Novel-process dual-curing printing ink capable of resisting electrolytic etching

Abstract

The invention belongs to the technical field of printing ink, and provides dual-curing printing ink capable of resisting an electrolytic etching new process. Comprising dual-curing modified epoxy resin CUV-A, dual-curing acrylic acid modified epoxy resin CUV-B, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, trimethylolpropane triacrylate, trifunctional acid ester, tripropylene glycol diacrylate, gamma-methacryloxypropyltrimethoxysilane, 3-(2, 2, 6-trimethyl-1, 3-pentanediol)-1, 3, 4-trimethyl-1, 3-pentanediol diacrylate, 2, 3-pentanediol diacrylate, 2, 3-pentanediol diacrylate, 2, 3-pentanediol diacrylate, 2, 3-pentanediol diacrylate, 2, 3-pentanediol diacrylate, 2, 3-pentanediol The coating is prepared from 2, 3-epoxypropoxy propyl trimethoxy silane, 2-ethyl anthraquinone, a photoinitiator 651, a photoinitiator TPO, a photoinitiator 1173, hexafluoroantimonic acid blocked ammonium salt, trifluorosulfonic acid blocked ammonium salt, silica powder, talcum powder, barium sulfate, calcium magnesium carbonate, fumed silica, pigment green, a defoaming agent and a polyether siloxane copolymer. The obtained dual-curing ink has good dual-curing performance, printing performance, adhesive force, scratch resistance and wave-soldering thermal shock resistance, and can be used for laser windowing.

Description

Technical Field

[0001] The invention belongs to the technical field of inks, and in particular relates to a dual-curing ink capable of withstanding a new electrolytic etching process. Background Art

[0002] The dual-curing ink that can withstand the new electrolytic etching process is a special dual-curing ink designed for the printed circuit board (PCB) process of the new electrolytic etching process. It responds to the environmental protection and low VOC requirements and combines the dual-curing mechanism (light curing and heat curing), while improving the ink grade, so that the circuit ink and solder mask ink can be used as one ink. The light-curing circuit ink that is mainly used in the new electrolytic etching process combines the three processes of electrolytic etching, metal recovery, and chemical etching. The process is to screen-print the ink onto the copper foil substrate. It only needs to be photocured to form the circuit pattern. The electrochemical reaction in the electrolytic etching is used to dissolve the exposed copper foil without ink coverage, and the copper plate is used as the cathode to deposit and recover the metal copper. Chemical etching is then applied to remove the small amount of residual copper on the circuit board that cannot be electrolytically etched, which not only completes the production of fine circuits, but also realizes the recovery of a large amount of metal copper. It can also be directly applied to dual-curing solder mask ink. Following the aforementioned process, the invented dual-curing ink is directly screen-printed and coated on the circuit board to replace the traditional solder mask ink. Through the dual-curing mechanism of light curing and heat curing, the circuits on the printed circuit board are permanently protected to prevent the circuits from being open or short-circuited due to oxidation and scratches, and provide excellent electrical insulation performance. The dual-curing ink has good laser absorption and thermal stability, and can achieve precise processing without damaging the circuit board during the laser windowing process.

[0003] At present, dual-cure inks that can withstand the new electrolytic etching process can be widely used in printed circuit board manufacturing, automotive electronics, communication equipment, aerospace and other applications that require the new electrolytic etching process. Its advantages are environmentally friendly recycling of a large amount of metal for recycling, improved processing efficiency, reduced additional curing equipment and material consumption, and enhanced product quality. Therefore, dual-cure inks need to ensure that the two curing mechanisms can work together in the ink to achieve the ideal curing effect and performance, and after curing, they need to have good adhesion, hardness, chemical resistance and other properties.

[0004] Therefore, a dual-curing ink that can withstand the new electrolytic etching process was developed to meet the PCB industry's demand for a new electrolytic etching metal recovery process. Summary of the invention

[0005] In order to ensure that the two curing mechanisms can work synergistically in the ink to achieve the desired curing effect and performance, the present invention provides a dual-cure ink that can withstand the new electrolytic etching process.

[0006] The purpose of the present invention can be achieved through the following technical solutions:

[0007] A dual-curing ink resistant to a new electrolytic etching process comprises the following raw materials in parts by weight:

[0008] 30.0-70.0 parts of dual-cure modified epoxy resin CUV-A, 5.0-65.0 parts of dual-cure acrylic modified epoxy resin CUV-B, 15.0-25.0 parts of dipentaerythritol hexaacrylate, 10.0-20.0 parts of pentaerythritol tetraacrylate, 5.0-15.0 parts of trimethylolpropane triacrylate, 0.5-5.0 parts of trifunctional acid ester, 5.0-15.0 parts of tripropylene glycol diacrylate, 0.1-3.0 parts of γ-methacryloxypropyl trimethoxysilane, 0.1-3.0 parts of 3-(2,3-epoxypropoxy)propyl trimethoxysilane, 1.0-7.0 parts of 2-ethyl anthraquinone, 11.0-7.0 parts of photoinitiator 651, and photoinitiator TPO 1.0-7.0 parts, photoinitiator 11731.0-7.0 parts, hexafluoroantimonic acid blocked ammonium salt 0.1-3.0 parts, trifluorosulfonic acid blocked ammonium salt 0.1-3.0 parts, silica powder 5.0-40.0 parts, talc powder 5.0-40.0 parts, barium sulfate 5.0-40.0 parts, calcium magnesium carbonate 5.0-40.0 parts, fumed silica 0.2-5.0 parts, pigment green 0.5-2.0 parts, defoamer 0.2-2.0 parts, polyether siloxane copolymer (wetting and leveling agent) 0.2-2.0 parts.

[0009] Furthermore, the dual-curing modified epoxy resin CUV-A is prepared by the following steps:

[0010] Step 1, o-cresol epoxy resin and phenolic epoxy resin are put into a four-necked flask, filled with dry air, and heated to 100° C. When the o-cresol epoxy resin and phenolic epoxy resin are in liquid state, acrylic acid is added; then antioxidant, triphenylphosphine and polymerization inhibitor are added into the four-necked flask, and the temperature is slowly raised to 125-130° C. for reaction for 3-6 hours. After the acid value is determined to be less than 2.0, an epoxy acrylate copolymer hybridized with o-cresol epoxy and phenolic epoxy is obtained;

[0011] Step 2, adding the epoxy acrylate copolymer of o-cresol epoxy and phenolic epoxy hybrid into a four-necked flask, maintaining 80-100° C., adding IPDI and MDI-50, maintaining 80-100° C. for reaction for 2-6 hours, measuring NCO every hour for control confirmation, and after measuring NCO% <0.2, obtaining a multifunctional o-cresol epoxy-phenolic epoxy polyurethane acrylate copolymer;

[0012] Step 3, add the multifunctional o-cresol epoxy-phenolic epoxy polyurethane acrylate copolymer into a four-necked flask, and then add the multifunctional amino compound condensation resin. Fill with dry air and nitrogen during the process, maintain 120-130°C for reaction for 3-8 hours, measure the hydroxyl equivalent (OHV) and viscosity every hour during the reaction for control confirmation, and cool down when the measured OHV reaches the target specification value to obtain the dual-cure modified epoxy resin CUV-A.

[0013] Furthermore, in step 1, the weight ratio of the o-cresol epoxy resin and the phenolic epoxy resin is (1:9) to (9:1); in step 1, the equivalent ratio of (the total amount of the o-cresol epoxy resin and the phenolic epoxy resin) to acrylic acid is 1:(0.8 to 1.2).

[0014] Furthermore, in step 1, the amount of antioxidant is 0.5% to 2.0% of (the total amount of o-cresol epoxy resin, phenolic epoxy resin and acrylic acid); the amount of triphenylphosphine is 0.5% to 2.0% of (the total amount of o-cresol epoxy resin, phenolic epoxy resin and acrylic acid); and the amount of inhibitor is 500 to 1000 ppm of (the total amount of o-cresol epoxy resin, phenolic epoxy resin and acrylic acid).

[0015] Furthermore, in step 2, the equivalent ratio of the epoxy acrylate copolymer hybridized with o-cresol epoxy and phenolic epoxy, IPDI and MDI-50 is (1:0.2:0.2) to (1:0.5:0.5).

[0016] Furthermore, in step 3, the equivalent ratio of the multifunctional o-cresol epoxy-phenolic epoxy polyurethane acrylate copolymer to the multifunctional amino compound polycondensation resin is (1:0.1) to (1:1.2).

[0017] Furthermore, the dual-curing acrylic modified epoxy resin CUV-B is prepared by the following steps:

[0018] A dual-curing acrylic modified epoxy resin CUV-B comprises the following raw materials in parts by weight:

[0019] Step 1, weigh the following components by weight: hydroxyethyl methacrylate, hydroxypropyl methacrylate, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, and o-cresol-formaldehyde epoxy resin;

[0020] Step 2: First, fill a four-necked flask with dry air, add hydroxyethyl methacrylate, hydroxypropyl methacrylate, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride and methylhexahydrophthalic anhydride, then add an antioxidant and a polymerization inhibitor, heat to 100-130° C., react for 2-5 hours to perform a ring-opening reaction, then add o-cresol epoxy resin to react with the other end carboxyl group of tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride and methylhexahydrophthalic anhydride after ring opening, the reaction temperature is 120-150° C., the reaction time is 3-5 hours, and after the acid value is measured twice and remains unchanged, an acrylic acid-modified epoxy resin is obtained;

[0021] Step 3: Add the acrylic modified epoxy resin into a four-necked flask and maintain the temperature at 100°C. Then, add the alicyclic epoxy resin and bisphenol A epoxy resin into the four-necked flask in sections to carry out a sequential IPN structure (Sequential IPN) preparation process. After the addition is completed, the viscosity is tested every hour. When there is no change in the viscosity between the two measurements, the dual-curing acrylic modified epoxy resin CUV-B is obtained.

[0022] Furthermore, in the first step, the weight ratio of hydroxyethyl methacrylate, hydroxypropyl methacrylate, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride and o-cresol-formaldehyde epoxy resin is 30-70 parts: 29-80 parts: 50-75 parts: 10-40 parts: 35-55 parts: 60-120 parts.

[0023] Furthermore, in the second step, the amount of the antioxidant is 0.5% to 2.0% of the total amount of hydroxyethyl methacrylate, hydroxypropyl methacrylate, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride and methylhexahydrophthalic anhydride; and the amount of the inhibitor is 500 to 1000 ppm of the total amount of hydroxyethyl methacrylate, hydroxypropyl methacrylate, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride and methylhexahydrophthalic anhydride.

[0024] Furthermore, in step 3, the weight ratio of the acrylic modified epoxy resin, the alicyclic epoxy resin and the bisphenol A epoxy resin is (5:3:2) to (8:1:1).

[0025] In the above technical scheme, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, trimethylolpropane triacrylate, trifunctional acid ester (brand SR9051), tripropylene glycol diacrylate, γ-methacryloxypropyltrimethoxysilane and 3-(2,3-epoxypropoxy)propyltrimethoxysilane are selected as monomer polymers; the above monomer polymers have low bulk viscosity, which can effectively adjust the viscosity of the ink and avoid serious problems such as loss of ink adhesion and ink embrittlement due to excessive monomer amount.

[0026] In the above technical scheme, 2-ethylanthraquinone, photoinitiator 651, photoinitiator TPO and photoinitiator 1173 are selected as photoinitiators. The purpose of combining photoinitiators with multiple characteristics and different wavelengths is to produce a synergistic effect and improve the efficiency and quality of photocuring. Free radical photoinitiators can quickly generate free radicals and promote free radical polymerization reactions, thereby accelerating the curing process, improving the curing efficiency and ink bridging density, and then improving its corrosion resistance, mechanical properties and physical and chemical properties.

[0027] In the above technical scheme, hexafluoroantimonate blocked ammonium salt and trifluorosulfonic acid blocked ammonium salt are selected as cationic thermal initiators. The purpose of combining multiple types of cationic thermal initiators with different structures, different DSC exothermic peaks and different use temperatures is to improve the cationic thermal curing effect and quality of alicyclic epoxy resin and bisphenol A epoxy resin in the IPN structure of the homemade dual-cured acrylic modified epoxy resin CUV-B, accelerate the thermal curing process, improve the thermal curing efficiency and ink bridging density, and enhance the corrosion resistance, mechanical properties and physical and chemical properties of the overall dual-cured ink.

[0028] In the above technical solution, silicon micropowder, talcum powder, barium sulfate, calcium magnesium carbonate and fumed silica are selected as fillers. The above fillers are selected mainly to improve the key properties of ink such as shrinkage resistance, aging resistance, color development, hiding power, thixotropy and glossiness.

[0029] In the above technical solution, pigment green, defoamer and polyether siloxane copolymer are selected as additives. Pigment green is a dyeing raw material, which provides visual effects and recognition, and different dyeing raw materials can be selected according to different recognition colors. Defoamer and polyether siloxane copolymer (leveling wetting agent) are used to adjust the suitability of ink for screen printing.

[0030] Beneficial effects of the present invention:

[0031] The dual-curing modified epoxy resin CUV-A provided by the present invention uses phenolic epoxy resin and o-cresol epoxy resin as the skeleton, and aims to complement the different crosslinking densities, mechanical strengths, insulation properties, corrosion resistance and other properties of different types of epoxy resins, and then grafts with acrylic acid to provide unsaturated double bonds for dual-curing bridging mechanisms of light curing and heat curing. In addition, the epoxy group of the epoxy resin reacts with acrylic acid to generate hydroxyl groups, and the hydroxyl groups are used to graft with various isocyanates and multifunctional amino compound polycondensation resins. The first purpose is to extend the chains of various isocyanates to increase the molecular weight, thereby improving the physical and chemical properties of the resin, and the second purpose is to graft the multifunctional amino compound polycondensation resin to generate imino groups for use in a heat curing mechanism. Therefore, the self-made dual-curing modified epoxy resin CUV-A has basic properties such as dual curing, excellent metal adhesion, low shrinkage, physical and chemical resistance, corrosion resistance, and solder resistance.

[0032] The dual-curing acrylic modified epoxy resin CUV-B provided by the present invention is synthesized by copolymerizing various hydroxy methacrylates, various phthalic anhydrides, o-cresol epoxy, bisphenol A epoxy resin, and alicyclic epoxy resin, and has the advantages of a dual curing mechanism of being photocurable and heat curable with a cationic thermal initiator, metal adhesion, physical and chemical resistance, etc.

[0033] The dual-curing ink provided by the present invention can be widely used in photocurable circuit inks, has the advantages of fast photocuring speed, and the ink after photocuring film formation has good adhesion to the copper foil substrate, and has good electrolytic etching resistance ink circuits, no ink shedding and peeling, and good chemical etching resistance. It is also applied to dual-curing solder mask inks, and has good dual-curing performance, printing performance, adhesion, scratch resistance, chemical resistance, wave soldering thermal shock resistance, laser windowing and other effects. DETAILED DESCRIPTION

[0034] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0035] Example 1

[0036] The raw materials and purchasers used in this embodiment are as follows:

[0037] o-Cresol epoxy resin, purchased from Shengquan, epoxy equivalent: 200-215;

[0038] o-Cresol epoxy resin, purchased from Shengquan, epoxy equivalent: 200-215;

[0039] Acrylic acid was purchased from Shanghai Yongzhengpin;

[0040] Antioxidant BHT, purchased from Jiangsu Ningkangpin;

[0041] Triphenylphosphine (TPH) was purchased from Suzhou Jinyuanpin;

[0042] The inhibitor MEHQ was purchased from Changzhou Shuojinpin;

[0043] IPDI was purchased from Yantai Wanhua;

[0044] MDI-50, purchased from Yantai Wanhua;

[0045] The polycondensation resin of multifunctional amino compound was purchased from Allkins.

[0046] This embodiment provides a dual-curing modified epoxy resin CUV-A, and the preparation steps are as follows:

[0047] Step 1, o-cresol epoxy resin and phenolic epoxy resin are added into a four-necked flask according to a weight ratio of 1:9, filled with dry air, and heated to 100°C. When the o-cresol epoxy resin and the phenolic epoxy resin are in liquid state, the weight ratio is calculated according to the (total amount of o-cresol epoxy resin and phenolic epoxy resin) and acrylic acid according to an equivalent ratio of 1:0.8, and acrylic acid is added; then, according to the total amount of the above raw materials, 0.5% of antioxidant BHT, 0.5% of triphenylphosphine and 500ppm of polymerization inhibitor MEHQ are added into the four-necked flask, and the temperature is slowly raised to 125°C for reaction for 6 hours. After the acid value is determined to be less than 2.0, an epoxy acrylate copolymer hybridized with o-cresol epoxy and phenolic epoxy is obtained;

[0048] Step 2, add the epoxy acrylate copolymer of o-cresol epoxy and phenolic epoxy hybrid into a four-necked flask, maintain 100° C., and then convert the weight ratio according to the equivalent ratio of o-cresol epoxy and phenolic epoxy hybrid epoxy acrylate copolymer: IPDI: MDI-50 of 1:0.2:0.2, add IPDI and MDI-50, maintain 100° C. for reaction for 3 hours, measure NCO every hour for control confirmation, and after measuring NCO% <0.2, obtain a multifunctional o-cresol epoxy-phenolic epoxy polyurethane acrylate copolymer;

[0049] Step 3, put the multifunctional o-cresol epoxy-phenolic epoxy polyurethane acrylate copolymer into a four-necked flask, calculate the hydroxyl equivalent, and calculate the weight ratio with the multifunctional amino compound condensation resin according to the equivalent ratio of 1:0.1, and put the multifunctional amino compound condensation resin into it. Fill with dry air and nitrogen during the process, keep the temperature at 120℃ for 8h, measure the hydroxyl equivalent (OHV) and viscosity every hour during the reaction for control confirmation, and cool down when the OHV reaches the target specification value to obtain the dual-cure modified epoxy resin CUV-A.

[0050] Example 2

[0051] The raw materials and purchasers used in this embodiment are as follows:

[0052] Hydroxyethyl methacrylate, purchased from Anhui Lianhua;

[0053] Hydroxypropyl methacrylate, purchased from Anhui Lianhua;

[0054] Tetrahydrophthalic anhydride, purchased from Jiangsu Haolong;

[0055] Methyltetrahydrophthalic anhydride, purchased from Tiancheng Chemical;

[0056] Methylhexahydrophthalic anhydride, purchased from Jiangsu Taitel;

[0057] o-cresol epoxy resin, purchased from Shengquan, epoxy equivalent 200-215;

[0058] Antioxidant BHT, purchased from Jiangsu Ningkangpin;

[0059] The polymerization inhibitor MEHQ was purchased from Changzhou Shuojinpin.

[0060] This embodiment provides a dual-curing acrylic modified epoxy resin CUV-B, and the preparation steps are as follows:

[0061] Step 1, weigh the following components by weight: 30 parts of hydroxyethyl methacrylate, 29 parts of hydroxypropyl methacrylate, 50 parts of tetrahydrophthalic anhydride, 10 parts of methyltetrahydrophthalic anhydride, 35 parts of methylhexahydrophthalic anhydride, and 60 parts of o-cresol epoxy resin;

[0062] Step 2: First, fill a four-necked flask with dry air, add hydroxyethyl methacrylate, hydroxypropyl methacrylate, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride and methylhexahydrophthalic anhydride, and then add 0.5% of antioxidant BHT and 500ppm of polymerization inhibitor MEHQ in sequence according to the total amount of the above raw materials, heat to 100° C., react for 5 hours to perform a ring-opening reaction, then add o-cresol-formaldehyde epoxy resin to react with the other end carboxyl group of tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride and methylhexahydrophthalic anhydride after ring-opening, the reaction temperature is 120° C., the reaction time is 5 hours, and after the acid value is measured twice and remains unchanged, an acrylic acid-modified epoxy resin is obtained;

[0063] Step 3: Add acrylic modified epoxy resin, alicyclic epoxy resin and bisphenol A epoxy resin according to the weight ratio of 5:3:2 into a four-necked flask and keep it at 100°C. Then add alicyclic epoxy resin and bisphenol A epoxy resin into the four-necked flask in sections to carry out the sequential IPN structure (Sequential IPN) preparation process. After the addition is completed, the viscosity is tested every hour. When there is no change in the two viscosity measurements, the dual-curing acrylic modified epoxy resin CUV-B is obtained.

[0064] Example 3

[0065] This embodiment provides a dual-cure ink that can withstand a new electrolytic etching process. The specific raw materials and usage weight parts are shown in Table 2.

[0066] Example 4

[0067] This embodiment provides a dual-cure ink that can withstand a new electrolytic etching process. The specific raw materials and usage weight parts are shown in Table 2.

[0068] Example 5

[0069] This embodiment provides a dual-cure ink that can withstand a new electrolytic etching process. The specific raw materials and usage weight parts are shown in Table 2.

[0070] 1. The sources of raw materials used in the dual-curing inks resistant to electrolytic etching obtained in Examples 3-5 are shown in Table 1:

[0071] Table 1

[0072]

[0073]

[0074] 2. The specific raw materials and weight proportions of the dual-curing ink obtained in Examples 3-5 and resistant to electrolytic etching are shown in Table 2.

[0075] Table 2

[0076]

[0077]

[0078] 3. Performance test of the dual-curing ink obtained in Example 3-5 that is resistant to the new electrolytic etching process:

[0079] 1. Test process of light-curing circuit ink: ink screen printing on copper foil substrate, light curing energy: 900~1300Mj / cm 2 The electrolytic etching resistance and chemical etching resistance were tested. The test results are shown in Table 3:

[0080] 2. Dual-curing solder mask ink test process: The circuit board after the dual-curing ink obtained in the embodiment is subjected to electrolytic etching resistance and chemical etching resistance, and then the full-plate silk screen solder mask is printed according to the dual-curing ink obtained in the embodiment. The dual-curing conditions are as follows: light curing energy: 900-1300Mj / cm 2 After that, heat curing was performed at 150℃ / 30min, and the basic solder resistance and laser window opening effect were tested. The test results are shown in Table 4:

[0081] Table 3

[0082]

[0083]

[0084] Table 4

[0085]

[0086] From the data in Tables 2-4, it can be seen that the dual-curing ink provided by the present invention that can resist the new electrolytic etching process can be widely used in photocurable circuit inks, and has the advantages of fast photocuring speed, good adhesion to copper foil substrates after photocuring film formation, complete electrolytic etching resistance ink circuits, no ink shedding and peeling, and good chemical etching resistance. It is also applied to dual-curing solder mask inks, and has good dual-curing performance, printing performance, adhesion, scratch resistance, chemical resistance, wave soldering thermal shock resistance, and laser windowing.

[0087] It should be noted that, in this article, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprises" or any other variations thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device.

[0088] 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 dual-cure ink that can withstand a new electrolytic etching process, characterized in that: It includes the following raw materials in parts by weight: 30.0-70.0 parts of dual-cure modified epoxy resin CUV-A, 35.0-65.0 parts of dual-cure acrylic modified epoxy resin CUV-B, 15.0-25.0 parts of dipentaerythritol hexaacrylate, 10.0-20.0 parts of pentaerythritol tetraacrylate, 5.0-15.0 parts of trimethylolpropane triacrylate, 0.5-5.0 parts of trifunctional acid ester, 5.0-15.0 parts of tripropylene glycol diacrylate, 0.1-3.0 parts of γ-methacryloxypropyl trimethoxysilane, 0.1-3.0 parts of 3-(2,3-epoxypropoxy)propyl trimethoxysilane, 1.0-7.0 parts of 2-ethyl anthraquinone, 11.0-7.0 parts of photoinitiator 651, and photoinitiator TPO 1.0-7.0 parts, photoinitiator 11731.0-7.0 parts, hexafluoroantimonic acid blocked ammonium salt 0.1-3.0 parts, trifluorosulfonic acid blocked ammonium salt 0.1-3.0 parts, silica powder 5.0-40.0 parts, talc powder 5.0-40.0 parts, barium sulfate 5.0-40.0 parts, calcium magnesium carbonate 5.0-40.0 parts, fumed silica 0.2-5.0 parts, pigment green 0.5-2.0 parts, defoamer 0.2-2.0 parts, polyether siloxane copolymer 0.2-2.0 parts.

2. A dual-cure ink resistant to electrolytic etching according to claim 1, characterized in that: The dual-cured modified epoxy resin CUV-A is prepared by the following steps: Step 1, o-cresol epoxy resin and phenolic epoxy resin are put into a four-necked flask, filled with dry air, and heated to 100° C. When the o-cresol epoxy resin and phenolic epoxy resin are in liquid state, acrylic acid is added; then antioxidant, triphenylphosphine and polymerization inhibitor are added into the four-necked flask, and the temperature is slowly raised to 125-130° C. for reaction for 3-6 hours. After the acid value is determined to be less than 2.0, an epoxy acrylate copolymer hybridized with o-cresol epoxy and phenolic epoxy is obtained; Step 2, adding the epoxy acrylate copolymer of o-cresol epoxy and phenolic epoxy hybrid into a four-necked flask, maintaining 80-100° C., adding IPDI and MDI-50, maintaining 80-100° C. for reaction for 2-6 hours, measuring NCO every hour for control confirmation, and after measuring NCO% <0.2, obtaining a multifunctional o-cresol epoxy-phenolic epoxy polyurethane acrylate copolymer; Step 3, add the multifunctional o-cresol epoxy-phenolic epoxy polyurethane acrylate copolymer into a four-necked flask, and then add the multifunctional amino compound condensation resin. Fill with dry air and nitrogen during the process, maintain 120-130°C for reaction for 3-8 hours, measure the hydroxyl equivalent and viscosity every hour during the reaction for control confirmation, and cool down when the measured OHV reaches the target specification value to obtain the dual-cure modified epoxy resin CUV-A.

3. A dual-cure ink resistant to electrolytic etching according to claim 2, characterized in that: The weight ratio of o-cresol epoxy resin and phenolic epoxy resin in step 1 is (1:9) to (9:1); the equivalent ratio of (the total amount of o-cresol epoxy resin and phenolic epoxy resin) and acrylic acid in step 1 is 1:(0.8 to 1.2).

4. A dual-cure ink resistant to electrolytic etching according to claim 2, characterized in that: In step 1, the amount of antioxidant is 0.5% to 2.0% of (the total amount of o-cresol epoxy resin, phenolic epoxy resin and acrylic acid); triphenylphosphine is 0.5% to 2.0% of (the total amount of o-cresol epoxy resin, phenolic epoxy resin and acrylic acid); and the inhibitor is 500 to 1000ppm of (the total amount of o-cresol epoxy resin, phenolic epoxy resin and acrylic acid).

5. The dual-cure ink resistant to electrolytic etching according to claim 2, characterized in that: In step 2, the equivalent ratio of the epoxy acrylate copolymer hybridized with o-cresol epoxy and phenolic epoxy, IPDI and MDI-50 is (1:0.2:0.2) to (1:0.5:0.5).

6. A dual-cure ink resistant to electrolytic etching according to claim 2, characterized in that: In step 3, the equivalent ratio of the multifunctional o-cresol epoxy-phenolic epoxy polyurethane acrylate copolymer and the multifunctional amino compound condensation resin is (1:0.1) to (1:1.2).

7. The dual-cure ink resistant to electrolytic etching according to claim 1, characterized in that: The dual-curing acrylic modified epoxy resin CUV-B is prepared by the following steps: Step 1, weigh the following components by weight: hydroxyethyl methacrylate, hydroxypropyl methacrylate, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, and o-cresol-formaldehyde epoxy resin; Step 2: First, fill a four-necked flask with dry air, add hydroxyethyl methacrylate, hydroxypropyl methacrylate, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride and methylhexahydrophthalic anhydride, then add an antioxidant and a polymerization inhibitor, heat to 100-130° C., react for 2-5 hours to perform a ring-opening reaction, then add o-cresol epoxy resin to react with the other end carboxyl group of tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride and methylhexahydrophthalic anhydride after ring opening, the reaction temperature is 120-150° C., the reaction time is 3-5 hours, and after the acid value is measured twice and remains unchanged, an acrylic acid-modified epoxy resin is obtained; Step 3: Add the acrylic modified epoxy resin into a four-necked flask and maintain it at 100°C. Then add the alicyclic epoxy resin and bisphenol A epoxy resin into the four-necked flask in sections to carry out a step-by-step IPN structure preparation process. After the addition is completed, test the viscosity every hour. When there is no change in the two viscosity measurements, the dual-cured acrylic modified epoxy resin CUV-B is obtained.

8. The dual-cure ink resistant to electrolytic etching according to claim 7, characterized in that: In the first step, the weight ratio of hydroxyethyl methacrylate, hydroxypropyl methacrylate, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride and o-cresol-formaldehyde epoxy resin is 30-70 parts: 29-80 parts: 50-75 parts: 10-40 parts: 35-55 parts: 60-120 parts.

9. The dual-cure ink resistant to electrolytic etching according to claim 7, characterized in that: In the second step, the amount of the antioxidant is 0.5% to 2.0% of the total amount of hydroxyethyl methacrylate, hydroxypropyl methacrylate, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride and methylhexahydrophthalic anhydride; the amount of the inhibitor is 500 to 1000 ppm of the total amount of hydroxyethyl methacrylate, hydroxypropyl methacrylate, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride and methylhexahydrophthalic anhydride.

10. The dual-cure ink resistant to electrolytic etching according to claim 7, characterized in that: In step 3, the weight ratio of the acrylic modified epoxy resin, the alicyclic epoxy resin and the bisphenol A epoxy resin is (5:3:2) to (8:1:1).

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