.

[0016] In step S2, the feeding molar ratio of the polyurethane to glycidyl acrylate is 1:(2-2.2).

[0017] In step S3, the feeding molar ratio of the polyurethane acrylate to succinic anhydride is 1:(2-2.1).

[0018] The active diluent is prepared by the following method:

[0019] N1: 2,2-bis(4-aminophenyl)hexafluoropropane reacts with 3-bromopropene to form a bis-tertiary amine compound; the reaction equation is shown as follows:

[0020]

[0021] N2: the bis-tertiary amine compound reacts under the action of formic acid and hydrogen peroxide to form a tetra-epoxide compound; the reaction equation is shown as follows:

[0022]

[0023] N3: the tetra-epoxide compound reacts with 10-undecenoic acid to obtain an active diluent; the reaction equation is shown as follows:

[0024]

[0025] In step N1, the feeding molar ratio of the 2,2-bis(4-aminophenyl)hexafluoropropane to 3-bromopropene is 1:4.3; in step N2, the feeding molar ratio of the bis-tertiary amine compound to formic acid is 1:4.8; in step N3, the feeding molar ratio of the tetra-epoxide compound to 10-undecenoic acid is 1:4.5.

[0026] The photoinitiator is one of TPO, photoinitiator 184.

[0027] The defoaming agent is one of BYK-066N, DF-680.

[0028] The leveling agent is one of BYK-358N, BYK-333; the silane coupling agent is 3-(isobutyryloxy) propyl trimethoxysilane.

[0029] A preparation method of a UV-cured acid-resistant protective ink, comprising the following steps:

[0030] S1: weigh by weight parts: carboxylated polyurethane acrylate 50-60 parts, active diluent 10-15 parts, photoinitiator 4-7 parts, silane coupling agent 2-4 parts, nano-silicon dioxide 12-18 parts, defoaming agent 1-1.5 parts, leveling agent 1-1.5 parts;

[0031] S2: the carboxylated polyurethane acrylate, active diluent, silane coupling agent, nano-silicon dioxide, defoaming agent, leveling agent are added into the reaction kettle, stirred and mixed uniformly, then the photoinitiator is added, stirred uniformly, filtered through a filter screen, and the UV-cured acid-resistant protective ink is obtained.

[0032] Due to the adoption of the above technical scheme, the beneficial effects of the present application include:

[0033] The carboxylated polyurethane acrylate of the present application resists UTG laser cutting damage through the hard segment-soft segment alternating structure, enhances acid resistance through hydrophobicity, and reduces acid etching through carboxyl groups and facilitates alkaline stripping. The active diluent prepared in the present application contains fluorine atoms, which can reduce the surface tension of the ink and enhance acid resistance, the four-arm unsaturated double bond structure accelerates the curing speed, the flexible long-chain alkyl group relieves the volume shrinkage stress and reduces the edge shrinkage phenomenon. The UV-cured acid-resistant protective ink prepared in the present application has short curing time, smooth surface after curing, and good acid resistance and rapid deinking performance. DETAILED DESCRIPTION

[0034] The present application will be further described below in conjunction with examples, but the present application is not limited to these examples.

[0035] Example 1: Preparation of carboxylated polyurethane acrylate:

[0036] S1: 400ml of anhydrous DMF, 0.11mol of 4,4'-methylenebis(isocyanate phenyl ester), 0.1mol of 1,11-undecanediol are added into a reaction kettle, stirred and mixed uniformly, heated to 70℃, 1g of dibutyltin dilaurate is added, reacted for 8h, 0.05mol of lactic acid is added and reacted for 2h, cooled to room temperature, 800ml of deionized water is added to precipitate the solid, filtered, washed with 200ml of deionized water, and vacuum dried at 60℃ for 24h to obtain polyurethane with a number average molecular weight of 4282;

[0037] S2: 2000 ml of toluene, 0.1 mol of polyurethane, 0.2 mol of glycidyl acrylate were added into the reaction kettle, stirred and mixed, 4 g of tetramethylammonium chloride was added, heated to 100°C, reacted for 8 h, cooled to room temperature, washed with 0.1 M HCl solution three times (200 ml each time), distilled at 60°C under reduced pressure for 3 h, and polyurethane acrylate with a number average molecular weight of 4536 was obtained;

[0038] S3: 2000 ml of tetrahydrofuran, 0.1 mol of polyurethane acrylate, 5 g of sodium propionate were added into the reaction kettle, heated to 50°C under nitrogen protection, 0.2 mol of succinic anhydride was added in batches (divided into 4 batches, each batch interval 10 min), heated to reflux, reacted for 6 h, cooled to room temperature, washed with saturated brine three times (100 ml each time), distilled at 40°C under reduced pressure for 2 h, and carboxylated polyurethane acrylate was obtained.

[0039] Preparation of carboxylated polyurethane acrylate in Example 2:

[0040] S1: 400 ml of anhydrous DMF, 0.115 mol of 4,4'-methylenebis(isocyanate), 0.1 mol of 1,11-undecanediol were added into the reaction kettle, stirred and mixed, heated to 75°C, 1 g of dibutyltin dilaurate was added, reacted for 7 h, 0.05 mol of lactic acid was added and reacted for 2 h, cooled to room temperature, 800 ml of deionized water was added to precipitate the solid, filtered, washed with 200 ml of deionized water, and vacuum dried at 60°C for 24 h to obtain polyurethane with a number average molecular weight of 2976;

[0041] S2: 2000 ml of toluene, 0.1 mol of polyurethane, 0.21 mol of glycidyl acrylate were added into the reaction kettle, stirred and mixed, 4 g of tetramethylammonium chloride was added, heated to 105°C, reacted for 7 h, cooled to room temperature, washed with 0.1 M HCl solution three times (200 ml each time), distilled at 60°C under reduced pressure for 3 h, and polyurethane acrylate with a number average molecular weight of 3227 was obtained.

[0042] S3: 2000 ml of tetrahydrofuran, 0.1 mol of polyurethane acrylate, 5 g of sodium propionate were added into the reaction kettle, heated to 50°C under nitrogen protection, 0.205 mol of succinic anhydride was added in batches (divided into 4 batches, each batch interval 10 min), heated to reflux, reacted for 7 h, cooled to room temperature, washed with saturated brine three times (200 ml each time), distilled at 40°C under reduced pressure for 2 h, and carboxylated polyurethane acrylate was obtained.

[0043] Preparation of carboxylated polyurethane acrylate in Example 3:

[0044] S1 : 400 ml of anhydrous DMF, 0.12 mol of 4,4'-methylenebis(phenyl isocyanate), 0.1 mol of 1,11-undecanediol were added into a reaction kettle, stirred and mixed, heated to 80°C, 1 g of dibutyltin dilaurate was added, reacted for 6 h, 0.05 mol of lactic acid was added and reacted for 2 h, cooled to room temperature, 800 ml of deionized water was added to precipitate the solid, filtered, washed with 200 ml of deionized water, and dried at 60°C under vacuum for 24 h to obtain a polyurethane with a number average molecular weight of 2317;

[0045] S2: 2000 ml of toluene, 0.1 mol of polyurethane, 0.22 mol of glycidyl acrylate were added into a reaction kettle, stirred and mixed, 4 g of tetramethylammonium chloride was added, heated to reflux, reacted for 6 h, cooled to room temperature, washed with 0.1 M HC1 solution three times (200 ml each time), distilled at 60°C under reduced pressure for 3 h to obtain a polyurethane acrylate with a number average molecular weight of 2574;

[0046] S3: 2000 ml of tetrahydrofuran, 0.1 mol of polyurethane acrylate, 5 g of sodium propionate were added into a reaction kettle, heated to 50°C under nitrogen protection, 0.21 mol of succinic anhydride was added in batches (divided into 4 batches, with an interval of 10 min), heated to reflux, reacted for 8 h, cooled to room temperature, washed with saturated brine three times (200 ml each time), distilled at 40°C under reduced pressure for 2 h to obtain a carboxylated polyurethane acrylate.

[0047] Example 4 Preparation of active diluent:

[0048] N1 : 300 ml of chloroform, 0.1 mol of 2,2-bis(4-aminophenyl)hexafluoropropane, 0.45 mol of triethylamine were added into a reaction kettle, stirred and mixed, heated to 60°C, 0.43 mol of 3-bromopropene was added dropwise, reacted for 5 h, washed with saturated sodium bicarbonate solution three times (100 ml each time), the organic phase was distilled at 40°C under reduced pressure for 2 h to obtain a bis-tertiary amine compound; its nuclear magnetic resonance hydrogen spectrum data are as follows: 1 H NMR (300 MHz, DMSO-d6) δ 7.24-7.14 (m, 4H), 6.97-6.87 (m, 4H), 5.78 (ddt, J = 16.9, 11.3, 5.6 Hz, 4H), 5.32-4.95 (m, 8H), 3.86 (dt, J = 5.6, 1.4 Hz, 8H);

[0049] N2: 500 ml DMF, 0.1 mol of the bis(tertiary) amine compound, and 2 g of strong acid cation exchange resin were sequentially added to a reaction vessel. The mixture was stirred and heated to 60 °C. 0.48 mol of formic acid and 85 g of a 30 wt% H₂O₂ solution were added dropwise over 1 hour. The reaction was allowed to proceed for 6 hours, then cooled to room temperature. The mixture was filtered, distilled under reduced pressure at 60 °C for 4 hours, washed three times with 300 ml of deionized water each time, and dried under vacuum at 60 °C for 10 hours to obtain the tetraepoxide compound. Its 1H NMR spectrum data are as follows: 1 H NMR(300MHz,DMSO-d6)δ7.24-7.14(m,4H),6.90-6.80(m,4H),3.61(dd,J=11.9,3.6Hz,4H),3.44(t t,J=3.6,2.7Hz,4H),3.36(dd,J=11.8,3.6Hz,4H),3.24-3.17(m,4H),2.96(dd,J=7.5,2.7Hz,4H);

[0050] N3: Add 600 ml toluene, 0.1 mol tetraepoxide, and 0.45 mol 10-undecenoic acid to a reaction vessel, stir and mix well, add 8 g tetramethylammonium bromide, heat to reflux, react for 5 h, cool to room temperature, wash three times with saturated sodium bicarbonate solution (200 ml each time), and distill under reduced pressure at 70 °C for 3 h to obtain the active diluent; its 1H NMR data are as follows: 1 H NMR (300MHz, DMSO-d6) δ7.24-7.14(m,4H),6.88-6.79(m,4H),5.92(d,J=5.0Hz,3H),5.86-5.70(m,8H),5.18-4.92(m ,8H),3.72-3.37(m,7H),2.47-2.27(m,7H),2.03(tdt,J=8.1,6.8,1.4Hz,9H),1.57-1.41(m,9H),1.40-1.21(m,39H).

[0051] Example 5: UV-cured acid-resistant protective ink

[0052] S1: Weigh out: 50g of carboxylated polyurethane acrylate (prepared in Example 1), 10g of reactive diluent (prepared in Example 4), 4g of TPO, 2g of 3-(isobutenoyloxy)propyltrimethoxysilane, 12g of nano silica, 1g of BYK-066N, and 1g of BYK-358N;

[0053] S2: Carboxylated polyurethane acrylate, active diluent, 3-(isobutenoyloxy) propyl trimethoxysilane, nano-silica, BYK-066N, BYK-358N were added into a reaction kettle, stirred at room temperature at a speed of 1200 r / min for 20 min, then TPO was added, and stirring was continued for 2 h, and filtration was performed using a 350-mesh filter to obtain a UV-cured acid-resistant protective ink.

[0054] Example 6 UV-cured acid-resistant protective ink:

[0055] S1: Carboxylated polyurethane acrylate (prepared in Example 2): 56 g, active diluent (prepared in Example 4): 12 g, photoinitiator 184: 6 g, 3-(isobutenoyloxy) propyl trimethoxysilane: 3 g, nano-silica 16 g, DF-680: 1.2 g, BYK-333: 1.2 g were weighed.

[0056] S2: Carboxylated polyurethane acrylate, active diluent, 3-(isobutenoyloxy) propyl trimethoxysilane, nano-silica, DF-680, BYK-333 were added into a reaction kettle, stirred at room temperature at a speed of 1400 r / min for 20 min, then photoinitiator 184 was added, and stirring was continued for 2 h, and filtration was performed using a 350-mesh filter to obtain a UV-cured acid-resistant protective ink.

[0057] Example 7 UV-cured acid-resistant protective ink:

[0058] S1: Carboxylated polyurethane acrylate (prepared in Example 3): 60 g, active diluent (prepared in Example 4): 15 g, photoinitiator 184: 7 g, 3-(isobutenoyloxy) propyl trimethoxysilane: 4 g, nano-silica 18 g, DF-680: 1.5 g, BYK-333: 1.5 g were weighed.

[0059] S2: Carboxylated polyurethane acrylate, active diluent, 3-(isobutenoyloxy) propyl trimethoxysilane, nano-silica, DF-680, BYK-333 were added into a reaction kettle, stirred at room temperature at a speed of 1500 r / min for 20 min, then photoinitiator 184 was added, and stirring was continued for 2 h, and filtration was performed using a 350-mesh filter to obtain a UV-cured acid-resistant protective ink.

[0060] Comparative Example 1

[0061] The raw material components and proportions of the UV-cured acid-resistant protective ink were basically the same as in Example 6, except that the carboxylated polyurethane acrylate (prepared in Example 2) added in the components was replaced with an equal weight of polyurethane acrylate (prepared in Example 2, step S2).

[0062] Comparative Example 2

[0063] The raw material components and the ratio of the UV-curable acid-resistant protective ink are basically the same as those of Example 6, except that the carboxylated polyurethane acrylate (prepared in Example 2) added in the component is replaced with the same weight of carboxylated polyurethane acrylate prepared by the following method:

[0064] The preparation method of the carboxylated polyurethane acrylate is basically the same as that of Example 2, except that the 1,11-undecanediol in step S1 is replaced with the same molar amount of hexaethylene glycol.

[0065] Comparative Example 3

[0066] The raw material components and the ratio of the UV-curable acid-resistant protective ink are basically the same as those of Example 6, except that the carboxylated polyurethane acrylate (prepared in Example 2) added in the component is replaced with the same weight of carboxylated polyurethane acrylate prepared by the following method:

[0067] The preparation method of the carboxylated polyurethane acrylate is basically the same as that of Example 2, except that the succinic anhydride in step S3 is replaced with the same molar amount of maleic anhydride.

[0068] Comparative Example 4

[0069] The raw material components and the ratio of the UV-curable acid-resistant protective ink are basically the same as those of Example 6, except that the active diluent (prepared in Example 4) added in the component is replaced with the same weight of active diluent prepared by the following method:

[0070] The preparation method of the active diluent is basically the same as that of Example 4, except that the amount of 3-bromopropene added in step N1 is reduced to 0.21 mol.

[0071] Comparative Example 5

[0072] The raw material components and the ratio of the UV-curable acid-resistant protective ink are basically the same as those of Example 6, except that the active diluent (prepared in Example 4) added in the component is replaced with the same weight of active diluent prepared by the following method:

[0073] The preparation method of the active diluent is basically the same as that of Example 4, except that the 2,2-bis(4-aminophenyl)hexafluoropropane in step N1 is replaced with the same molar amount of 4,4'-diaminodiphenylmethane.

[0074] Comparative Example 6

[0075] The raw material components and the ratio of the UV-curable acid-resistant protective ink are basically the same as those of Example 6, except that the active diluent (prepared in Example 4) added in the component is replaced with the same weight of active diluent prepared by the following method:

[0076] The method for preparing the active diluent is basically the same as that in Embodiment 4, except that 10-undecenoic acid in step N3 is replaced by equimolar amount of acrylic acid.

[0077] The nano-silica used in the present application has a model number of DK-SiO2-30, is produced by Suzhou Meilbang Nanometer Material Co., Ltd., and has an average particle size of 30 nm; the strong-acid cation exchange resin is a polymer of divinylbenzene and sodium vinylbenzenesulfonate, and has a model number of IMAC HP1110 resin.

[0078] The UV-cured acid-resistant protective inks prepared in Embodiments 5-7 and Comparative Examples 1-6 are uniformly coated on the surface of UTG (12×12 mm) with a thickness of 30 μm by using a silk-screen process, and the coating thickness is 20 μm. Then, the inks are cured by using a UV mercury lamp (curing energy 1200 mJ / cm 2 ) to obtain UTG samples coated with cured inks, the curing time is recorded, and whether the surface is flat and whether there is edge shrinkage is observed. The curing time is shown in Table 1.

[0079] The UTG samples coated with cured inks prepared by the above method are subjected to adhesion, acid resistance and deinking tests, and the test results are shown in Table 1.

[0080] Adhesion test: the test is performed according to the standard of GB / T 9286-1998, a cross-hatch tester is used to draw 100 1 mm×1 mm squares on the ink film layer of the sample, and then a 3M tape is pasted firmly and quickly peeled off to test the adhesion grade.

[0081] Acid resistance test: the sample is immersed in a 5wt% HF solution, the immersion temperature is 25℃, after immersion for 20 min, the sample is washed with clean water, and whether the ink on the UTG surface is complete is observed.

[0082] Deinking test: the sample is immersed in a 5wt% sodium hydroxide solution, the immersion temperature is 50℃, and the time required for complete ink removal is recorded.

[0083] Table 1 Performance test data

[0084]

[0085]

[0086] As can be seen from Table 1 Embodiments 5, 6 and 7, the UV-cured acid-resistant protective ink prepared in the present application has a short curing time, a flat surface after curing, and good acid resistance and rapid deinking performance.

[0087] The rigid benzene ring and long chain alkyl in the carboxylated polyurethane acrylate prepared by the application jointly constitute a hard segment-soft segment alternating structure, which can effectively resist the damage risk of the glass edge caused by the heat impact and debris splashing in the UTG laser cutting process; at the same time, the hydrophobic properties of the benzene ring and the long chain alkyl can enhance its resistance in acidic conditions. The carboxyl group in the carboxylated polyurethane acrylate can improve the interfacial adhesion of the material and the glass through polar force; at the same time, it can reduce the erosion of the ink by the acidic medium through dissociation, and easily undergoes neutralization reaction to generate water-soluble carboxylate under alkaline conditions, which is convenient for peeling from the UTG. In comparison, the carboxylated polyurethane acrylate used in Comparative Example 2 contains a polyether segment, which is poor in acid resistance; the carboxylated polyurethane acrylate containing multiple carbon-carbon double bonds used in Comparative Example 3 cannot release stress through molecular chain fine tuning during the curing process, resulting in edge shrinkage.

[0088] The active diluent prepared by the application contains fluorine atoms, and the low surface tension characteristics of which can effectively reduce the surface tension of the ink, thereby improving the leveling performance of the ink and making the cured ink smooth and flat; and the high bond energy of the C-F bond can enhance the acid resistance of the cured ink. The four-arm unsaturated double bond structure of the active diluent can improve the reactivity and thus accelerate the curing speed. In addition, the flexible long chain alkyl structure in the active diluent can relieve the volume shrinkage stress during the curing process through molecular chain movement, which helps to reduce the occurrence of edge shrinkage. In comparison, the active diluent used in Comparative Example 6 has a short flexible alkyl chain, and the surface after curing is not flat, with edge shrinkage.

[0089] The above is only a preferred embodiment of the application and is not intended to limit the application; but for ordinary skilled persons in the art, some minor changes, modifications and equivalent changes made within the scope of the technical solutions of the application using the technical content disclosed above are equivalent embodiments of the application; at the same time, any equivalent changes, modifications and evolution of the above embodiments made according to the essential technology of the application are still within the protection scope of the technical solutions of the application.

Claims

1. A UV-curable acid-resistant protective ink, characterized in that, The ingredients include the following parts by weight: Carboxylated polyurethane acrylate 50-60 parts, reactive diluent 10-15 parts, photoinitiator 4-7 parts, silane coupling agent 2-4 parts, nano silica 12-18 parts, defoamer 1-1.5 parts, leveling agent 1-1.5 parts; The carboxylated polyurethane acrylate is prepared by the following method: S1: 4,4'-methylenebis(phenyl isocyanate) and 1,11-undecanediol are reacted, and lactic acid is used as a capping agent to generate polyurethane; S2: Polyurethane reacts with glycidyl acrylate to produce polyurethane acrylate; S3: Polyurethane acrylate reacts with succinic anhydride to generate carboxylated polyurethane acrylate.

2. The UV-curable acid-resistant protective ink according to claim 1, characterized in that, In step S1, the molar ratio of 4,4'-methylenebis(phenyl isocyanate) to 1,11-undecanediol is (1.1-1.2):

1.

3. The UV-curable acid-resistant protective ink according to claim 1, characterized in that, In step S2, the molar ratio of polyurethane to glycidyl acrylate is 1:(2-2.2).

4. The UV-curable acid-resistant protective ink according to claim 1, characterized in that, In step S3, the molar ratio of polyurethane acrylate to succinic anhydride is 1:(2-2.1).

5. The UV-curable acid-resistant protective ink according to claim 1, characterized in that, The reactive diluent is prepared by the following method: N1: 2,2-bis(4-aminophenyl)hexafluoropropane reacts with 3-bromopropene to form a bistertiary amine compound; N2: Ditertiary amine compounds react with formic acid and hydrogen peroxide to form tetracyclic oxides; N3: Tetraepoxide reacts with 10-undecenoic acid to obtain an active diluent.

6. The UV-curable acid-resistant protective ink according to claim 5, characterized in that, In step N1, the molar ratio of 2,2-bis(4-aminophenyl)hexafluoropropane to 3-bromopropene is 1:4.3; in step N2, the molar ratio of the bis-tertiary amine compound to formic acid is 1:4.8; in step N3, the molar ratio of the tetraepoxide compound to 10-undecenoic acid is 1:4.

5.

7. The UV-curable acid-resistant protective ink according to claim 1, characterized in that, The photoinitiator is one of TPO and photoinitiator 184.

8. The UV-curable acid-resistant protective ink according to claim 1, characterized in that, The defoamer is one of BYK-066N and DF-680.

9. The UV-curable acid-resistant protective ink according to claim 1, characterized in that, The leveling agent is one of BYK-358N and BYK-333; the silane coupling agent is 3-(isobutenoyloxy)propyltrimethoxysilane.

10. A method for preparing a UV-curable acid-resistant protective ink according to any one of claims 1-9, characterized in that, Includes the following steps: S1: Weigh out the following by weight: 50-60 parts of carboxylated polyurethane acrylate, 10-15 parts of reactive diluent, 4-7 parts of photoinitiator, 2-4 parts of silane coupling agent, 12-18 parts of nano silica, 1-1.5 parts of defoamer, and 1-1.5 parts of leveling agent. S2: Add carboxylated polyurethane acrylate, reactive diluent, silane coupling agent, nano silica, defoamer, and leveling agent to a reaction vessel, stir and mix evenly, then add photoinitiator, stir evenly, and filter through a filter screen to obtain UV-curable acid-resistant protective ink.

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