Preparation method of water-based nanometal ink

Abstract

The application discloses a preparation method of water-based nano metal ink, which comprises the following steps: selecting raw materials, i.e. 20-30 parts of metal pigment, 40-45 parts of water-based polyurethane resin, 5-10 parts of an additive modifier, 2-4 parts of polyethylene wax and 20-30 parts of deionized water; stirring and uniformly mixing the metal pigment, the water-based polyurethane resin, the additive modifier, the polyethylene wax and the deionized water to obtain the water-based nano metal ink of the application. The product's adhesion, easy cleaning effect and acid corrosion resistance are obviously improved through the mutual coordination of the bentonite modifier and the nano barium metaborate agent doped with the wollastonite.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of metal ink, in particular to a preparation method of water-based nano metal ink. BACKGROUND

[0002] Metal ink refers to an ink prepared by using fine metal flakes to replace pigments or dyes in traditional ink, and the ink has a unique metal shining effect. Commonly said metal ink mainly refers to silver ink and gold ink. The silver ink is prepared by aluminum pigments; the gold ink is generally prepared by copper pigments and zinc pigments according to different proportions, and the Pantone metal color ink required can be produced by controlling and changing the proportions of the pigments.

[0003] The existing metal ink is prepared by using metal pigments and resin materials, and the prepared product has general adhesion to the base layer and poor cleaning ability. The adhesion and easy cleaning effect of the product are difficult to coordinate and improve, which limits the use efficiency of the product. In addition, the product has poor acid corrosion stability, which further limits the use efficiency of the product. SUMMARY

[0004] In view of the defects of the prior art, the purpose of the present application is to provide a preparation method of water-based nano metal ink to solve the problems in the background art.

[0005] The technical problem solved by the present application adopts the following technical scheme:

[0006] The present application provides a preparation method of water-based nano metal ink, comprising the following steps:

[0007] Step one, 3-5 parts of titanate coupling agent, 1-3 parts of yttrium nitrate solution and 5-10 parts of chitosan solution are stirred and uniformly mixed to obtain a coupling complex solution;

[0008] Step two, 2-5 parts of nano barium metaborate doped with wollastonite and 6-10 parts of bentonite modifier are first stirred and uniformly mixed, and then the coupling complex solution is added and fully mixed;

[0009] Step three, the product of step two is treated in a ball mill, the ball milling speed is 1000-1500 r / min, the ball milling time is 1-2 h, after the ball milling, the product is washed with water and dried to obtain an improved additive;

[0010] Step four, selection of raw materials: 20-30 parts of metal pigments, 40-45 parts of water-based polyurethane resin, 5-10 parts of improved additive, 2-4 parts of polyethylene wax and 20-30 parts of deionized water;

[0011] Step five, the metal pigments, water-based polyurethane resin, improved additive, polyethylene wax and deionized water are stirred and uniformly mixed to obtain the water-based nano metal ink of the present application.

[0012] Preferably, the mass fraction of the yttrium nitrate solution is 3-5%; the mass fraction of the chitosan solution is 5-8%; and the metal pigment is one of blue gold powder, red gold powder, and blue-red gold powder.

[0013] Preferably, the preparation method of the nano-barium metaborate doped with wollastonite is as follows:

[0014] S01: 2-5 parts of a dopamine hydrochloride solution with a mass concentration of 1-1.2 mol / L, 1-4 parts of a sodium dodecyl sulfate solution, and 0.45-0.55 parts of a phosphate buffer solution are fully stirred to obtain a pretreatment agent;

[0015] S02: wollastonite is sent to heat treatment at 145-155℃ for 5-10 min, then cooled to 50℃ at a rate of 2-5℃ / min, and then immersed in the pretreatment agent for ultrasonic improvement treatment; after the ultrasonic treatment, the pretreatment agent is extracted, dried, and a pretreated wollastonite agent is obtained;

[0016] S03: 2-5 parts of nano-barium metaborate, 1-3 parts of a lanthanum sulfate solution with a mass fraction of 5%, 0.45-0.65 parts of sodium lignosulfonate, and 4-8 parts of a sodium citrate solution with a mass fraction of 10% are fully stirred to obtain a nano-barium metaborate adjusting agent;

[0017] S04: the pretreated wollastonite agent and the nano-barium metaborate adjusting agent are mixed in a weight ratio of (5-7):3, and ball milled at a speed of 1200-1500 r / min for 1-2 h; after the ball milling, the mixture is washed with water and dried to obtain a nano-barium metaborate agent doped with wollastonite.

[0018] Preferably, the mass fraction of the sodium dodecyl sulfate solution is 4-8%, and the pH value of the phosphate buffer solution is 5.0-5.5.

[0019] Preferably, the ultrasonic power of the ultrasonic improvement treatment is 450-500 W, and the ultrasonic time is 20-30 min.

[0020] Preferably, the preparation method of the bentonite modifier is as follows:

[0021] S101: bentonite is sent to high-frequency reaction treatment in concentrated sulfuric acid; after the treatment, the bentonite is washed with water and dried to obtain a bentonite pretreatment agent;

[0022] S102: the bentonite pretreatment agent is sent to heat treatment at 350-370℃ for 10-15 min, then cooled to 150-160℃ at a rate of 1-3℃ / min, and kept at the temperature for 5-10 min, and finally air-cooled to room temperature to obtain a heat-improved bentonite agent;

[0023] S103: The heat modified bentonite agent is stirred in a modifier solution of 5-10 times the total amount of the heat modified bentonite agent, and after stirring, the product is washed and dried to obtain the bentonite modifier.

[0024] Preferably, the frequency of the high-frequency reaction treatment is 175-180 KHz, and the treatment time is 1-3 min.

[0025] Preferably, the stirring speed of the stirring modification treatment is 500-1000 r / min, the stirring time is 30-40 min, and the stirring temperature is 48-52℃.

[0026] Preferably, the preparation method of the modifier solution is as follows:

[0027] The hydroxyapatite is stirred in a 2% hydrochloric acid solution of 4-8 times the total amount of the hydroxyapatite, and then washed and dried to obtain the hydroxyapatite agent.

[0028] 3-5 parts of the hydroxyapatite agent, 1-3 parts of diethanolamine, and 1-2 parts of silica sol are added to 6-10 parts of a sodium alginate solution, and stirred to obtain the modifier solution.

[0029] Preferably, the mass fraction of the sodium alginate solution is 8-14%.

[0030] Compared with the prior art, the present application has the following advantages:

[0031] 1. The water-based nano metal ink of the present application uses a titanate coupling agent, yttrium nitrate solution and chitosan solution to prepare a coupling complex solution, which can improve the interface of the doped nanosilica barium metaborate agent, bentonite modifier and water-based polyurethane resin, optimize the compatibility of the product raw materials, and improve the performance of the product. The bentonite modifier and the doped nanosilica barium metaborate agent can mutually coordinate and synergize, the adhesion and easy cleaning effect of the product are improved, and the acid corrosion resistance of the product is significantly enhanced.

[0032] 2. The chitosan solution has the effect of permeating the raw materials, enhancing the permeability of the raw materials, and the titanate coupling agent has the effect of improving the interface, which, together with the yttrium nitrate solution, improves the interface of the system raw materials and improves the performance of the product.

[0033] 3、bentonite modifier is prepared by the following steps: the bentonite is reacted with concentrated sulfuric acid, and the activity and dispersity of the bentonite are optimized; the bentonite is heated at 350-370℃ for 10-15min, then cooled to 150-160℃ at a rate of 1-3℃ / min, and kept for 5-10min, and finally air-cooled to room temperature; the interlayer spacing of the bentonite is improved, the activity of the bentonite is optimized, the hydroxyapatite is dispersed in hydrochloric acid solution, the activity of the hydroxyapatite is improved, the modified solution of diethanolamine, silica sol, sodium alginate solution and hydroxyapatite agent is used to optimize and improve the bentonite, so that the bentonite modifier is dispersed in the matrix, the interlayer spacing is inserted into the system, the stability of the system is improved, the interlayer structure is distributed in the system, the contact force between the system and the surface is optimized, the adhesion of the product is improved, the hydroxyapatite is cooperated, the product adhesion is further improved.

[0034] 4、bentonite modifier is prepared by the following steps: the bentonite is reacted with concentrated sulfuric acid, and the activity and dispersity of the bentonite are optimized; the bentonite is heated at 350-370℃ for 10-15min, then cooled to 150-160℃ at a rate of 1-3℃ / min, and kept for 5-10min, and finally air-cooled to room temperature; the interlayer spacing of the bentonite is improved, the activity of the bentonite is optimized, the hydroxyapatite is dispersed in hydrochloric acid solution, the activity of the hydroxyapatite is improved, the modified solution of diethanolamine, silica sol, sodium alginate solution and hydroxyapatite agent is used to optimize and improve the bentonite, so that the bentonite modifier is dispersed in the matrix, the interlayer spacing is inserted into the system, the stability of the system is improved, the interlayer structure is distributed in the system, the contact force between the system and the surface is optimized, the adhesion of the product is improved, the hydroxyapatite is cooperated, the product adhesion is further improved. DETAILED DESCRIPTION

[0035] The technical solutions in the embodiments of the present application will be clearly and completely described below in combination with specific embodiments. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0036] The preparation method of the water-based nano-metal ink in the embodiment comprises the following steps:

[0037] Step one, 3-5 parts of titanium ester coupling agent, 1-3 parts of yttrium nitrate solution and 5-10 parts of chitosan solution are stirred and mixed uniformly to obtain a coupling complex solution;

[0038] Step two, 2-5 parts of the nano barium metaborate doped with wollastonite, 6-10 parts of bentonite modifier are first stirred and mixed uniformly, then the coupling complexing liquid is added and mixed fully;

[0039] Step three, the product of step two is treated in a ball mill, the ball milling speed is 1000-1500 r / min, the ball milling time is 1-2 h, after the ball milling, the product is washed with water and dried to obtain the additive improver;

[0040] Step four, the selection of raw materials: 20-30 parts of metal pigment, 40-45 parts of water-based polyurethane resin, 5-10 parts of additive improver, 2-4 parts of polyethylene wax and 20-30 parts of deionized water;

[0041] Step five, the metal pigment, water-based polyurethane resin, additive improver, polyethylene wax and deionized water are stirred and mixed uniformly to obtain the water-based nano metal ink of the application.

[0042] The mass fraction of the yttrium nitrate solution of the embodiment is 3-5%; the mass fraction of the chitosan solution is 5-8%; and the metal pigment is one of blue gold powder, red gold powder and blue-red gold powder.

[0043] The preparation method of the nano barium metaborate doped with wollastonite of the embodiment is as follows:

[0044] S01: 2-5 parts of a dopamine hydrochloride solution with a mass concentration of 1-1.2 mol / L, 1-4 parts of a sodium dodecyl sulfate solution and 0.45-0.55 parts of a phosphate buffer solution are stirred fully to obtain a pretreatment agent;

[0045] S02: the wollastonite is sent into a heat treatment at 145-155℃ for 5-10 min, then cooled to 50℃ at a rate of 2-5℃ / min, then immersed into the pretreatment agent for ultrasonic improvement treatment, after the ultrasonic treatment, the pretreatment agent is filtered and dried to obtain a pretreated wollastonite agent;

[0046] S03: 2-5 parts of nano barium metaborate, 1-3 parts of a lanthanum sulfate solution with a mass fraction of 5%, 0.45-0.65 parts of sodium lignosulfonate and 4-8 parts of a sodium citrate solution with a mass fraction of 10% are stirred and mixed uniformly to obtain a nano barium metaborate adjusting agent;

[0047] S04: the pretreated wollastonite agent and the nano barium metaborate adjusting agent are mixed uniformly according to a weight ratio of (5-7):3, and ball milling is carried out at a rotating speed of 1200-1500 r / min for 1-2 h; after the ball milling, the product is washed with water and dried to obtain the nano barium metaborate doped with wollastonite.

[0048] The mass fraction of the sodium dodecyl sulfate solution of the embodiment is 4-8%; and the pH value of the phosphate buffer solution is 5.0-5.5.

[0049] The ultrasonic power of the ultrasonic improved treatment of the embodiment is 450-500 W, and the ultrasonic time is 20-30 min.

[0050] The preparation method of the bentonite modifier of the embodiment is as follows:

[0051] S101: The bentonite is sent into concentrated sulfuric acid for high-frequency reaction treatment, and after the treatment is completed, water washing and drying are performed to obtain a bentonite pretreatment agent;

[0052] S102: The bentonite pretreatment agent is sent into heat treatment at 350-370℃ for 10-15 min, then cooled to 150-160℃ at a rate of 1-3℃ / min, and kept for 5-10 min, and finally air-cooled to room temperature to obtain a heat improved bentonite agent;

[0053] S103: The heat improved bentonite agent is sent into a modifier liquid which is 5-10 times the total amount of the heat improved bentonite agent for stirring modification treatment, and after the stirring is completed, water washing and drying are performed to obtain a bentonite modifier.

[0054] The frequency of the high-frequency reaction treatment of the embodiment is 175-180 KHz, and the treatment time is 1-3 min.

[0055] The stirring speed of the stirring modification treatment of the embodiment is 500-1000 r / min, the stirring time is 30-40 min, and the stirring temperature is 48-52℃.

[0056] The preparation method of the modifier liquid of the embodiment is as follows:

[0057] The hydroxyapatite is placed in a 2% hydrochloric acid solution with a mass fraction of 4-8 times the total amount of the hydroxyapatite for stirring and uniform dispersion, and then water washing and drying are performed to obtain a hydroxyapatite agent;

[0058] 3-5 parts of the hydroxyapatite agent, 1-3 parts of diethanolamine, and 1-2 parts of silica sol are added to 6-10 parts of a sodium alginate solution, and stirring is performed to obtain a modifier liquid.

[0059] The mass fraction of the sodium alginate solution of the embodiment is 8-14%.

[0060] Embodiment 1.

[0061] The preparation method of the aqueous nanometal ink of the embodiment includes the following steps:

[0062] Step one, 3 parts of a titanate coupling agent, 1 part of a yttrium nitrate solution, and 5 parts of a chitosan solution are stirred and uniformly mixed to obtain a coupling complexing liquid;

[0063] Step two, 2 parts of a nanometer barium metaborate agent doped with wollastonite and 6 parts of a bentonite modifier are first stirred and uniformly mixed, and then the coupling complexing liquid is added and fully mixed.

[0064] Step 3: The product from Step 2 is then ball-milled in a ball mill at a speed of 1000 r / min for 1 hour. After the ball milling is completed, the product is washed with water and dried to obtain the additive improver.

[0065] Step 4, Selection of raw materials: 20 parts metallic pigment, 40 parts waterborne polyurethane resin, 5 parts additive modifier, 2 parts polyethylene wax and 20 parts deionized water;

[0066] Step 5: Mix the metallic pigment, waterborne polyurethane resin, additive modifier, polyethylene wax, and deionized water to obtain the waterborne nano-metal ink of the present invention.

[0067] In this embodiment, the yttrium nitrate solution has a mass fraction of 3%; the chitosan solution has a mass fraction of 5%; and the metallic pigment is lapis lazuli powder.

[0068] The preparation method of the wollastonite-doped barium metaborate nanoparticles in this embodiment is as follows:

[0069] S01: Mix 2 parts of a 1 mol / L dopamine hydrochloride solution, 1 part of a sodium dodecyl sulfate solution, and 0.45 parts of a phosphate buffer solution thoroughly to obtain a pretreatment agent;

[0070] S02: Wollastonite is heat-treated at 145°C for 5 min, then cooled to 50°C at a rate of 2°C / min, and then immersed in a pretreatment agent for ultrasonic improvement treatment. After ultrasonic treatment, the mixture is filtered and dried to obtain the pretreated wollastonite agent.

[0071] S03: Mix 2 parts of barium metaborate nanoparticles, 1 part of 5% lanthanum sulfate solution, 0.45 parts of sodium lignosulfonate and 4 parts of 10% sodium citrate solution to obtain barium metaborate nanoparticle regulator.

[0072] S04: The pretreated wollastonite agent and the nano-barium metaborate modifier are mixed at a weight ratio of 5:3 and ball-milled at a speed of 1200 r / min for 1 h. After ball milling, the mixture is washed with water and dried to obtain the wollastonite-doped nano-barium metaborate agent.

[0073] In this embodiment, the sodium dodecyl sulfate solution has a mass fraction of 4%; the pH value of the phosphate buffer solution is 5.0.

[0074] In this embodiment, the ultrasonic power of the ultrasonic improvement process is 450W, and the ultrasonic time is 20min.

[0075] The preparation method of the bentonite modifier in this embodiment is as follows:

[0076] S101: Bentonite is fed into concentrated sulfuric acid for high-frequency reaction treatment. After the treatment is completed, it is washed with water and dried to obtain bentonite pretreatment agent.

[0077] S102: The bentonite pretreatment agent is then heat-treated at 350℃ for 10 minutes, then cooled to 150℃ at a rate of 1℃ / min, held for 5 minutes, and finally air-cooled to room temperature to obtain the heat-modified bentonite agent.

[0078] S103: The thermally modified bentonite agent is added to a modifying liquid five times the total amount of the thermally modified bentonite agent and stirred for modification treatment. After stirring, the bentonite is washed with water and dried to obtain the bentonite modifier.

[0079] In this embodiment, the high-frequency reaction processing frequency is 175KHz and the processing time is 1min.

[0080] In this embodiment, the stirring speed for the stirring modification treatment is 500 r / min, the stirring time is 30 min, and the stirring temperature is 48℃.

[0081] The preparation method of the modified liquid in this embodiment is as follows:

[0082] Hydroxyapatite was placed in a 2% hydrochloric acid solution (4 times the total amount of hydroxyapatite) and stirred until evenly dispersed. Then, it was washed with water and dried to obtain the hydroxyapatite agent.

[0083] Add 3 parts hydroxyapatite, 1 part diethanolamine and 1 part silica sol to 6 parts sodium alginate solution and stir thoroughly to obtain the modified solution.

[0084] The sodium alginate solution in this embodiment has a mass fraction of 8%.

[0085] Example 2.

[0086] The preparation method of the water-based nano-metal ink of this embodiment includes the following steps:

[0087] Step 1: Mix 5 parts titanate coupling agent, 3 parts yttrium nitrate solution and 10 parts chitosan solution to obtain a coupling compound solution;

[0088] Step 2: First, stir and mix 5 parts of wollastonite-doped nano-barium metaborate agent and 10 parts of bentonite modifier evenly, then add the coupling compounding solution and continue to mix thoroughly.

[0089] Step 3: The product from Step 2 is then ball-milled in a ball mill at a speed of 1500 r / min for 2 hours. After ball milling, the product is washed with water and dried to obtain the additive modifier.

[0090] Step 4, Selection of raw materials: 30 parts metallic pigment, 45 parts waterborne polyurethane resin, 10 parts additive modifier, 4 parts polyethylene wax and 30 parts deionized water.

[0091] Step 5: Mix the metallic pigment, waterborne polyurethane resin, additive modifier, polyethylene wax, and deionized water to obtain the waterborne nano-metal ink of the present invention.

[0092] In this embodiment, the yttrium nitrate solution has a mass fraction of 5%; the chitosan solution has a mass fraction of 8%; and the metallic pigment is red gold powder.

[0093] The preparation method of the wollastonite-doped barium metaborate nanoparticles in this embodiment is as follows:

[0094] S01: Mix 5 parts of a 1.2 mol / L dopamine hydrochloride solution, 4 parts of a sodium dodecyl sulfate solution, and 0.55 parts of a phosphate buffer solution thoroughly to obtain a pretreatment agent;

[0095] S02: Wollastonite is heat-treated at 155°C for 10 min, then cooled to 50°C at a rate of 5°C / min, and then immersed in a pretreatment agent for ultrasonic improvement treatment. After ultrasonic treatment, the mixture is filtered and dried to obtain the pretreated wollastonite agent.

[0096] S03: Mix 5 parts of nano barium metaborate, 3 parts of 5% lanthanum sulfate solution, 0.65 parts of sodium lignosulfonate and 8 parts of 10% sodium citrate solution to obtain nano barium metaborate regulator.

[0097] S04: The pretreated wollastonite agent and the nano-barium metaborate modifier are mixed at a weight ratio of 7:3 and ball-milled at a speed of 1500 r / min for 2 h. After ball milling, the mixture is washed with water and dried to obtain the wollastonite-doped nano-barium metaborate agent.

[0098] In this embodiment, the sodium dodecyl sulfate solution has a mass fraction of 8%; the pH value of the phosphate buffer solution is 5.5.

[0099] In this embodiment, the ultrasonic power of the ultrasonic improvement process is 500W, and the ultrasonic time is 30min.

[0100] The preparation method of the bentonite modifier in this embodiment is as follows:

[0101] S101: Bentonite is fed into concentrated sulfuric acid for high-frequency reaction treatment. After the treatment is completed, it is washed with water and dried to obtain bentonite pretreatment agent.

[0102] S102: The bentonite pretreatment agent is then heat-treated at 370℃ for 15 minutes, then cooled to 160℃ at a rate of 3℃ / min, held for 10 minutes, and finally air-cooled to room temperature to obtain the heat-modified bentonite agent.

[0103] S103: The thermally modified bentonite agent is added to a modifying liquid of 5 to 10 times the total amount of the thermally modified bentonite agent and stirred for modification treatment. After stirring, the bentonite is washed with water and dried to obtain the bentonite modifier.

[0104] In this embodiment, the high-frequency reaction processing frequency is 180KHz and the processing time is 3min.

[0105] In this embodiment, the stirring speed for the stirring modification treatment is 1000 r / min, the stirring time is 40 min, and the stirring temperature is 52℃.

[0106] The preparation method of the modified liquid in this embodiment is as follows:

[0107] Hydroxyapatite was placed in a 2% hydrochloric acid solution (8 times the total amount of hydroxyapatite) and stirred until evenly dispersed. Then, it was washed with water and dried to obtain the hydroxyapatite agent.

[0108] Add 5 parts hydroxyapatite, 3 parts diethanolamine and 2 parts silica sol to 10 parts sodium alginate solution and stir thoroughly to obtain the modified solution.

[0109] The sodium alginate solution in this embodiment has a mass fraction of 14%.

[0110] Example 3.

[0111] The preparation method of the water-based nano-metal ink of this embodiment includes the following steps:

[0112] Step 1: Mix 4 parts titanate coupling agent, 2 parts yttrium nitrate solution and 7.5 parts chitosan solution to obtain a coupling compound solution;

[0113] Step 2: First, stir and mix 3.5 parts of wollastonite-doped nano-barium metaborate agent and 8 parts of bentonite modifier evenly, then add the coupling compounding solution and continue to mix thoroughly.

[0114] Step 3: The product from Step 2 is then ball-milled in a ball mill at a speed of 1250 r / min for 1.5 h. After ball milling, the product is washed with water and dried to obtain the additive modifier.

[0115] Step 4, Selection of raw materials: 25 parts metallic pigment, 42.5 parts waterborne polyurethane resin, 7.5 parts additive modifier, 3 parts polyethylene wax and 25 parts deionized water;

[0116] Step 5: Mix the metallic pigment, waterborne polyurethane resin, additive modifier, polyethylene wax, and deionized water to obtain the waterborne nano-metal ink of the present invention.

[0117] In this embodiment, the yttrium nitrate solution has a mass fraction of 4%; the chitosan solution has a mass fraction of 6.5%; and the metallic pigment is cyan-red gold powder.

[0118] The preparation method of the wollastonite-doped barium metaborate nanoparticles in this embodiment is as follows:

[0119] S01: Mix 3.5 parts of a 1.1 mol / L dopamine hydrochloride solution, 2.5 parts of a sodium dodecyl sulfate solution, and 0.50 parts of a phosphate buffer solution thoroughly to obtain a pretreatment agent;

[0120] S02: Wollastonite is heat-treated at 150°C for 7.5 min, then cooled to 50°C at a rate of 3.5°C / min, and then immersed in a pretreatment agent for ultrasonic improvement treatment. After ultrasonic treatment, the mixture is filtered and dried to obtain the pretreated wollastonite agent.

[0121] S03: Mix 3.5 parts of nano barium metaborate, 2 parts of 5% lanthanum sulfate solution, 0.50 parts of sodium lignosulfonate and 6 parts of 10% sodium citrate solution to obtain nano barium metaborate regulator.

[0122] S04: The pretreated wollastonite agent and the nano-barium metaborate modifier are mixed at a weight ratio of 2:1 and ball-milled at a speed of 1350 r / min for 1.5 h. After ball milling, the mixture is washed with water and dried to obtain the wollastonite-doped nano-barium metaborate agent.

[0123] In this embodiment, the sodium dodecyl sulfate solution has a mass fraction of 6%; the pH value of the phosphate buffer solution is 5.2.

[0124] In this embodiment, the ultrasonic power of the ultrasonic improvement process is 470W, and the ultrasonic time is 25min.

[0125] The preparation method of the bentonite modifier in this embodiment is as follows:

[0126] S101: Bentonite is fed into concentrated sulfuric acid for high-frequency reaction treatment. After the treatment is completed, it is washed with water and dried to obtain bentonite pretreatment agent.

[0127] S102: The bentonite pretreatment agent is then heat-treated at 360℃ for 12 minutes, then cooled to 155℃ at a rate of 2℃ / min, held for 7.5 minutes, and finally air-cooled to room temperature to obtain the heat-modified bentonite agent.

[0128] S103: The thermally modified bentonite agent is added to a modifying liquid of 5 to 10 times the total amount of the thermally modified bentonite agent and stirred for modification treatment. After stirring, the bentonite is washed with water and dried to obtain the bentonite modifier.

[0129] In this embodiment, the high-frequency reaction processing frequency is 178KHz and the processing time is 2min.

[0130] In this embodiment, the stirring speed for the stirring modification treatment is 750 r / min, the stirring time is 35 min, and the stirring temperature is 50℃.

[0131] The preparation method of the modified liquid in this embodiment is as follows:

[0132] Hydroxyapatite was placed in a 2% hydrochloric acid solution (6 times the total amount of hydroxyapatite) and stirred until evenly dispersed. Then, it was washed with water and dried to obtain the hydroxyapatite agent.

[0133] Add 4 parts hydroxyapatite, 2 parts diethanolamine and 1.5 parts silica sol to 8 parts sodium alginate solution and stir thoroughly to obtain the modified solution.

[0134] The sodium alginate solution in this embodiment has a mass fraction of 10%.

[0135] Comparative Example 1.

[0136] Unlike Example 3, this example did not use a bentonite modifier.

[0137] Comparative Example 2.

[0138] Unlike Example 3, no modifying liquid was added during the preparation of the bentonite modifier.

[0139] Comparative Example 3.

[0140] Unlike Example 3, S102 treatment was not used in the preparation of the bentonite modifier.

[0141] Comparative Example 4.

[0142] Unlike Example 3, this one does not contain nano-barium metaborate agent doped with wollastonite.

[0143] Comparative Example 5.

[0144] The preparation method of the nano-barium metaborate agent doped with wollastonite is different from that of Example 3: the ultrasonic improvement treatment in the pretreatment agent was not used.

[0145] Comparative Example 6.

[0146] Unlike Example 3, the pretreatment agent in the preparation of the wollastonite-doped barium metaborate nanoparticles did not include dopamine hydrochloride solution.

[0147] Comparative Example 7.

[0148] Unlike Example 3, the preparation of the wollastonite-doped barium metaborate nanoparticles did not use a barium metaborate nanoparticle modifier.

[0149] Comparative Example 8.

[0150] Unlike Example 3, the preparation method of the nano-barium metaborate regulator is different, and nano-barium metaborate is not added.

[0151] Comparative Example 9.

[0152] Unlike Example 3, the preparation method of the nano-barium metaborate regulator is different, and lanthanum sulfate solution and sodium lignosulfonate were not added.

[0153] Comparative Example 10.

[0154] Unlike Example 3, no coupling compounding solution treatment was used.

[0155] Comparative Example 11.

[0156] Unlike Example 3, yttrium nitrate solution was not added in the preparation of the coupling compound solution.

[0157] Performance tests were conducted on the products of Examples 1-3 and Comparative Examples 1-11. A mixture of oil and dust at a weight ratio of 2:1 was applied to the test products, which were then left at 35°C for 6 hours. The products were then wiped clean, and the adhesion strength between the product and the substrate was tested. Simultaneously, the products were placed in a 2% hydrochloric acid solution for 12 hours to test their acid resistance. The test results are as follows.

[0158]

[0159] As can be seen from Comparative Examples 1-11 and Examples 1-3;

[0160] Example 3: Under normal conditions, the product can achieve a maximum bonding strength of 13.8 MPa and a minimum wiping force of 2.2 N. The product has excellent adhesion and easy cleaning ability, and its performance can be improved in a coordinated manner. At the same time, the product has excellent performance stability under acidic conditions.

[0161] As can be seen from Comparative Examples 1-3 and Example 3, the performance of the product deteriorated significantly when the bentonite modifier was not used in the present invention. At the same time, the performance of the product also deteriorated when the modifier was not treated with the modifying liquid or with S102. Only the bentonite modifier prepared by the method of the present invention showed the most significant performance effect.

[0162] As can be seen from Comparative Examples 1, 6 and 11, and Example 3, the performance of the products in this invention showed a significant trend of deterioration when no bentonite modifier, no addition of nano-barium metaborate agent doped with wollastonite, and no coupling compounding solution treatment were used. Only by using the three factors in a coordinated and synergistic manner can the performance of the product be most significantly improved, achieving a coordinated improvement in product adhesion and easy cleaning ability. At the same time, the product exhibits excellent performance stability under acidic conditions.

[0163] As seen in Comparative Examples 4-9 and Example 3, the performance of the product without the addition of wollastonite-doped barium metaborate nano-agent also showed a significant deterioration trend. Different preparation methods for the wollastonite-doped barium metaborate nano-agent resulted in deterioration in all cases: ultrasonic improvement treatment was not used in the pretreatment agent; dopamine hydrochloride solution was not added to the pretreatment agent; barium metaborate nano-agent treatment was not used; the preparation method of the barium metaborate nano-agent was different, and barium metaborate nano-agent was not added; lanthanum sulfate solution and sodium lignosulfonate were not added. Only the product performance showed the most significant improvement when using the specific pretreatment agent of this invention for ultrasonic improvement treatment and in conjunction with the barium metaborate nano-agent prepared by the method of this invention. Other methods used to replace the product did not show the same significant performance improvement as the method of this invention.

[0164] As can be seen from Comparative Examples 10-11 and Example 3, the performance of the product deteriorated when yttrium nitrate solution was not added during the preparation of the coupling compounding solution. Only the coupling compounding solution prepared by the method of the present invention showed the most significant performance effect.

[0165] This invention further explores the product performance through the preparation of the modified liquid;

[0166] Experimental Example 1.

[0167] Same as Example 3, except that hydroxyapatite was not added during the preparation of the modified liquid.

[0168] Experimental Example 2.

[0169] Same as Example 3, except that diethanolamine was not added in the preparation of the modified liquid.

[0170] Experimental Example 3.

[0171] Same as Example 3, except that no silica sol was added in the preparation of the modified liquid.

[0172] Experimental Example 4.

[0173] Same as Example 3, except that carbon nanotubes were used instead of hydroxyapatite as the raw material.

[0174]

[0175] As can be seen from Examples 1-4, the adhesion and easy-to-clean properties of the modified liquid were significantly worse under normal and corrosion-resistant conditions when hydroxyapatite was not added during preparation. The performance of the product also tended to deteriorate when diethanolamine, silica sol, or carbon nanotubes were used instead of hydroxyapatite. Furthermore, the inventors of this invention discovered that the performance of the product deteriorated even more significantly under acidic conditions when carbon nanotubes were used instead of hydroxyapatite. The selection of hydroxyapatite is proprietary; it cannot be replaced by other raw materials. Only by using the process formulation and conditions of this invention can the product achieve the most significant performance effect. Modified liquids prepared by other methods are not as effective as those prepared by this invention.

[0176] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, it is intended that all variations falling within the meaning and scope of equivalents of the claims be included within the present invention.

[0177] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A method for preparing an aqueous nano-metallic ink, characterized in that, Includes the following steps: Step 1: Mix 3-5 parts of titanate coupling agent, 1-3 parts of yttrium nitrate solution and 5-10 parts of chitosan solution to obtain a coupling complex solution; Step 2: First, stir and mix 2-5 parts of wollastonite-doped nano-barium metaborate agent and 6-10 parts of bentonite modifier evenly, then add the coupling compounding solution and continue to mix thoroughly. Step 3: The product from Step 2 is then ball-milled in a ball mill at a speed of 1000-1500 r / min for 1-2 hours. After ball milling, the product is washed with water and dried to obtain the additive modifier. Step 4, Selection of raw materials: 20-30 parts metallic pigment, 40-45 parts waterborne polyurethane resin, 5-10 parts additive modifier, 2-4 parts polyethylene wax and 20-30 parts deionized water; Step 5: Mix the metallic pigment, waterborne polyurethane resin, additive modifier, polyethylene wax and deionized water to obtain the waterborne nano-metal ink of the present invention. The preparation method of the barium metaborate nanoparticle doped with wollastonite is as follows: S01: Mix 2-5 parts of a 1-1.2 mol / L dopamine hydrochloride solution, 1-4 parts of a sodium dodecyl sulfate solution, and 0.45-0.55 parts of a phosphate buffer solution thoroughly to obtain a pretreatment agent; S02: Wollastonite is heat-treated at 145-155℃ for 5-10 min, then cooled to 50℃ at a rate of 2-5℃ / min, and then immersed in a pretreatment agent for ultrasonic improvement treatment. After ultrasonic treatment, the mixture is filtered and dried to obtain the pretreated wollastonite agent. S03: Mix 2-5 parts of nano barium metaborate, 1-3 parts of 5% lanthanum sulfate solution, 0.45-0.65 parts of sodium lignosulfonate and 4-8 parts of 10% sodium citrate solution to obtain nano barium metaborate regulator. S04: Mix the pretreated wollastonite agent and the nano barium metaborate modifier at a weight ratio of (5-7):3, and ball mill at a speed of 1200-1500 r / min for 1-2 h; after ball milling, wash with water and dry to obtain the wollastonite-doped nano barium metaborate agent. The preparation method of the bentonite modifier is as follows: S101: Bentonite is fed into concentrated sulfuric acid for high-frequency reaction treatment. After the treatment is completed, it is washed with water and dried to obtain bentonite pretreatment agent. S102: The bentonite pretreatment agent is then heat-treated at 350-370℃ for 10-15 minutes, then cooled to 150-160℃ at a rate of 1-3℃ / min, held for 5-10 minutes, and finally air-cooled to room temperature to obtain the heat-modified bentonite agent. S103: The thermally modified bentonite agent is added to a modification liquid of 5 to 10 times the total amount of the thermally modified bentonite agent and stirred for modification treatment. After stirring, the bentonite is washed with water and dried to obtain the bentonite modifier. The modified liquid is prepared by: Hydroxyapatite was placed in a 2% hydrochloric acid solution (4-8 times the total amount of hydroxyapatite) and stirred until evenly dispersed. Then, it was washed with water and dried to obtain the hydroxyapatite agent. Add 3-5 parts of hydroxyapatite, 1-3 parts of diethanolamine and 1-2 parts of silica sol to 6-10 parts of sodium alginate solution, stir thoroughly to obtain the modified solution.

2. The method for preparing the water-based nano-metal ink according to claim 1, characterized in that, The yttrium nitrate solution has a mass fraction of 3-5%; the chitosan solution has a mass fraction of 5-8%; and the metallic pigment is one of lapis lazuli, red gold, or lapis lazuli-red gold.

3. The method for preparing the water-based nano-metal ink according to claim 1, characterized in that, The sodium dodecyl sulfate solution has a mass fraction of 4-8%; the phosphate buffer solution has a pH value of 5.0-5.

5.

4. The method for preparing the water-based nano-metal ink according to claim 1, characterized in that, The ultrasonic power of the ultrasonic improvement treatment is 450-500W, and the ultrasonic time is 20-30min.

5. The method for preparing water-based nano-metallic ink according to claim 1, characterized in that, The high-frequency reaction process has a frequency of 175–180 kHz and a processing time of 1–3 minutes.

6. The method for preparing water-based nano-metallic ink according to claim 1, characterized in that, The stirring speed for the stirring modification treatment is 500-1000 r / min, the stirring time is 30-40 min, and the stirring temperature is 48-52℃.

7. The method for preparing the water-based nano-metal ink according to claim 1, characterized in that, The sodium alginate solution has a mass fraction of 8-14%.

Images