Silver-based material surface imprinting forming process

Abstract

The invention relates to the technical field of silver-based material coining forming, in particular to a silver-based material surface coining forming technology. The invention discloses a silver-based material surface imprinting forming process. The process comprises the steps of silver-based material pretreatment, release agent spraying, imprinting forming, demolding and cleaning. The lauric acid and the diethylenetriamine react under the catalysis of aluminum oxide to prepare the corrosion inhibition additive, then the corrosion inhibition additive and the anti-wear additive are added into the release agent together, and after the surface of the silver-based material is coated with the release agent, a thiadiazole ring in the anti-wear additive is more easily adsorbed to high-activity sites on the surface of the silver-based material, a compact molecular barrier is formed, and the anti-wear property of the silver-based material is improved. And the corrosion inhibition additive molecules are more easily adsorbed on a flat area on the surface of the silver-based material to inhibit oxidation corrosion of the silver-based material, and when the corrosion inhibition additive molecules and the silver-based material are combined for use, the corrosion inhibition additive molecules and the silver-based material can jointly cover the whole area of the silver surface, and local corrosion of the silver-based material in the imprinting forming process is avoided.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of silver-based material imprint forming, in particular to a silver-based material surface imprint forming process. BACKGROUND

[0002] The silver-based material imprint forming process is a precision machining technology that uses a mold to apply pressure to a silver-based material to cause plastic deformation, thereby replicating the micro-nano structure on the surface of the mold. This process transfers the texture, pattern or functional structure on the surface of the mold efficiently, achieving low-cost and large-scale production of high-precision micro-nano topography on the surface of the silver-based material.

[0003] However, the surface energy of silver-based materials is high, and adhesion between the mold and the silver-based material is prone to occur during the imprinting process, resulting in scratches and defects on the formed surface, even damage to the mold, which seriously affects the precision and yield of the product. In the prior art, a release agent is usually coated in the mold to form a low-surface-energy isolation layer between the mold and the silver-based material, significantly reducing the interfacial friction and adsorption force, ensuring that the mold and the silver-based material can be separated smoothly after imprinting, reducing defects such as scratches and microstructure defects on the formed surface, and protecting the precision texture of the mold cavity. However, silver-based materials are prone to oxidation or corrosion by corrosive media in the imprinting environment, especially under high temperature and humid conditions, forming an oxide layer or corrosion spots, and coating a release agent in the mold cannot achieve surface protection for the silver-based material.

[0004] Therefore, it is necessary to propose a silver-based material surface imprint forming process that can perform surface corrosion protection for the silver-based material to improve the quality of silver-based material imprint forming. SUMMARY

[0005] In view of the deficiencies in the prior art, the purpose of the present application is to provide a silver-based material surface imprint forming process.

[0006] The present application provides a silver-based material surface imprint forming process, comprising the following steps: Step 1: Soak the silver-based material in acetone for 10-20 min, then ultrasonic clean for 5-10 min, dry, then soak in 5% dilute nitric acid solution for 20-30 s, wash with deionized water until neutral, dry the surface moisture with nitrogen, and then vacuum dry to obtain a pretreated silver-based material; Step 2: Uniformly spray the photodegradable release agent on the surface of the pretreated silver-based material using a spray gun, and dry at 50-60°C for 30-40 min, then cool to obtain a release-coated silver-based material; Step 3: Fix the release-coated silver-based material and the mold in the imprinting equipment respectively, perform imprinting, then perform demolding, then irradiate with 365 nm ultraviolet light for 10-15 min, finally clean with ethanol for 2-3 times and dry. The raw material composition of the photodegradable release agent, by mass fraction, is: 40-50 parts of modified heptadecafluorodecyltrimethoxysilane, 6-8 parts of anti-wear additive, 3-5 parts of corrosion inhibitor, 46-52 parts of mixed solvent, 1-2 parts of dilute hydrochloric acid solution, and 10-20 parts of deionized water, wherein the mixed solvent is prepared by mixing ethanol and isopropyl alcohol in a volume ratio of (2-4):1.

[0007] Further, the preparation steps of the photodegradable release agent are as follows: S1: Preparation of anti-wear additive S1.1: n-Hexanol is added to dimethylbenzene in a volume ratio of 1:(6-8), after stirring and mixing uniformly, boric acid is added, and heating and stirring reflux reaction is carried out at 130-150℃ for 7-8h to obtain an intermediate solution; S1.2: When the temperature of the above-mentioned intermediate solution decreases to 110-120℃, 2-amino-5-mercapto-1,3,4-thiadiazole is added, and the reaction is carried out after heat preservation and stirring for 5-6h, after cooling, filtration, washing and drying, the anti-wear additive is obtained; S2: Preparation of corrosion inhibitor Laurylic acid is dissolved in dimethylbenzene, and then diethylenetriamine and aluminum oxide are added to react to obtain the corrosion inhibitor; S3: Preparation of modified heptadecafluorodecyltrimethoxysilane 4-Vinylaniline and concentrated hydrochloric acid are added to deionized water, after stirring and mixing, sodium nitrite solution is added to react, then a mixture of aniline, glacial acetic acid and deionized water is added to continue the reaction, a modifier is prepared, then heptadecafluorodecyltrimethoxysilane and the modifier are mixed to react to obtain the modified heptadecafluorodecyltrimethoxysilane; S4: Preparation of photodegradable release agent The modified heptadecafluorodecyltrimethoxysilane is added to the mixed solvent, after fully stirring and dissolving, 0.1mol / L dilute hydrochloric acid solution and deionized water are added, heating and stirring is carried out at 30-35℃ for 60-90min, then the anti-wear additive and the corrosion inhibitor are added, continue to stir and mix uniformly, and ultrasonic treatment is carried out for 20-30min, after standing for 1-2h, the photodegradable release agent is obtained.

[0008] Further, the specific preparation steps of the corrosion inhibitor are as follows: S2.1: Laurylic acid is added to dimethylbenzene in a mass ratio of (3-5):1, after fully stirring and mixing, diethylenetriamine and aluminum oxide are added, after fully stirring and mixing, the mixed reaction product is obtained; S2.2: The above-mentioned mixed reaction product is transferred to a reaction kettle, under the protection of nitrogen, heating and stirring is carried out at 130-140℃ for 1-2h, then heating is carried out at 145-155℃ for 30-40min, and then heating is carried out at 180-190℃ for 1-2h to obtain the precursor; S2.3: The precursor is reacted at 0.5-0.54 MPa and 210-220℃ for 60-70 min, the gas pressure is adjusted to 0.12-0.14 MPa, and the reaction is continued for 60-70 min, and after cooling, the corrosion inhibitor additive is obtained.

[0009] Further, the specific preparation steps of the modified heptadecafluorodecyltrimethoxysilane are as follows: S3.1: 4-vinylaniline and concentrated hydrochloric acid are added to deionized water according to (1.2-1.3) g: (3-4) mL: (30-40) mL, fully stirred and dissolved, then hydroquinone is added, and then placed in an ice bath at 1-3℃, while stirring, sodium nitrite solution is added, and stirred for 30-40 min, to obtain an intermediate solution; S3.2: Aniline and glacial acetic acid are added to deionized water according to (0.9-1) g: (1.8-2.2) mL: (10-20) mL, fully stirred and dissolved, then the above intermediate solution is added, and the reaction is continued for 1-2 h, and after filtration, washing, recrystallization, filtration and vacuum drying, the modifier is obtained; S3.3: Heptadecafluorodecyltrimethoxysilane and the above modifier are added to anhydrous toluene according to (2.3-2.5) g: 1 g: (20-30) mL, fully stirred and dissolved, then azobisisobutyronitrile is added, and heated and stirred at 65-75℃ for 4-6 h under the protection of nitrogen, then deionized water and 0.1 mol / L dilute hydrochloric acid solution are added, and the reaction is continued for 8-12 h while stirring at 80-90℃, then after cooling, triethylamine is added to adjust the pH to 7-8, and after alcohol precipitation, filtration, washing and vacuum drying, the modified heptadecafluorodecyltrimethoxysilane is obtained.

[0010] Further, the molar ratio of n-hexanol to boric acid is (1.8-2):1, and the molar ratio of 2-amino-5-mercapto-1,3,4-thiadiazole to boric acid is 2:1.

[0011] Further, the molar ratio of diethylenetriamine to lauric acid is 2:1, and the mass ratio of aluminum oxide to lauric acid is 1: (100-200).

[0012] Further, the amount of hydroquinone added is 8-10% of the mass of 4-vinylaniline.

[0013] Further, the sodium nitrite solution is prepared by dissolving sodium nitrite in deionized water at 0.07-0.08 g / mL, and the mass ratio of sodium nitrite to 4-vinylaniline is 1: (1.6-1.7).

[0014] Further, the mass ratio of aniline to 4-vinylaniline is 1: (1.2-1.3), and the amount of azobisisobutyronitrile added is 1-3% of the total mass of heptadecafluorodecyltrimethoxysilane and the modifier.

[0015] Further, the molar ratio of deionized water to heptadecafluorodecyltrimethoxysilane is (3-5):1, and the amount of dilute hydrochloric acid solution added is 1.5-2% of the total mass of the system.

[0016] The present application has the following advantages: 1、In the present application, after the corrosion inhibitor additive is prepared by reacting lauric acid with diethylene triamine under the catalysis of aluminum oxide, the corrosion inhibitor additive and the anti-wear additive are added into the release agent together, and then coated on the surface of the silver-based material, the thiazole ring in the anti-wear additive is more easily adsorbed on the "high active site" on the surface of the silver-based material, forming a dense molecular barrier to reduce the penetration channel of the corrosion medium, and the corrosion inhibitor additive molecules are more easily adsorbed on the "flat area" on the surface of the silver-based material to inhibit the oxidation corrosion of the silver-based material. When the two are used together, they can jointly cover the entire area of the silver surface and avoid local corrosion of the silver-based material during the compression molding process.

[0017] 2、In the present application, by first reacting n-hexanol with boric acid to form an intermediate solution, then adding 2-amino-5-mercapto-1,3,4-thiadiazole to the intermediate solution to react, an anti-wear additive is prepared. After the anti-wear additive is added into the release agent and coated on the surface of the silver-based material, it can chelate with the surface of the silver-based material to form a dense passivation film, separating the silver-based material from the mold and reducing direct contact between the two, weakening the intermolecular forces and mechanical interlocking forces at the friction interface, reducing the friction coefficient, and at the same time, the n-hexyl borate chain can slide at the friction interface to reduce the interfacial shear force and reduce wear, thereby avoiding scratches or adhesion of the silver-based material to the mold during the compression process, ensuring the surface finish of the silver-based material, and reducing the release force and mold wear rate.

[0018] 3、In the present application, by adding 4-vinylaniline and concentrated hydrochloric acid into deionized water, stirring and dissolving, then adding sodium nitrite solution to react to form a diazonium salt intermediate, and then adding a mixed solution of aniline, glacial acetic acid and deionized water to react, 4-vinyl azobenzene is prepared. Then, under the initiation of an initiator, copolymerization of 4-vinyl azobenzene and heptadecafluorodecyltrimethoxysilane is carried out to obtain modified heptadecafluorodecyltrimethoxysilane. After the release agent is prepared using the modified heptadecafluorodecyltrimethoxysilane as the main raw material, it will undergo cis-trans isomerization under ultraviolet light irradiation, causing molecular chain rupture and degradation. After the silver-based material is compression molded, the release agent coating is irradiated with ultraviolet light to degrade it into small molecules, which are then washed away with ethanol, achieving residue-free removal of the release agent, thereby avoiding damage to the surface of the silver-based material caused by mechanical scraping or strong solvent cleaning. DETAILED DESCRIPTION

[0019] To enable those skilled in the art to better understand the technical solutions of this invention, the technical solutions in the embodiments of this invention will be clearly and completely described below in conjunction with the embodiments of this invention.

[0020] Example 1: A process for embossing a silver-based material surface, comprising the following steps: Step 1: Soak the silver-based material in acetone for 10 minutes, then ultrasonically clean it for 5 minutes, dry it, then soak it in 5% dilute nitric acid solution for 20 seconds, wash it with deionized water until neutral, blow the surface moisture with nitrogen, and then vacuum dry it to obtain the pretreated silver-based material. Step 2: Use a spray gun to evenly spray the photodegradable release agent onto the surface of the pretreated silver-based material, and dry it at 50°C for 30 minutes. After cooling, the release coating silver-based material is obtained. Step 3: Fix the above-mentioned release coating silver-based material and mold in the embossing equipment for embossing. After embossing, demold, then irradiate with 365nm ultraviolet light for 10 minutes, and finally clean with ethanol twice and dry. The preparation steps of the photodegradable release agent are as follows: S1: Preparation of anti-wear additives S1.1: Add n-hexanol to xylene at a volume ratio of 1:6, stir and mix evenly, add boric acid, and heat and reflux at 130℃ for 7 hours to obtain an intermediate solution, wherein the molar ratio of n-hexanol to boric acid is 1.8:1; S1.2: When the temperature of the above intermediate solution drops to 110℃, add 2-amino-5-mercapto-1,3,4-thiadiazole and keep it warm and stir for 5 hours. After cooling, filter, wash and dry to obtain the anti-wear additive, wherein the molar ratio of 2-amino-5-mercapto-1,3,4-thiadiazole to boric acid is 2:1. S2: Preparation of corrosion inhibitor additives S2.1: Add lauric acid to xylene at a mass ratio of 3:1, stir and mix thoroughly, then add diethylenetriamine and alumina, stir and mix thoroughly to obtain a mixed reactant, wherein the molar ratio of diethylenetriamine to lauric acid is 2:1, and the mass ratio of alumina to lauric acid is 1:100; S2.2: Transfer the above mixed reactants to a reaction vessel, heat and stir at 130°C for 1 hour under nitrogen protection, then heat at 145°C for 30 minutes, and then heat at 180°C for 1 hour to obtain the precursor; S2.3: The above precursor was reacted at 0.5 MPa and 210 °C for 60 min, then the gas pressure was adjusted to 0.12 MPa, and the reaction was continued at the temperature for another 60 min. After cooling, the corrosion inhibitor was obtained. S3: Preparation of modified heptadecafluorodecyltrimethoxysilane S3.1: 4-vinylaniline and concentrated hydrochloric acid are added into deionized water according to 1.2g: 3mL: 30mL, after being fully stirred and dissolved, hydroquinone is added, then it is placed in a 1℃ ice bath, while stirring, sodium nitrite solution is added, and it is incubated and stirred for 30min to obtain an intermediate solution, wherein the amount of hydroquinone added is 8% of the mass of 4-vinylaniline, the sodium nitrite solution is prepared by dissolving sodium nitrite in deionized water at 0.07g / mL, and the mass ratio of sodium nitrite to 4-vinylaniline is 1:1.6; S3.2: aniline and glacial acetic acid are added into deionized water according to 0.9g: 1.8mL: 10mL, after being fully stirred and dissolved, the above-mentioned intermediate solution is added, and the reaction is continued for 1h, after filtration, washing, recrystallization, filtration and vacuum drying, the modifier is obtained, wherein the mass ratio of aniline to 4-vinylaniline is 1:1.2; S3.3: heptadecafluorodecyltrimethoxysilane and the above-mentioned modifier are added into anhydrous toluene according to 2.3g: 1g: 20mL, after being fully stirred and dissolved, azobisisobutyronitrile is added, and under the protection of nitrogen, it is heated and stirred at 65℃ for 4h, then deionized water and 0.1mol / L dilute hydrochloric acid solution are added, and the reaction is continued for 8h while being heated to 80℃, after cooling, triethylamine is added to adjust the pH to 7, after alcohol precipitation, filtration, washing and vacuum drying, the modified heptadecafluorodecyltrimethoxysilane is obtained, wherein the amount of azobisisobutyronitrile added is 1% of the total mass of heptadecafluorodecyltrimethoxysilane and the modifier, wherein the molar ratio of deionized water to heptadecafluorodecyltrimethoxysilane is 3:1, and the amount of dilute hydrochloric acid solution added is 1.5% of the total mass of the system; S4: preparation of photodegradable release agent The modified heptadecafluorodecyltrimethoxysilane is added into a mixed solvent, after being fully stirred and dissolved, 0.1mol / L dilute hydrochloric acid solution and deionized water are added, and it is heated and stirred at 30℃ for 60min, then wear-resistant additive and corrosion-resistant additive are added, and it is continuously stirred and mixed uniformly, and ultrasonic treatment is carried out for 20min, and it is left to stand for 1h to obtain the photodegradable release agent, wherein the raw material composition of the photodegradable release agent is: 40 parts of modified heptadecafluorodecyltrimethoxysilane, 6 parts of wear-resistant additive, 3 parts of corrosion-resistant additive, 46 parts of mixed solvent, 1 part of dilute hydrochloric acid solution and 10 parts of deionized water, wherein the mixed solvent is prepared by mixing ethanol and isopropyl alcohol at a volume ratio of 2:1.

[0021] Example 2, a silver-based material surface imprinting forming process, comprising the following steps: Step one: the silver-based material is soaked in acetone for 15min, then ultrasonic cleaned for 7min, dried, then soaked in 5% dilute nitric acid solution for 25s, washed with deionized water until neutral, after nitrogen blowing to dry the surface moisture, vacuum drying is carried out to obtain a pretreated silver-based material; Step two: the photodegradable release agent is evenly sprayed on the surface of the pretreated silver-based material by using a spray gun, and is dried at 55℃ for 35min, and after cooling, a release coating silver-based material is obtained; Step three: the release coating silver-based material and the mold are respectively fixed in the stamping equipment, and stamping is performed, after stamping is completed, demolding is performed, then 365nm ultraviolet light is irradiated for 12min, finally, ethanol is cleaned for 3 times, and drying is performed; The preparation steps of the photodegradable release agent are as follows: S1: preparation of anti-wear additive S1.1: n-hexanol is added to dimethylbenzene at a volume ratio of 1:7, after stirring and mixing uniformly, boric acid is added, and reflux reaction is carried out at 140℃ for 7.5h to obtain an intermediate solution, wherein the molar ratio of n-hexanol to boric acid is 1.9:1; S1.2: when the temperature of the above-mentioned intermediate solution decreases to 115℃, 2-amino-5-mercapto-1,3,4-thiadiazole is added, and the reaction is stirred for 5.5h, after cooling, filtration, washing and drying, the anti-wear additive is obtained, wherein the molar ratio of 2-amino-5-mercapto-1,3,4-thiadiazole to boric acid is 2:1; S2: preparation of corrosion inhibitor additive S2.1: lauric acid is added to dimethylbenzene at a mass ratio of 4:1, and is fully stirred and mixed, then diethylene triamine and aluminum oxide are added, and after fully stirring and mixing, a mixed reactant is obtained, wherein the molar ratio of diethylene triamine to lauric acid is 2:1, and the mass ratio of aluminum oxide to lauric acid is 1:150; S2.2: the above-mentioned mixed reactant is transferred to a reaction kettle, and is heated and stirred at 135℃ for 1.5h under nitrogen protection, then is heated for 35min at 150℃, and then is heated for 1.5h at 185℃ to obtain a precursor; S2.3: the above-mentioned precursor is reacted at 0.52MPa and 215℃ for 65min, then the gas pressure is adjusted to 0.13MPa, and the reaction is continued for 65min, and after cooling, the corrosion inhibitor additive is obtained; S3: preparation of modified heptadecafluorodecyltrimethoxysilane S3.1: 4-vinylaniline and concentrated hydrochloric acid are added to deionized water at a ratio of 1.25g:3.5mL:35mL, after fully stirring and dissolving, hydroquinone is added, then is placed in a 2℃ ice bath, sodium nitrite solution is added while stirring, and is stirred and heated for 35min to obtain an intermediate solution, wherein the amount of hydroquinone added is 9% of the mass of 4-vinylaniline, the sodium nitrite solution is prepared by dissolving sodium nitrite in deionized water at a concentration of 0.075g / mL, and the mass ratio of sodium nitrite to 4-vinylaniline is 1:1.65; S3.2: Aniline and glacial acetic acid are added to deionized water in a ratio of 0.95g: 2mL: 15mL, fully stirred and dissolved, then the above-mentioned intermediate solution is added, and the reaction is continued for 1.5h under warm stirring, then filtered, washed, recrystallized, filtered and vacuum dried to obtain the modifier, wherein the ratio of aniline to 4-vinylaniline is 1:1.25; S3.3: Heptadecafluorodecyltrimethoxysilane and the above-mentioned modifier are added to anhydrous toluene in a ratio of 2.4g: 1g: 25mL, fully stirred and dissolved, then azobisisobutyronitrile is added, and the reaction is carried out under the protection of nitrogen at 70℃ for 5h, then deionized water and 0.1mol / L dilute hydrochloric acid solution are added, and the reaction is continued for 10h under warm stirring at 85℃, then triethylamine is added to adjust the pH to 7.5 after cooling, and the product is obtained by alcohol precipitation, filtration, washing and vacuum drying, wherein the amount of azobisisobutyronitrile added is 2% of the total mass of heptadecafluorodecyltrimethoxysilane and the modifier, and the molar ratio of deionized water to heptadecafluorodecyltrimethoxysilane is 4:1, and the amount of dilute hydrochloric acid solution added is 1.7% of the total mass of the system; S4: Preparation of photodegradable release agent The modified heptadecafluorodecyltrimethoxysilane is added to the mixed solvent, fully stirred and dissolved, then 0.1mol / L dilute hydrochloric acid solution and deionized water are added, and the reaction is carried out under warm stirring at 33℃ for 75min, then anti-wear additives and corrosion inhibitors are added, and the mixture is stirred until uniform, and then ultrasonic treatment is carried out for 25min, and the product is obtained by standing and aging for 1.5h, wherein the raw material composition of the photodegradable release agent is 45 parts of modified heptadecafluorodecyltrimethoxysilane, 7 parts of anti-wear additives, 4 parts of corrosion inhibitors, 49 parts of mixed solvent, 1.5 parts of dilute hydrochloric acid solution and 15 parts of deionized water, wherein the mixed solvent is prepared by mixing ethanol and isopropanol in a volume ratio of 3:1.

[0022] Example 3, a silver-based material surface imprinting forming process, comprising the following steps: Step one: the silver-based material is soaked in acetone for 20min, then ultrasonic cleaned for 10min, dried, then soaked in 5% dilute nitric acid solution for 30s, washed with deionized water until neutral, then nitrogen dried, and vacuum dried to obtain a pretreated silver-based material; Step two: the photodegradable release agent is uniformly sprayed on the surface of the pretreated silver-based material by using a spray gun, and then dried at 60℃ for 40min, and the silver-based material with release coating is obtained after cooling; Step three: the silver-based material with release coating and the mold are fixed in the imprinting equipment respectively, and then the imprinting is carried out, and after the imprinting is completed, the mold is removed, then the product is irradiated by 365nm ultraviolet light for 15min, and finally cleaned with ethanol for 3 times and dried; The preparation steps of the photo-degradable release agent are as follows: S1: preparing an anti-wear additive S1.1: n-hexanol is added into dimethylbenzene at a volume ratio of 1:8, after being stirred and uniformly mixed, boric acid is added, and heating and stirring reflux reaction is carried out at 150 DEG C for 8h to obtain an intermediate solution, wherein the molar ratio of n-hexanol to boric acid is 2:1; S1.2: when the temperature of the above intermediate solution is reduced to 120 DEG C, 2-amino-5-sulfhydryl-1, 3, 4-thiadiazole is added, and the reaction is carried out for 6h under the condition of heat preservation and stirring, after cooling, filtration, washing and drying, the anti-wear additive is obtained, wherein the molar ratio of 2-amino-5-sulfhydryl-1, 3, 4-thiadiazole to boric acid is 2:1; S2: preparing an anti-corrosion additive S2.1: lauric acid is added into dimethylbenzene at a mass ratio of 5:1, and is fully stirred and mixed, then diethylene triamine and aluminum oxide are added, and after being fully stirred and mixed, a mixed reactant is obtained, wherein the molar ratio of diethylene triamine to lauric acid is 2:1, and the mass ratio of aluminum oxide to lauric acid is 1:200; S2.2: the above mixed reactant is transferred into a reaction kettle, and is heated and stirred under the protection of nitrogen at 140 DEG C for 2h, then is heated at 155 DEG C for 40min, and is heated at 190 DEG C for 2h to obtain a precursor; S2.3: the above precursor is reacted at 0.54MPa and 220 DEG C for 70min, then the gas pressure is adjusted to 0.14MPa, and the reaction is continued for 70min under the condition of heat preservation, and after cooling, the anti-corrosion additive is obtained; S3: preparing modified heptadecafluorodecyl trimethoxysilane S3.1: 4-vinylaniline and concentrated hydrochloric acid are added into deionized water at 1.3g:4mL:40mL, after being fully stirred and dissolved, hydroquinone is added, then the mixture is placed in a 3 DEG C ice bath, sodium nitrite solution is added while stirring, and the mixture is heat preserved and stirred for 40min to obtain an intermediate solution, wherein the amount of hydroquinone added is 10% of the mass of 4-vinylaniline, the sodium nitrite solution is prepared by dissolving sodium nitrite in deionized water at 0.08g / mL, and the mass ratio of sodium nitrite to 4-vinylaniline is 1:1.7; S3.2: aniline and glacial acetic acid are added into deionized water at 1g:2.2mL:20mL, after being fully stirred and dissolved, the above intermediate solution is added, and the reaction is continued for 2h under the condition of heat preservation and stirring, and after being suction filtered, washed, recrystallized, filtered and vacuum dried, the modifier is obtained, wherein the mass ratio of aniline to 4-vinylaniline is 1:1.3; S3.3: The heptadecafluorodecyltrimethoxysilane and the above modifier are added into anhydrous toluene at 2.5g: 1g: 30mL, after being fully stirred and dissolved, azobisisobutyronitrile is added, and heated and stirred at 75℃ for 6h under the protection of nitrogen, then deionized water and 0.1mol / L dilute hydrochloric acid solution are added, and the reaction is continued to be stirred at 90℃ for 12h, after cooling, triethylamine is added to adjust the pH to 8, and after alcohol precipitation, filtration, washing and vacuum drying, the modified heptadecafluorodecyltrimethoxysilane is obtained, wherein the addition amount of azobisisobutyronitrile is 3% of the total mass of heptadecafluorodecyltrimethoxysilane and modifier, wherein the molar ratio of deionized water to heptadecafluorodecyltrimethoxysilane is 5:1, and the addition amount of dilute hydrochloric acid solution is 2% of the total mass of the system; S4: Preparation of photodegradable release agent The modified heptadecafluorodecyltrimethoxysilane is added into the mixed solvent, after being fully stirred and dissolved, 0.1mol / L dilute hydrochloric acid solution and deionized water are added, and heated and stirred at 35℃ for 90min, then the anti-wear additive and the corrosion inhibitor are added, and continue to be stirred and mixed uniformly, and ultrasonic treatment is carried out for 30min, and aging is carried out for 2h, to obtain the photodegradable release agent, wherein the raw material composition of the photodegradable release agent is: 50 parts of modified heptadecafluorodecyltrimethoxysilane, 8 parts of anti-wear additive, 5 parts of corrosion inhibitor, 52 parts of mixed solvent, 2 parts of dilute hydrochloric acid solution and 20 parts of deionized water, wherein the mixed solvent is prepared by mixing ethanol and isopropanol at a volume ratio of 4:1.

[0023] Comparative Example 1, the difference between this comparative example 1 and example 1 is that the corrosion inhibitor in step S4 is replaced by an equal amount of anti-wear additive.

[0024] Comparative Example 2, the difference between this comparative example 2 and example 1 is that the anti-wear additive in step S4 is replaced by an equal amount of corrosion inhibitor.

[0025] Comparative Example 3, the difference between this comparative example 3 and example 1 is that the anti-wear additive in step S4 is removed.

[0026] Comparative Example 4, the difference between this comparative example 4 and example 1 is that the modified heptadecafluorodecyltrimethoxysilane in step S4 is replaced by an equal amount of heptadecafluorodecyltrimethoxysilane.

[0027] Test Example: Test 1: After the silver-based material in examples 1-3 and comparative examples 1-2 is imprinted and the release agent is washed off, the surface corrosion is detected, and the results are shown in Table 1.

[0028] Table 1: Surface corrosion of silver-based material after imprinting

[0029] From the above Table 1, it can be seen that in Comparative Example 1 and Comparative Example 2, when only one of the anti-wear additive or the corrosion inhibitor additive is added, pitting occurs on the silver-based material after the completion of the coining, and thus it can be seen that the corrosion inhibitor additive and the anti-wear additive have a synergistic effect when used together, and can jointly cover the entire area of the surface of the silver, thereby avoiding local corrosion of the silver-based material during the coining process.

[0030] Test 2: The surface finish of the silver-based material after the completion of the coining and the removal of the release agent in Example 1-3 and Comparative Example 3 was detected, and the results are shown in Table 2.

[0031] Table 2: Test results of the surface finish of the silver-based material after coining

[0032] From the above Table 2, it can be seen that in Comparative Example 3, after not adding the anti-wear additive to the photodegradable release agent, the surface roughness of the silver-based material after the completion of the coining is significantly higher than that of Example 1, and thus it can be seen that by first reacting n-hexanol with boric acid to generate an intermediate solution, then adding 2-amino-5-mercapto-1,3,4-thiadiazole to the intermediate solution to generate the anti-wear additive, and then adding the anti-wear additive to the release agent and coating it on the surface of the silver-based material, it can be avoided that the surface of the silver-based material is scratched or adhered to the mold during the coining process due to friction, and the surface finish of the silver-based material is ensured.

[0033] Test 3: The surface release agent residue of the silver-based material after the completion of the coining in Example 1-3 and Comparative Example 4 was detected after ultraviolet light irradiation and anhydrous ethanol cleaning, and the results are shown in Table 3.

[0034] Table 3: Test results of the ultraviolet aging resistance of the polyurethane composite coating

[0035] From the above Table 3, it can be seen that in Comparative Example 4, after not modifying the heptadecafluorodecyltrimethoxysilane, the release agent prepared therefrom has surface release agent residue after ultraviolet light irradiation and anhydrous ethanol cleaning, and thus it can be seen that by adding 4-vinylaniline and concentrated hydrochloric acid to deionized water, stirring and dissolving, then adding sodium nitrite solution to react to generate a diazonium salt intermediate, then adding a mixed solution of aniline, glacial acetic acid and deionized water to react to generate 4-vinyl azobenzene, and then copolymerizing the 4-vinyl azobenzene with the heptadecafluorodecyltrimethoxysilane under the initiation of an initiator to obtain modified heptadecafluorodecyltrimethoxysilane, and using the modified heptadecafluorodecyltrimethoxysilane as the main raw material to prepare the release agent, when the silver-based material is coining completed, the release agent coating is irradiated with ultraviolet light, and then washed with ethanol, the release agent can be removed without residue, thereby avoiding damage to the surface of the silver-based material caused by mechanical scratching or strong solvent cleaning.

[0036] It is to be understood that all of the above modifications and alterations can be made to the above-described arrangements and that all such modifications and alterations are intended to be included within the scope of the present application. Those skilled in the art will readily appreciate that other modifications and alterations can be made to the present application without departing from the scope of the application.

Claims

1. A process for embossing molding on the surface of a silver-based material, characterized in that, Includes the following steps: Step 1: Soak the silver-based material in acetone for 10-20 minutes, then ultrasonically clean it for 5-10 minutes, dry it, then soak it in 5% dilute nitric acid solution for 20-30 seconds, wash it with deionized water until neutral, blow the surface moisture with nitrogen, and then vacuum dry it to obtain the pretreated silver-based material. Step 2: Use a spray gun to evenly spray the photodegradable release agent onto the surface of the pretreated silver-based material, and dry it at 50-60℃ for 30-40 minutes. After cooling, the release coating silver-based material is obtained. Step 3: Fix the above-mentioned release coating silver-based material and mold in the embossing equipment for embossing. After embossing, demold, then irradiate with 365nm ultraviolet light for 10-15 minutes, and finally clean with ethanol 2-3 times and dry. The raw material composition of the photodegradable release agent, by mass, is as follows: 40-50 parts modified heptadecafluorodecyltrimethoxysilane, 6-8 parts anti-wear additive, 3-5 parts corrosion inhibitor, 46-52 parts mixed solvent, 1-2 parts dilute hydrochloric acid solution and 10-20 parts deionized water. The mixed solvent is prepared by mixing ethanol and isopropanol in a volume ratio of (2-4):

1.

2. The silver-based material surface embossing molding process according to claim 1, characterized in that, The preparation steps of the photodegradable release agent are as follows: S1: Preparation of anti-wear additives S1.1: Add n-hexanol to xylene at a volume ratio of 1:(6-8), stir and mix evenly, then add boric acid, and heat and reflux at 130-150℃ for 7-8 hours to obtain an intermediate solution; S1.2: When the temperature of the above intermediate solution drops to 110-120℃, add 2-amino-5-mercapto-1,3,4-thiadiazole, and keep it warm and stir for 5-6 hours. After cooling, filter, wash and dry to obtain the anti-wear additive. S2: Preparation of corrosion inhibitor additives Lauric acid is dissolved in xylene, and then diethylenetriamine and alumina are added to react and obtain a corrosion inhibitor. S3: Preparation of modified heptadecafluorodecyltrimethoxysilane 4-Vinylaniline and concentrated hydrochloric acid were added to deionized water and stirred. Sodium nitrite solution was added to react with the mixture. A mixture of aniline, glacial acetic acid and deionized water was then added to continue the reaction to prepare a modifier. Heptadecanofluorodecyltrimethoxysilane was then mixed with the modifier and reacted to obtain modified heptadecanofluorodecyltrimethoxysilane. S4: Preparation of photodegradable release agent Modified heptadecafluorodecyltrimethoxysilane was added to a mixed solvent and stirred thoroughly to dissolve. Then, 0.1 mol / L dilute hydrochloric acid solution and deionized water were added. The mixture was heated and stirred at 30-35℃ for 60-90 min. Anti-wear additives and corrosion inhibitors were then added, and the mixture was stirred and mixed evenly. The mixture was then ultrasonically treated for 20-30 min and allowed to stand for 1-2 h to obtain a photodegradable release agent.

3. The silver-based material surface embossing molding process according to claim 2, characterized in that, The specific preparation steps for corrosion inhibitors are as follows: S2.1: Add lauric acid to xylene at a mass ratio of (3-5):1, stir and mix thoroughly, then add diethylenetriamine and aluminum oxide, stir and mix thoroughly to obtain a mixed reactant; S2.2: Transfer the above mixed reactants to a reaction vessel, heat and stir at 130-140℃ for 1-2 hours under nitrogen protection, then heat at 145-155℃ for 30-40 minutes, and then heat at 180-190℃ for 1-2 hours to obtain the precursor. S2.3: React the above precursor at 0.5-0.54 MPa and 210-220℃ for 60-70 min, then adjust the gas pressure to 0.12-0.14 MPa and continue the reaction at this temperature for another 60-70 min. After cooling, the corrosion inhibitor is obtained.

4. The silver-based material surface embossing molding process according to claim 3, characterized in that, The specific preparation steps for modified heptadecafluorodecyltrimethoxysilane are as follows: S3.1: Add 4-vinylaniline and concentrated hydrochloric acid to deionized water at a ratio of (1.2-1.3) g: (3-4) mL: (30-40) mL. After stirring and dissolving thoroughly, add hydroquinone and place in an ice bath at 1-3℃. While stirring, add sodium nitrite solution and keep warm and stirring for 30-40 min to obtain the intermediate solution. S3.2: Add aniline and glacial acetic acid to deionized water at a ratio of (0.9-1) g: (1.8-2.2) mL: (10-20) mL, stir to dissolve, then add to the above intermediate solution, continue to keep warm and stir for 1-2 h, and obtain the modifier by suction filtration, washing, recrystallization, filtration and vacuum drying; S3.3: Add heptadecafluorodecyltrimethoxysilane and the above modifier to anhydrous toluene at a ratio of (2.3-2.5) g: 1 g: (20-30) mL. After thorough stirring and dissolution, add azobisisobutyronitrile and heat and stir at 65-75℃ for 4-6 h under nitrogen protection. Then add deionized water and 0.1 mol / L dilute hydrochloric acid solution, raise the temperature to 80-90℃ and continue stirring for 8-12 h. After cooling, add triethylamine to adjust the pH to 7-8. After alcohol precipitation, filtration, washing and vacuum drying, the modified heptadecafluorodecyltrimethoxysilane is obtained.

5. The silver-based material surface embossing molding process according to claim 2, characterized in that, The molar ratio of hexanol to boric acid is (1.8-2):1, and the molar ratio of 2-amino-5-mercapto-1,3,4-thiadiazole to boric acid is 2:

1.

6. The silver-based material surface embossing molding process according to claim 3, characterized in that, The molar ratio of diethylenetriamine to lauric acid is 2:1, and the mass ratio of alumina to lauric acid is 1:(100-200).

7. The silver-based material surface embossing molding process according to claim 4, characterized in that, The amount of hydroquinone added is 8-10% of the mass of 4-vinylaniline.

8. The silver-based material surface embossing molding process according to claim 4, characterized in that, The sodium nitrite solution is prepared by dissolving sodium nitrite in deionized water at a concentration of 0.07-0.08 g / mL, and the mass ratio of sodium nitrite to 4-vinylaniline is 1:(1.6-1.7).

9. The silver-based material surface embossing molding process according to claim 4, characterized in that, Aniline and 4-vinylaniline 1: (1.2-1.3), and the amount of azobisisobutyronitrile added is 1-3% of the total mass of heptadecafluorodecyltrimethoxysilane and modifier.

10. The silver-based material surface embossing molding process according to claim 4, characterized in that, The molar ratio of deionized water to heptadecafluorodecyltrimethoxysilane is (3-5):1, and the amount of dilute hydrochloric acid solution added is 1.5-2% of the total mass of the system.

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