阅读说明：本技术 一种耐腐蚀光固化油墨及其制备工艺 (Corrosion-resistant photocureable ink and preparation process thereof ) 是由 不公告发明人 于 2021-02-02 设计创作，主要内容包括：本发明公开了一种耐腐蚀光固化油墨及其制备工艺,该耐腐蚀光固化油墨包括以下重量份原料：改性酚醛环氧树脂40-60份、双酚A环氧丙烯酸酯80-100份、活性稀释剂5-6份、光引发剂5-7份、改性消泡剂4-6份、纳米锌粉4-6份、着色颜料15-30份、BYK333流平剂1-2份、AKN-2280分散剂1-3份；包括以下步骤制备：步骤S1、混合光固化树脂的制备；步骤S2、添加纳米锌粉和着色颜料搅拌分散,得到耐腐蚀光固化油墨初料；步骤S3、研磨、过滤,得到耐腐蚀光固化油墨；本发明制得的光固化油墨具有较好的耐腐蚀性能和固化性能,涂布到金属制品表面固化后,可有效对金属制品外观进行防护。(The invention discloses corrosion-resistant photo-curing ink and a preparation process thereof, wherein the corrosion-resistant photo-curing ink comprises the following raw materials in parts by weight: 40-60 parts of modified phenolic epoxy resin, 80-100 parts of bisphenol A epoxy acrylate, 5-6 parts of active diluent, 5-7 parts of photoinitiator, 4-6 parts of modified defoaming agent, 4-6 parts of nano zinc powder, 15-30 parts of coloring pigment, 1-2 parts of BYK333 leveling agent and 1-3 parts of AKN-2280 dispersant; the preparation method comprises the following steps: step S1, preparing mixed light-cured resin; step S2, adding nano zinc powder and coloring pigment, stirring and dispersing to obtain a corrosion-resistant photo-curing ink primary material; step S3, grinding and filtering to obtain the corrosion-resistant photo-curing ink; the photo-curing ink prepared by the invention has better corrosion resistance and curing performance, and can effectively protect the appearance of a metal product after being coated on the surface of the metal product and cured.)

1. The corrosion-resistant photo-curing printing ink is characterized in that: the feed comprises the following raw materials in parts by weight: 40-60 parts of modified phenolic epoxy resin, 80-100 parts of bisphenol A epoxy acrylate, 5-6 parts of active diluent, 5-7 parts of photoinitiator, 4-6 parts of modified defoaming agent, 4-6 parts of nano zinc powder, 15-30 parts of coloring pigment, 1-2 parts of BYK333 leveling agent and 1-3 parts of AKN-2280 dispersant;

the corrosion-resistant photo-curing printing ink is prepared by the following steps:

step S1: adding modified novolac epoxy resin, bisphenol A epoxy acrylate, a photoinitiator, a modified defoaming agent, a BYK333 leveling agent and an AKN-2280 dispersing agent in parts by weight into a mixing tank, raising the temperature to 40-45 ℃, and then uniformly stirring and dispersing at the rotating speed of 2500 plus 3000r/min for 1-2h to obtain mixed photocuring resin;

step S2: adding nano zinc oxide powder and coloring pigment in the formula weight parts into the mixed photo-curing resin, and uniformly stirring and dispersing at the rotating speed of 2500-;

step S3: and adding the corrosion-resistant photo-curing ink primary material into a three-roll grinder, grinding for 4-6 times until the fineness of the ink is less than 5 mu m, and filtering to obtain the corrosion-resistant photo-curing ink.

2. The corrosion-resistant photocurable ink according to claim 1, wherein: the modified novolac epoxy resin is prepared by the following method:

step A1: placing phenol and tung oil in a four-neck flask according to the mass ratio of 10:1, placing the four-neck flask in an oil bath, stirring at a constant speed at the rotation speed of 200-400r/min, simultaneously raising the temperature to 45-55 ℃ to melt the phenol in the tung oil, adding oxalic acid which is 0.75 percent of the total weight of reactants in the four-neck flask, continuously raising the temperature to 108-112 ℃, after reacting for 3-4h, stopping heating, stirring under the condition of unchanged rotation speed, and naturally cooling to room temperature to obtain a product a;

step A2: placing the product a and formaldehyde with the mass fraction of 40% in a four-neck flask, placing the four-neck flask in an oil bath pot, stirring at a constant speed at the rotation speed of 200 plus 400r/min, heating the oil bath to 80 ℃, measuring, adjusting the pH value of a reactant to 1-1.5 by using oxalic acid, stopping heating after reacting for 5.5 hours, keeping stirring and cooling to room temperature, washing the reactant to be neutral by using deionized water, standing and separating, and taking a lower-layer oil phase to obtain a product b;

step A3: adding the product b and epoxy chloropropane into a four-neck flask according to the volume ratio of 1:7, placing the four-neck flask into an oil bath, heating the four-neck flask to 70 ℃ in an oil bath, dropwise adding a sodium hydroxide solution with the mass fraction of 40% into the four-neck flask, wherein the volume ratio of the sodium hydroxide solution to the product b is 2:1, heating the solution to 75 ℃ for 1-2h, heating the solution to 85 ℃ after dropwise adding, keeping the temperature, stopping heating when white sodium chloride crystals are separated out, stirring the solution at the rotating speed of 400r/min for cooling to room temperature, washing the solution with deionized water, standing the solution for layering, removing the sodium chloride and the sodium chloride solution, and then carrying out reduced pressure distillation at the vacuum degree of 0.1MPa and the temperature of 120 ℃ to recover the epoxy chloropropane, thus obtaining the modified phenolic epoxy resin.

3. The corrosion-resistant photocurable ink according to claim 1, wherein: the modified defoaming agent is prepared by the following method:

step B1: adding octamethylcyclotetrasiloxane and tetramethyldihydrosiloxane into a four-mouth flask, uniformly stirring and mixing for 30min under the condition that the rotation speed is 200 plus materials and the speed is 300r/min, then adding concentrated sulfuric acid accounting for 98% of the total weight of the substances in the four-mouth flask, keeping the rotation speed to continue stirring, heating the temperature to 30-40 ℃, preserving the temperature for 4-5h, transferring a reaction product into a separating funnel after preserving the temperature, neutralizing the sulfuric acid by using a sodium carbonate solution accounting for 45% of the mass fraction until the sulfuric acid is neutral, washing for 2-3 times by using deionized water, removing a water layer, heating an oil layer to 180 plus materials and 200 ℃, and removing impurities in vacuum to obtain light yellow oil liquid;

step B2: adding allyl glycidyl ether and light yellow oil into a four-neck flask, uniformly stirring and mixing at a constant speed under the condition that the rotating speed is 200-95 ℃, adding chloroplatinic acid accounting for 0.45 percent of the total weight of substances in the four-neck flask, heating to 100-95 ℃, keeping the rotating speed unchanged, preserving the temperature for 5-6h, and removing low-boiling-point substances and unreacted reactants under reduced pressure to obtain viscous liquid;

step B3: adding dimethyl silicone oil and fumed silica into a four-mouth flask, uniformly stirring and mixing at a constant speed under the condition that the rotating speed is 800-class sand 1000r/min, raising the temperature to 180-class sand 220 ℃, keeping the rotating speed for stirring and preserving the heat for 3-6h, then cooling to room temperature to obtain an organic silicon paste, uniformly stirring and mixing the organic silicon paste, an emulsifier, a viscous liquid and polyvinyl alcohol at the rotating speed of 2000-class sand 3000r/min to obtain a mixed emulsion, adding deionized water accounting for 35% of the total mass of the mixed emulsion into the mixed emulsion, and uniformly stirring and mixing at the rotating speed of 1000-class sand 1500r/min to obtain the modified defoaming agent.

4. The corrosion-resistant photo-curable ink according to claim 3, wherein: the mass ratio of the octamethylcyclotetrasiloxane to the tetramethyldihydrosiloxane in step B1 is 49: 1; in the step B2, the mol ratio of the allyl glycidyl ether to the light yellow oil liquid is 2: 1; in the step B3, the mass ratio of the dimethyl silicone oil to the fumed silica is 19: 1; the weight ratio of the organic silicon paste to the emulsifier to the viscous liquid to the polyvinyl alcohol is 2:1:0.5: 0.1.

5. The corrosion-resistant photo-curable ink according to claim 3, wherein: the emulsifier is formed by mixing span 60 and tween 60 according to the mass ratio of 2-3: 1.

6. The corrosion-resistant photocurable ink according to claim 1, wherein: the reactive diluent is any one of trimethylolpropane triacrylate or biquaternary tetraalcohol hexaacrylate.

7. The corrosion-resistant photocurable ink according to claim 1, wherein: the photoinitiator is any one of 1-hydroxycyclohexyl benzyl, 2, 4, 6-trimethylbenzoyl diphenyl phosphine oxide, bis 2, 6-difluoro-3-pyrrolyl phenyl titanocene, 2, 4, 6-trimethylbenzoyl phosphine oxide and 2-hydroxy-2-methyl-1-phenyl-1-acetone.

8. The corrosion-resistant photocurable ink according to claim 1, wherein: the coloring pigment is any one of carbon black, titanium dioxide, phthalocyanine blue, gamboge and alizarin red.

9. The process for preparing a corrosion-resistant photo-curable ink according to claim 1, wherein: the method specifically comprises the following steps:

step S1: adding modified novolac epoxy resin, bisphenol A epoxy acrylate, a photoinitiator, a modified defoaming agent, a BYK333 leveling agent and an AKN-2280 dispersing agent in parts by weight into a mixing tank, raising the temperature to 40-45 ℃, and then uniformly stirring and dispersing at the rotating speed of 2500 plus 3000r/min for 1-2h to obtain mixed photocuring resin;

step S2: adding nano zinc oxide powder and coloring pigment in the formula weight parts into the mixed photo-curing resin, and uniformly stirring and dispersing at the rotating speed of 2500-;

step S3: and adding the corrosion-resistant photo-curing ink primary material into a three-roll grinder, grinding for 4-6 times until the fineness of the ink is less than 5 mu m, and filtering to obtain the corrosion-resistant photo-curing ink.

Technical Field

The invention belongs to the technical field of photo-curing ink, and particularly relates to corrosion-resistant photo-curing ink and a preparation process thereof.

Background

The photo-curing ink is ink which can be formed into a film and dried under the irradiation of ultraviolet light, and has good mechanical property and chemical property after the ink is formed into the film. The metal mobile phone cover is widely used in industries such as metal mobile phone covers, digital cameras, MP4, notebook covers and the like. At present, UV printing ink becomes a mature printing ink technology, and the pollutant emission is almost zero. Besides no solvent, the UV printing ink has the advantages of difficult plate pasting, clear dot, bright and bright ink color, excellent chemical resistance, use amount saving and the like, and has wide application field.

UV inks have the property of selective absorption of UV light. Drying is affected by the total energy of the light radiated by the UV light source and the energy distribution of the light of different wavelengths. Under the irradiation of UV light, the UV ink photopolymerization initiator absorbs photons with certain wavelengths, and is excited to an excited state to form free radicals or ions. The polymerized prepolymer and the photosensitive monomers and polymers are then brought into an excited state by intermolecular energy transfer, resulting in a charge transfer complex. These complex particles are continuously cross-linked and polymerized to be cured into a film.

The stainless steel craft product is often collided, scratched, deformed and the like in the process of conveying and packaging, and the corrosion resistance of the surface of the stainless steel craft product is reduced due to the corrosion, denaturation and other problems of the stainless steel when the stainless steel craft product is placed and displayed for a long time, so that corroded spots appear, the attractiveness of the stainless steel craft product is affected, and therefore an anti-oxidation and anti-corrosion protective layer is usually coated on the surface of metal, and the appearance performance of the stainless steel craft product is maintained as far as possible. Therefore, a photo-curing ink with good curing performance and corrosion resistance needs to be prepared for surface protection of metal craft products.

Disclosure of Invention

The invention aims to provide corrosion-resistant photo-curing ink and a preparation process thereof.

The technical problems to be solved by the invention are as follows: how to improve the corrosion resistance and the curing performance of the photo-curing printing ink so as to realize the appearance protection of metal products.

The purpose of the invention can be realized by the following technical scheme:

the corrosion-resistant photo-curing printing ink comprises the following raw materials in parts by weight: 40-60 parts of modified phenolic epoxy resin, 80-100 parts of bisphenol A epoxy acrylate, 5-6 parts of active diluent, 5-7 parts of photoinitiator, 4-6 parts of modified defoaming agent, 4-6 parts of nano zinc powder, 15-30 parts of coloring pigment, 1-2 parts of BYK333 leveling agent and 1-3 parts of AKN-2280 dispersant;

the corrosion-resistant photo-curing printing ink is prepared by the following steps:

step S1: adding modified novolac epoxy resin, bisphenol A epoxy acrylate, a photoinitiator, a modified defoaming agent, a BYK333 leveling agent and an AKN-2280 dispersing agent in parts by weight into a mixing tank, raising the temperature to 40-45 ℃, and then uniformly stirring and dispersing at the rotating speed of 2500 plus 3000r/min for 1-2h to obtain mixed photocuring resin;

step S2: adding nano zinc oxide powder and coloring pigment in the formula weight parts into the mixed photo-curing resin, and uniformly stirring and dispersing at the rotating speed of 2500-;

step S3: and adding the corrosion-resistant photo-curing ink primary material into a three-roll grinder, grinding for 4-6 times until the fineness of the ink is less than 5 mu m, and filtering to obtain the corrosion-resistant photo-curing ink.

Further, the modified novolac epoxy resin is prepared by the following method:

step A1: placing phenol and tung oil in a four-neck flask according to the mass ratio of 10:1, placing the four-neck flask in an oil bath, stirring at a constant speed at the rotation speed of 200-400r/min, simultaneously raising the temperature to 45-55 ℃ to melt the phenol in the tung oil, adding oxalic acid which is 0.75 percent of the total weight of reactants in the four-neck flask, continuously raising the temperature to 108-112 ℃, after reacting for 3-4h, stopping heating, stirring under the condition of unchanged rotation speed, and naturally cooling to room temperature to obtain a product a;

step A2: placing the product a and formaldehyde with the mass fraction of 40% in a four-neck flask, placing the four-neck flask in an oil bath pot, stirring at a constant speed at the rotation speed of 200 plus 400r/min, heating the oil bath to 80 ℃, measuring, adjusting the pH value of a reactant to 1-1.5 by using oxalic acid, stopping heating after reacting for 5.5 hours, keeping stirring and cooling to room temperature, washing the reactant to be neutral by using deionized water, standing and separating, and taking a lower-layer oil phase to obtain a product b;

step A3: adding the product b and epoxy chloropropane into a four-neck flask according to the volume ratio of 1:7, placing the four-neck flask into an oil bath, heating the four-neck flask to 70 ℃ in an oil bath, dropwise adding a sodium hydroxide solution with the mass fraction of 40% into the four-neck flask, wherein the volume ratio of the sodium hydroxide solution to the product b is 2:1, heating the solution to 75 ℃ for 1-2h, heating the solution to 85 ℃ after dropwise adding, keeping the temperature, stopping heating when white sodium chloride crystals are separated out, stirring the solution at the rotating speed of 400r/min for cooling to room temperature, washing the solution with deionized water, standing the solution for layering, removing the sodium chloride and the sodium chloride solution, and then carrying out reduced pressure distillation at the vacuum degree of 0.1MPa and the temperature of 120 ℃ to recover the epoxy chloropropane, thus obtaining the modified phenolic epoxy resin.

Further, the modified defoaming agent is prepared by the following method:

step B1: adding octamethylcyclotetrasiloxane and tetramethyldihydrosiloxane into a four-mouth flask, uniformly stirring and mixing for 30min under the condition that the rotation speed is 200 plus materials and the speed is 300r/min, then adding concentrated sulfuric acid accounting for 98% of the total weight of the substances in the four-mouth flask, keeping the rotation speed to continue stirring, heating the temperature to 30-40 ℃, preserving the temperature for 4-5h, transferring a reaction product into a separating funnel after preserving the temperature, neutralizing the sulfuric acid by using a sodium carbonate solution accounting for 45% of the mass fraction until the sulfuric acid is neutral, washing for 2-3 times by using deionized water, removing a water layer, heating an oil layer to 180 plus materials and 200 ℃, and removing impurities in vacuum to obtain light yellow oil liquid;

step B2: adding allyl glycidyl ether and light yellow oil into a four-neck flask, uniformly stirring and mixing at a constant speed under the condition that the rotating speed is 200-95 ℃, adding chloroplatinic acid accounting for 0.45 percent of the total weight of substances in the four-neck flask, heating to 100-95 ℃, keeping the rotating speed unchanged, preserving the temperature for 5-6h, and removing low-boiling-point substances and unreacted reactants under reduced pressure to obtain viscous liquid;

step B3: adding dimethyl silicone oil and fumed silica into a four-mouth flask, uniformly stirring and mixing at a constant speed under the condition that the rotating speed is 800-class sand 1000r/min, raising the temperature to 180-class sand 220 ℃, keeping the rotating speed for stirring and preserving the heat for 3-6h, then cooling to room temperature to obtain an organic silicon paste, uniformly stirring and mixing the organic silicon paste, an emulsifier, a viscous liquid and polyvinyl alcohol at the rotating speed of 2000-class sand 3000r/min to obtain a mixed emulsion, adding deionized water accounting for 35% of the total mass of the mixed emulsion into the mixed emulsion, and uniformly stirring and mixing at the rotating speed of 1000-class sand 1500r/min to obtain the modified defoaming agent.

Further, the mass ratio of the octamethylcyclotetrasiloxane to the tetramethyldihydrosiloxane in step B1 is 49: 1; in the step B2, the mol ratio of the allyl glycidyl ether to the light yellow oil liquid is 2: 1; in the step B3, the mass ratio of the dimethyl silicone oil to the fumed silica is 19: 1; the weight ratio of the organic silicon paste to the emulsifier to the viscous liquid to the polyvinyl alcohol is 2:1:0.5: 0.1.

Further, the emulsifier is formed by mixing span 60 and tween 60 according to the mass ratio of 2-3: 1.

Further, the reactive diluent is any one of trimethylolpropane triacrylate or di-quaternary tetraalcohol hexaacrylate.

Further, the photoinitiator is any one of 1-hydroxycyclohexyl benzyl, 2, 4, 6-trimethylbenzoyl diphenyl phosphine oxide, bis 2, 6-difluoro-3-pyrrol-phenyl titanocene, 2, 4, 6-trimethylbenzoyl phosphine oxide and 2-hydroxy-2-methyl-1-phenyl-1-acetone.

Further, the coloring pigment is any one of carbon black, titanium dioxide, phthalocyanine blue, gamboge and alizarin red.

A preparation process of corrosion-resistant photo-curing ink specifically comprises the following steps:

step S1: adding modified novolac epoxy resin, bisphenol A epoxy acrylate, a photoinitiator, a modified defoaming agent, a BYK333 leveling agent and an AKN-2280 dispersing agent in parts by weight into a mixing tank, raising the temperature to 40-45 ℃, and then uniformly stirring and dispersing at the rotating speed of 2500 plus 3000r/min for 1-2h to obtain mixed photocuring resin;

step S2: adding nano zinc oxide powder and coloring pigment in the formula weight parts into the mixed photo-curing resin, and uniformly stirring and dispersing at the rotating speed of 2500-;

step S3: and adding the corrosion-resistant photo-curing ink primary material into a three-roll grinder, grinding for 4-6 times until the fineness of the ink is less than 5 mu m, and filtering to obtain the corrosion-resistant photo-curing ink.

The invention has the beneficial effects that:

the zinc powder is used as the filler, so that on one hand, the electrochemical protection effect can be achieved; on the other hand, after zinc powder in the ink coating is oxidized as an anode sacrificial material, the formed oxide can fill structural gaps formed by organic matters in the coating, so that external water and oxygen are blocked, a corrosive medium is shielded, a metal matrix is protected from being corroded, and the corrosion resistance of the photocuring ink is improved.

The invention carries out substitution reaction on tung oil and phenol under the acidic catalysis condition to obtain a product a, then carries out polymerization reaction on the product a and formaldehyde under the acidic catalysis condition to obtain a product b, and finally carries out ring opening and ring closing reaction on the product b and epoxy chloropropane to obtain the modified novolac epoxy resin, the defects of large brittleness, poor impact resistance and poor corrosion resistance of the novolac epoxy resin are overcome by utilizing the characteristic that tung oil conjugated double bonds have larger activity, the product b and the epoxy chloropropane carry out the ring opening and ring closing reaction, a large amount of epoxy groups are introduced into the modified novolac epoxy resin, the increase of the concentration of the epoxy groups is beneficial to accelerating the photocuring speed and simultaneously showing the post-curing phenomenon, and after an ink coating film is not irradiated by ultraviolet light, cation active centers which cause resin polymerization in an ink system can be generated again when the reaction at the chain ends, continuing to initiate the polymerization of the unreacted resin, namely after the ultraviolet light source is removed, continuing to polymerize the coating system until the coating system is completely dried; the post-curing of the resin can effectively solve the influence of the addition of the nano zinc powder on the light transmittance of the resin and effectively improve the curing performance of the ink;

according to the invention, the polyether chain segment is introduced to the organic silicon chain segment for modification to obtain the modified defoaming agent, the modified defoaming agent is mixed with the printing ink raw material to effectively inhibit the generation of foam in the printing ink and improve the dispersibility of the printing ink raw material components, and meanwhile, due to the introduction of the polyether chain segment, the formed polyether compound can effectively improve the strong alkalinity resistance and chemical inertia resistance of the photo-curing printing ink and improve the stability of the photo-protecting printing ink.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

The corrosion-resistant photo-curing printing ink comprises the following raw materials in parts by weight: 40 parts of modified phenolic epoxy resin, 80 parts of bisphenol A epoxy acrylate, 5 parts of active diluent, 5 parts of photoinitiator, 4 parts of modified defoaming agent, 4 parts of nano zinc powder, 15 parts of coloring pigment, 1 part of BYK333 leveling agent and 1 part of AKN-2280 dispersant;

the corrosion-resistant photo-curing printing ink is prepared by the following steps:

step S1: adding modified novolac epoxy resin, bisphenol A epoxy acrylate, a photoinitiator, a modified defoaming agent, a BYK333 leveling agent and an AKN-2280 dispersing agent in parts by weight into a mixing tank, raising the temperature to 40 ℃, and uniformly stirring and dispersing at a rotating speed of 2500r/min for 1h to obtain mixed photocuring resin;

step S2: adding nano zinc oxide powder and coloring pigment in the formula weight parts into the mixed photo-curing resin, and uniformly stirring and dispersing for 40min at a rotating speed of 2500r/min to obtain a corrosion-resistant photo-curing ink primary material;

step S3: and adding the corrosion-resistant photo-curing ink primary material into a three-roll grinder, grinding for 4 times until the fineness of the ink is 4 mu m, and filtering to obtain the corrosion-resistant photo-curing ink.

The modified novolac epoxy resin is prepared by the following method:

step A1: placing phenol and tung oil in a four-neck flask according to the mass ratio of 10:1, placing the four-neck flask in an oil bath pot, stirring at a constant speed at a rotation speed of 200r/min, simultaneously raising the temperature to 45 ℃ to melt the phenol in the tung oil, adding oxalic acid which is 0.75 percent of the total weight of reactants in the four-neck flask, continuously raising the temperature to 108 ℃, stopping heating after reacting for 3 hours, stirring at a constant rotation speed, and naturally cooling to room temperature to obtain a product a;

step A2: placing the product a and 40% by mass of formaldehyde into a four-neck flask, placing the four-neck flask into an oil bath pot, stirring at a constant speed of 200r/min, heating the four-neck flask to 80 ℃, measuring, adjusting the pH value of a reactant to 1 with oxalic acid, reacting for 5.5 hours, stopping heating, keeping stirring and cooling to room temperature, washing the reactant to be neutral with deionized water, standing and separating, and taking a lower-layer oil phase to obtain a product b;

step A3: adding the product b and epoxy chloropropane into a four-neck flask according to the volume ratio of 1:7, placing the four-neck flask into an oil bath, heating the four-neck flask to 70 ℃ in an oil bath, dropwise adding a sodium hydroxide solution with the mass fraction of 40% into the four-neck flask, wherein the volume ratio of the sodium hydroxide solution to the product b is 2:1, heating the solution to 75 ℃ for 1h, after dropwise adding, heating the solution to 85 ℃ for heat preservation, stopping heating when white sodium chloride crystals are separated out, stirring the solution at the rotating speed of 200r/min, cooling the solution to room temperature, washing the solution with deionized water, standing the solution for layering, removing the sodium chloride and the sodium chloride solution, and then carrying out reduced pressure distillation and epoxy chloropropane recovery under the conditions that the vacuum degree is 0.1MPa and the temperature is 120 ℃, thus obtaining the modified.

The modified defoaming agent is prepared by the following method:

step B1: adding octamethylcyclotetrasiloxane and tetramethyldihydrosiloxane into a four-mouth flask, uniformly stirring and mixing for 30min at a constant speed under the condition of a rotation speed of 200r/min, then adding concentrated sulfuric acid accounting for 2.5% of the total weight of substances in the four-mouth flask, keeping the mass fraction of the concentrated sulfuric acid at 98%, continuously stirring at the rotation speed, heating to 30 ℃, preserving heat for 4h, transferring a reaction product into a separating funnel after preserving heat, neutralizing the sulfuric acid with a sodium carbonate solution accounting for 45% of the mass fraction until the sulfuric acid is neutral, washing for 2 times with deionized water, removing a water layer, heating an oil layer to 180 ℃, and removing impurities in vacuum to obtain a light yellow oil liquid;

step B2: adding allyl glycidyl ether and light yellow oil into a four-neck flask, uniformly stirring and mixing at a constant speed under the condition that the rotating speed is 200r/min, raising the temperature to 85 ℃, adding chloroplatinic acid accounting for 0.45 percent of the total weight of substances in the four-neck flask, heating to 100 ℃, keeping the rotating speed unchanged, preserving the temperature for 5 hours, and removing low-boiling-point substances and unreacted reactants under reduced pressure to obtain viscous liquid;

step B3: adding dimethyl silicone oil and fumed silica into a four-neck flask, uniformly stirring and mixing at a constant speed under the condition that the rotating speed is 800r/min, raising the temperature to 180 ℃, keeping the rotating speed for stirring and keeping the temperature for 3 hours, then cooling to room temperature to obtain an organic silicon paste, uniformly stirring and mixing the organic silicon paste, an emulsifier, a viscous liquid and polyvinyl alcohol at the rotating speed of 2000r/min to obtain a mixed emulsion, adding deionized water accounting for 35 percent of the total mass of the mixed emulsion into the mixed emulsion, and uniformly stirring and mixing at the rotating speed of 1000r/min to obtain the modified defoaming agent.

The mass ratio of the octamethylcyclotetrasiloxane to the tetramethyldihydrosiloxane in step B1 is 49: 1; in the step B2, the mol ratio of the allyl glycidyl ether to the light yellow oil liquid is 2: 1; in the step B3, the mass ratio of the dimethyl silicone oil to the fumed silica is 19: 1; the weight ratio of the organic silicon paste to the emulsifier to the viscous liquid to the polyvinyl alcohol is 2:1:0.5: 0.1.

The emulsifier is formed by mixing span 60 and tween 60 according to the mass ratio of 2: 1.

The active diluent is trimethylolpropane triacrylate.

The photoinitiator is 2, 4, 6-trimethylbenzoyl diphenyl phosphine oxide.

The coloring pigment is titanium dioxide.

Example 2

The corrosion-resistant photo-curing printing ink comprises the following raw materials in parts by weight: 50 parts of modified phenolic epoxy resin, 90 parts of bisphenol A epoxy acrylate, 6 parts of active diluent, 6 parts of photoinitiator, 5 parts of modified defoamer, 5 parts of nano zinc powder, 22 parts of coloring pigment, 2 parts of BYK333 leveling agent and 2 parts of AKN-2280 dispersant;

the corrosion-resistant photo-curing printing ink is prepared by the following steps:

step S1: adding modified novolac epoxy resin, bisphenol A epoxy acrylate, a photoinitiator, a modified defoaming agent, a BYK333 leveling agent and an AKN-2280 dispersing agent in parts by weight into a mixing tank, raising the temperature to 40 ℃, and uniformly stirring and dispersing at a rotating speed of 2800r/min for 1h to obtain mixed photocuring resin;

step S2: adding nano zinc oxide powder and coloring pigment in parts by weight into the mixed photo-curing resin, and uniformly stirring and dispersing for 50min at the rotating speed of 2800r/min to obtain a corrosion-resistant photo-curing ink primary material;

step S3: and adding the corrosion-resistant photo-curing ink primary material into a three-roll grinder, grinding for 5 times until the fineness of the ink is 4 mu m, and filtering to obtain the corrosion-resistant photo-curing ink.

The modified novolac epoxy resin is prepared by the following method:

step A1: placing phenol and tung oil in a four-neck flask according to the mass ratio of 10:1, placing the four-neck flask in an oil bath pot, stirring at a constant speed of 300r/min, simultaneously raising the temperature to 50 ℃ to melt the phenol in the tung oil, adding oxalic acid which is 0.75 percent of the total weight of reactants in the four-neck flask, continuously raising the temperature to 110 ℃, stopping heating after reacting for 3 hours, stirring under the condition of constant rotation speed, and naturally cooling to room temperature to obtain a product a;

step A2: placing the product a and formaldehyde with the mass fraction of 40% in a four-neck flask, placing the four-neck flask in an oil bath pot, stirring at a constant speed of 300r/min, heating the four-neck flask to 80 ℃, measuring, adjusting the pH value of a reactant to 1.5 by oxalic acid, reacting for 5.5 hours, stopping heating, keeping stirring and cooling to room temperature, washing the reactant to be neutral by deionized water, standing for liquid separation, and taking a lower-layer oil phase to obtain a product b;

step A3: adding the product b and epoxy chloropropane into a four-neck flask according to the volume ratio of 1:7, placing the four-neck flask into an oil bath, heating the four-neck flask to 70 ℃ in an oil bath, dropwise adding a sodium hydroxide solution with the mass fraction of 40% into the four-neck flask, wherein the volume ratio of the sodium hydroxide solution to the product b is 2:1, the dropwise adding time is 1.5h, simultaneously heating the solution to 75 ℃, after the dropwise adding is completed, heating the solution to 85 ℃ for heat preservation, stopping heating when white sodium chloride crystals are separated out, stirring the solution at the rotating speed of 300r/min, cooling the solution to room temperature, washing the solution with deionized water, standing the solution for layering, removing the sodium chloride and the sodium chloride solution, and then carrying out reduced pressure distillation at the vacuum degree of 0.1MPa and the temperature of 120 ℃ to recover the epoxy.

The modified defoaming agent is prepared by the following method:

step B1: adding octamethylcyclotetrasiloxane and tetramethyldihydrosiloxane into a four-mouth flask, uniformly stirring and mixing for 30min at a rotation speed of 250r/min, then adding concentrated sulfuric acid accounting for 98% of the total weight of substances in the four-mouth flask, keeping the rotation speed to continue stirring, heating to 35 ℃, preserving heat for 4.5h, transferring a reaction product into a separating funnel after preserving heat, neutralizing the sulfuric acid with a sodium carbonate solution accounting for 45% of the mass fraction until the sulfuric acid is neutral, washing for 3 times with deionized water, removing a water layer, heating an oil layer to 190 ℃, and removing impurities in vacuum to obtain light yellow oil;

step B2: adding allyl glycidyl ether and light yellow oil into a four-neck flask, uniformly stirring and mixing at a constant speed under the condition that the rotating speed is 300r/min, raising the temperature to 90 ℃, adding chloroplatinic acid accounting for 0.45 percent of the total weight of substances in the four-neck flask, heating to 105 ℃, keeping the rotating speed unchanged, preserving the temperature for 5.5 hours, and removing low-boiling-point substances and unreacted reactants under reduced pressure to obtain viscous liquid;

step B3: adding dimethyl silicone oil and fumed silica into a four-neck flask, uniformly stirring and mixing at a constant speed under the condition that the rotating speed is 900r/min, raising the temperature to 200 ℃, keeping the rotating speed for stirring and keeping the temperature for 4 hours, then cooling to room temperature to obtain an organic silicon paste, uniformly stirring and mixing the organic silicon paste, an emulsifying agent, a viscous liquid and polyvinyl alcohol at the rotating speed of 2500r/min to obtain a mixed emulsion, adding deionized water accounting for 35% of the total mass of the mixed emulsion into the mixed emulsion, and uniformly stirring and mixing at the rotating speed of 1200r/min to obtain the modified defoaming agent.

The mass ratio of the octamethylcyclotetrasiloxane to the tetramethyldihydrosiloxane in step B1 is 49: 1; in the step B2, the mol ratio of the allyl glycidyl ether to the light yellow oil liquid is 2: 1; in the step B3, the mass ratio of the dimethyl silicone oil to the fumed silica is 19: 1; the weight ratio of the organic silicon paste to the emulsifier to the viscous liquid to the polyvinyl alcohol is 2:1:0.5: 0.1.

The emulsifier is formed by mixing span 60 and tween 60 according to the mass ratio of 2: 1.

The active diluent is trimethylolpropane triacrylate.

The photoinitiator is bis 2, 6-difluoro-3-pyrrolylphenyl titanocene.

The coloring pigment is carbon black.

Example 3

The corrosion-resistant photo-curing printing ink comprises the following raw materials in parts by weight: 60 parts of modified phenolic epoxy resin, 100 parts of bisphenol A epoxy acrylate, 6 parts of active diluent, 7 parts of photoinitiator, 6 parts of modified defoamer, 6 parts of nano zinc powder, 30 parts of coloring pigment, 2 parts of BYK333 leveling agent and 3 parts of AKN-2280 dispersant;

the corrosion-resistant photo-curing printing ink is prepared by the following steps:

step S1: adding modified novolac epoxy resin, bisphenol A epoxy acrylate, a photoinitiator, a modified defoaming agent, a BYK333 leveling agent and an AKN-2280 dispersing agent in parts by weight into a mixing tank, raising the temperature to 45 ℃, and uniformly stirring and dispersing at a rotating speed of 3000r/min for 2 hours to obtain mixed photocuring resin;

step S2: adding nano zinc oxide powder and coloring pigment in the formula weight parts into the mixed photo-curing resin, and uniformly stirring and dispersing for 60min at a rotating speed of 3000r/min to obtain a corrosion-resistant photo-curing ink primary material;

step S3: and adding the corrosion-resistant photo-curing ink primary material into a three-roll grinder, grinding for 6 times until the fineness of the ink is 3 mu m, and filtering to obtain the corrosion-resistant photo-curing ink.

The modified novolac epoxy resin is prepared by the following method:

step A1: placing phenol and tung oil in a four-neck flask according to the mass ratio of 10:1, placing the four-neck flask in an oil bath pot, stirring at a constant speed of 400r/min, simultaneously raising the temperature to 55 ℃ to melt the phenol in the tung oil, adding oxalic acid which is 0.75 percent of the total weight of reactants in the four-neck flask, continuously raising the temperature to 112 ℃, reacting for 4 hours, stopping heating, stirring under the condition of constant rotation speed, and naturally cooling to room temperature to obtain a product a;

step A2: placing the product a and formaldehyde with the mass fraction of 40% in a four-neck flask, placing the four-neck flask in an oil bath pot, stirring at a constant speed of 400r/min, heating the four-neck flask to 80 ℃, measuring, adjusting the pH value of a reactant to 1.5 by oxalic acid, reacting for 5.5 hours, stopping heating, keeping stirring and cooling to room temperature, washing the reactant to be neutral by deionized water, standing for liquid separation, and taking a lower-layer oil phase to obtain a product b;

step A3: adding the product b and epoxy chloropropane into a four-neck flask according to the volume ratio of 1:7, placing the four-neck flask into an oil bath, heating the four-neck flask to 70 ℃ in an oil bath, dropwise adding a sodium hydroxide solution with the mass fraction of 40% into the four-neck flask, wherein the volume ratio of the sodium hydroxide solution to the product b is 2:1, heating the solution to 75 ℃ at the same time for 2h, after dropwise adding, heating the solution to 85 ℃ for heat preservation, stopping heating when white sodium chloride crystals are separated out, stirring the solution at the rotating speed of 400r/min and cooling the solution to room temperature, washing the solution with deionized water, standing the solution for layering, removing the sodium chloride and the sodium chloride solution, and then carrying out reduced pressure distillation and epoxy chloropropane recovery under the conditions that the vacuum degree is 0.1MPa and the temperature is 120 ℃.

The modified defoaming agent is prepared by the following method:

step B1: adding octamethylcyclotetrasiloxane and tetramethyldihydrosiloxane into a four-mouth flask, uniformly stirring and mixing for 30min at a rotating speed of 300r/min, then adding concentrated sulfuric acid accounting for 98% of the total weight of substances in the four-mouth flask, keeping the rotating speed to continue stirring, heating to 40 ℃, preserving heat for 5h, transferring a reaction product into a separating funnel after preserving heat, neutralizing sulfuric acid with a sodium carbonate solution accounting for 45% of the mass fraction until the solution is neutral, washing for 3 times with deionized water, removing a water layer, heating an oil layer to 200 ℃, and removing impurities in vacuum to obtain a light yellow oil liquid;

step B2: adding allyl glycidyl ether and light yellow oil into a four-neck flask, uniformly stirring and mixing at a constant speed under the condition that the rotating speed is 400r/min, raising the temperature to 95 ℃, adding chloroplatinic acid accounting for 0.45 percent of the total weight of substances in the four-neck flask, heating to 110 ℃, keeping the rotating speed unchanged, preserving the temperature for 6 hours, and removing low-boiling-point substances and unreacted reactants under reduced pressure to obtain viscous liquid;

step B3: adding dimethyl silicone oil and fumed silica into a four-neck flask, uniformly stirring and mixing at a constant speed under the condition that the rotating speed is 1000r/min, raising the temperature to 220 ℃, keeping the rotating speed for stirring and keeping the temperature for 6 hours, then cooling to room temperature to obtain an organic silicon paste, uniformly stirring and mixing the organic silicon paste, an emulsifier, a viscous liquid and polyvinyl alcohol at the rotating speed of 3000r/min to obtain a mixed emulsion, adding deionized water accounting for 35 percent of the total mass of the mixed emulsion into the mixed emulsion, and uniformly stirring and mixing at the rotating speed of 1500r/min to obtain the modified defoaming agent.

The mass ratio of the octamethylcyclotetrasiloxane to the tetramethyldihydrosiloxane in step B1 is 49: 1; in the step B2, the mol ratio of the allyl glycidyl ether to the light yellow oil liquid is 2: 1; in the step B3, the mass ratio of the dimethyl silicone oil to the fumed silica is 19: 1; the weight ratio of the organic silicon paste to the emulsifier to the viscous liquid to the polyvinyl alcohol is 2:1:0.5: 0.1.

The emulsifier is formed by mixing span 60 and tween 60 according to the mass ratio of 3: 1.

The reactive diluent is biquaternary synthetic tetrol hexaacrylate.

The photoinitiator is 2-hydroxy-2-methyl-1-phenyl-1-acetone.

The coloring pigment is phthalocyanine blue.

Comparative example 1

Compared with the embodiment 3, the comparative example does not add nano zinc powder, and the other raw materials and the preparation process are the same.

Comparative example 2

This comparative example is a commercial photo-curable ink for metal articles.

Selecting a tinplate sheet with the specification of 50mm multiplied by 2mm as a sample matrix, carrying out alkali washing and drying, polishing by using 1000-mesh waterproof abrasive paper, wiping by using acetone, then respectively coating the photocuring ink of the examples 1-3 and the photocuring ink of the comparative examples 1-2 on the surface of the sample, wherein the coating thickness is 100 microns, carrying out ultraviolet irradiation curing, soaking the sample in an ammonium nitrate solution with the temperature of 70 ℃ and the mass fraction of 20%, counting the bubbling time of the surface of the sample, detecting the proportion of the corrosion area of the sample in the total area of the sample after soaking for 30 days, and the statistical data are shown in the following table:

detecting items	Example 1	Example 2	Example 3	Comparative example 1	Comparative example 2
						Foaming time (h)	41	43	44	32	20
Corrosion ratio (%)	10%	9%	8%	78%	92%

According to the tables, the phenolic epoxy resin is modified and the nano zinc powder is added, so that the protection time of the surface of a metal product can be effectively prolonged, and corrosive liquid can be effectively reduced from entering the surface of a coating and a substrate; as can be seen from the data of the embodiment 3 and the comparative example 1, the protection time of the coating film on the metal matrix can be effectively prolonged by adding the nano zinc powder, the corrosion proportion of the metal matrix is greatly reduced, and the corrosion resistance protection of the metal matrix is realized.

In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.