Conductive UV ink-jet ink containing silver nanowires and preparation method of conductive UV ink-jet ink

Abstract

The invention belongs to the technical field of conductive ink, and particularly relates to conductive UV ink-jet ink containing silver nanowires and a preparation method of the conductive UV ink-jet ink. According to the preparation method, the carbon nanotubes are subjected to composite modification, silver loading is realized through a heating reduction method, photocuring performance is obtained by means of grafting of dopamine and acrylic acid, and the conductive UV ink-jet ink containing the silver nanowires is prepared by being matched with the modified silver nanowires for common use, so that the conductive UV ink-jet ink containing the silver nanowires is prepared on the basis of ensuring that the ink is dispersed stably and does not generate precipitates; and the conductivity is effectively improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of conductive inks, and in particular relates to a conductive UV inkjet ink containing nano silver wires and a preparation method thereof. Background Art

[0002] Conductive inks are a key material for the printed production of electronic devices. These inks require excellent electrical, thermal, and optical properties, as well as high viscosity, lightweight construction, and excellent adhesion. Silver nanomaterials offer excellent electrical conductivity, mechanical flexibility, and chemical stability. They can be stably dispersed in media, are easily formulated into inks, and are relatively low-cost, making them ideal materials for preparing conductive inks. Silver nanoconductive inks typically possess specific properties for flexibility, viscosity, resistivity, rheology, particle size distribution, drying conditions, and other printability, leading to their increasing application in industries such as flexible displays and semiconductors.

[0003] A Chinese patent (CN117186700A) discloses an inkjet-printable conductive ink, its preparation method, and its application. This invention first modifies the surface of carbon nanotubes by introducing acrylic acid groups, making them both photocurable and significantly improving their dispersibility. This results in photocurable carbon nanotubes, which are then used to prepare an inkjet-printable conductive ink. This significantly alleviates the difficulty in dispersing carbon nanotubes, resulting in a well-dispersed, photocurable conductive ink with excellent conductivity, stable performance, and effective wear resistance. This ink is widely used in fields such as circuit printing, electromagnetic shielding, electronic touch screens, and flexible displays. However, the conductive ink containing carbon nanotubes prepared using this patented technology fails to balance conductivity and stability, severely limiting its application scenarios and preventing its use in demanding applications.

[0004] Therefore, how to screen suitable main ingredients and introduce functional modified components to prepare conductive UV inkjet ink, and effectively improve the conductivity while ensuring that the ink is dispersed stably and does not precipitate, has become a direction that needs to be focused on. Summary of the Invention

[0005] In view of the shortcomings of the existing technology, the purpose of the present invention is to provide a conductive UV inkjet ink containing nano silver wires and a preparation method thereof, aiming to solve the problem that the conductive ink containing carbon nanotubes in the existing technology cannot take into account both conductivity and stability.

[0006] The present invention conducts composite modification on carbon nanotubes, firstly realizes silver loading by a heating reduction method, then obtains light-curing performance by means of grafting of dopamine and acrylic acid, and uses the modified nano silver wires together to prepare a conductive UV inkjet ink containing nano silver wires, which effectively improves the conductivity while ensuring that the ink is dispersed stably and does not precipitate.

[0007] The technical solutions adopted by the present invention to solve the above technical problems are as follows: In a first aspect of the present invention, a conductive UV inkjet ink containing silver nanowires is provided, comprising the following components in parts by weight: 40-50 parts of carbon nanotubes, 4-8 parts of modified nano silver wires, 2-6 parts of polyester acrylate resin, 2-4 parts of pentaerythritol triacrylate, 1-2 parts of photoinitiator and 50-70 parts of solvent.

[0008] As a preferred technical solution of the present invention, the weight proportion of the carbon nanotubes can be 40 parts, 42 parts, 44 parts, 46 parts, 48 parts or 50 parts.

[0009] As a preferred technical solution of the present invention, the weight proportions of the modified nano silver wires can be 4 parts, 5 parts, 6 parts, 7 parts or 8 parts.

[0010] As a preferred technical solution of the present invention, the weight proportion of the polyester acrylate resin can be 2 parts, 3 parts, 4 parts, 5 parts or 6 parts.

[0011] As a preferred technical solution of the present invention, the weight proportion of the pentaerythritol triacrylate can be 2 parts, 2.5 parts, 3 parts, 3.5 parts or 4 parts.

[0012] As a preferred technical solution of the present invention, the weight proportion of the photoinitiator can be 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts or 2 parts.

[0013] As a preferred technical solution of the present invention, the weight proportion of the solvent can be 50 parts, 55 parts, 60 parts, 65 parts or 70 parts.

[0014] As a preferred technical solution of the present invention, the preparation method of the modified nano silver wire includes: adding 1.2 to 1.6 parts of graphene oxide to 400 to 500 parts of ethylene glycol by weight and ultrasonically dispersing them, then adding 80 to 100 parts of silver nitrate and stirring to dissolve them to obtain liquid A; adding 0.6 to 0.8 parts of ferric chloride to 400 to 500 parts of ethylene glycol and fully dissolving them to obtain a ferric chloride solution, adding 10 to 16 parts of polyvinyl pyrrolidone to 400 to 500 parts of ethylene glycol and stirring to dissolve them, and then adding 10 to 20 parts of the ferric chloride solution and stirring evenly to obtain liquid B; adding 200 to 240 parts of liquid A to 400 to 500 parts of liquid B for high temperature reaction to obtain modified nano silver wire.

[0015] As a preferred technical solution of the present invention, the conditions of the high-temperature reaction include: reacting at 160-170° C. for 3-5 hours, cooling, centrifugally washing with acetone and anhydrous ethanol in sequence, and drying.

[0016] During the preparation process of modified nanosilver wires, graphene oxide has a large number of negatively charged oxygen-containing functional groups. The negatively charged graphene oxide adsorbs a large number of silver ions around it through electrostatic action. Under the solvent thermal reaction conditions, the silver ions adsorbed by graphene oxide are reduced to silver atoms and aggregated on the graphene oxide sheets. At the same time, under the joint action of iron ions and polyvinyl pyrrolidone, the reduced silver atoms can only be deposited on specific crystal planes, thus forming modified nanosilver wires.

[0017] As a preferred technical solution of the present invention, the photoinitiator is selected from at least one of diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, 2,4-diethylthioxanthone, and 2-isopropylthioxanthone.

[0018] As a preferred technical solution of the present invention, the solvent is selected from at least one of n-butanol, tert-butanol, and isopropanol.

[0019] As a preferred technical solution of the present invention, the carbon nanotubes are composite modified carbon nanotubes; The preparation method of the composite modified carbon nanotubes comprises: firstly subjecting 4 to 8 parts of multi-walled carbon nanotubes to acidification treatment, and then adding them to 400 to 600 parts of deionized water for ultrasonic dispersion to obtain a carbon nanotube dispersion; mixing 40 to 60 parts of 0.1 mol / L silver nitrate solution and 10 to 20 parts of 0.2 mol / L glucose solution, and then adding 0.4 to 0.8 parts of starch and 0.6 to 0.8 parts of trisodium citrate and stirring evenly to obtain a mixed solution; and then adding 50 to 80 parts of the The mixed liquid is dropwise added to 400-600 parts of the carbon nanotube dispersion for stirring and reaction to obtain silver-loaded carbon nanotubes; 4-8 parts of the silver-loaded carbon nanotubes are added to 500-600 parts of anhydrous ethanol and dispersed evenly, and then 2-4 parts of dopamine hydrochloride are added to carry out self-polymerization to obtain modified carbon nanotubes; 4-8 parts of the modified carbon nanotubes are added to 80-100 parts of deionized water, and then 20-30 parts of acrylic acid are added for grafting treatment to obtain composite modified carbon nanotubes.

[0020] As a preferred technical solution of the present invention, the acidification treatment step includes: adding 4 to 8 parts by weight of commercially available carbon nanotubes to a mixture of 100 to 120 parts of nitric acid and 280 to 300 parts of sulfuric acid, acidifying at 100 to 110° C. for 60 to 80 minutes, filtering, washing with water, centrifuging, and drying.

[0021] As a preferred technical solution of the present invention, the stirring reaction conditions include: first ultrasonic mixing for 50-60 minutes, then heating to 60-70°C, stirring at a speed of 80-100 r / min for 2-4 hours, high-speed centrifugation, water washing, and drying.

[0022] As a preferred technical solution of the present invention, the conditions for the self-polymerization include: adjusting the pH to 8.2-8.4, stirring at room temperature for 2-4 hours, centrifuging, and washing with water.

[0023] As a preferred technical solution of the present invention, the grafting treatment conditions include: placing in a nitrogen atmosphere, constant temperature reaction at 58-60° C. for 20-30 minutes, filtering, washing with water, and drying.

[0024] The composite modified carbon nanotubes use silver nitrate as a metal precursor, glucose as a reducing agent, and starch as a protective agent. The metal precursor liquid is filled into the interior of the multi-walled carbon nanotubes through ultrasonic dispersion and capillary action, and then the generated nanosilver particles are assembled inside the carbon nanotube lumen by heating and reduction; then dopamine is added and the pH is controlled to cause self-polymerization, and abundant catechol groups and amino groups are introduced on the surface of the modified carbon nanotubes. Acrylic acid is then grafted on through these functional groups to obtain composite modified carbon nanotubes with photocuring properties.

[0025] A second aspect of the present invention provides a method for preparing the conductive UV inkjet ink containing nanosilver wires as described in the first aspect, comprising the following steps: In parts by weight, 40-50 parts of carbon nanotubes, 4-8 parts of modified nanosilver wires, 2-6 parts of polyester acrylate resin, 2-4 parts of pentaerythritol triacrylate, 1-2 parts of photoinitiator and 50-70 parts of solvent are mixed, stirred at 70-76° C. for 50-60 minutes, and then transferred to a grinder for grinding for 100-120 minutes to obtain a conductive UV inkjet ink containing nanosilver wires.

[0026] The present invention also provides an application method of the above-mentioned conductive UV inkjet ink containing nanosilver wires, which specifically comprises injecting the ink into an ink cartridge, depositing the ink onto a substrate using a UV inkjet printer, and curing the ink to obtain a printed substrate.

[0027] Compared with the prior art, the present invention has the following beneficial effects: (1) The modified silver nanowires of the present invention can provide long-range electron transmission channels, form an efficient conductive network, and significantly improve the conductivity of the ink; a small amount of graphene oxide can adjust the surface tension of the ink, prevent agglomeration, and improve the dispersion stability of the modified silver nanowires.

[0028] (2) Dopamine in the composite modified carbon nanotubes of the present invention can form polydopamine through self-polymerization. Polydopamine can reduce the agglomeration of carbon nanotubes and improve the interfacial compatibility, thereby increasing the dispersion stability of the composite modified carbon nanotubes in the ink. Silver-loaded carbon nanotubes, due to their high electrical conductivity and unique nanostructure, can significantly improve the conductivity of the ink when added in small amounts.

[0029] (3) The graphene in the composite modified carbon nanotubes and nano silver wires of the present invention both have hybrid carbon structures. The π electron clouds of the two can form a physical bond through π-π interaction. The two materials work together to build a denser and more effective conductive network, thereby further improving the overall conductivity and stability of the UV inkjet ink. DETAILED DESCRIPTION

[0030] For the convenience of understanding the present invention, the present invention is given below with examples. It should be understood by those skilled in the art that the examples are only for the purpose of helping to understand the present invention and should not be regarded as specific limitations of the present invention.

[0031] The sources of some components in the Examples and Comparative Examples are as follows: Hydroxylated carbon nanotubes, product number 100311, were purchased from Jiangsu Xianfeng Nanomaterials Technology Co., Ltd. Nanosilver, product number 100422, was purchased from Jiangsu Xianfeng Nanomaterial Technology Co., Ltd.; Polyester acrylate resin, product number JS230, was purchased from Hunan Jinhai Technology Co., Ltd.; Pentaerythritol triacrylate, product number P189117, was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.; Diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, CAS No. 75980-60-8, was purchased from Shanghai MacLean Biochemical Technology Co., Ltd.; 2,4-Diethylthioxanthone, CAS No. 82799-44-8, was purchased from Shanghai MacLean Biochemical Technology Co., Ltd.; 2-Isopropylthioxanthone, CAS No. 5495-84-1, was purchased from Shanghai MacLean Biochemical Technology Co., Ltd.; n-Butanol, CAS No. 71-36-3, was purchased from Sinopharm Chemical Reagent Co., Ltd.; Tert-butyl alcohol, CAS No. 75-65-0, was purchased from Sinopharm Chemical Reagent Co., Ltd.; Isopropyl alcohol, CAS No. 67-63-0, was purchased from Sinopharm Chemical Reagent Co., Ltd.; Graphene oxide, product number G476611, was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd. Ethylene glycol, CAS No. 107-21-1, was purchased from Sinopharm Chemical Reagent Co., Ltd.; Silver nitrate, CAS No. 7761-88-8, was purchased from Sinopharm Chemical Reagent Co., Ltd.; Ferric chloride, CAS No. 10025-77-1, was purchased from Shanghai MacLean Biochemical Technology Co., Ltd.; Polyvinylpyrrolidone, product number P110611, was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.; Commercially available carbon nanotubes, product number C805984, were purchased from Shanghai MacLean Biochemical Technology Co., Ltd.; Nitric acid, CAS No. 7697-37-2, was purchased from Sinopharm Chemical Reagent Co., Ltd.; Sulfuric acid, CAS No. 7664-93-9, was purchased from Sinopharm Chemical Reagent Co., Ltd.; Silver nitrate, CAS No. 7761-88-8, was purchased from Sinopharm Chemical Reagent Co., Ltd.; Glucose, CAS No. 50-99-7, was purchased from Shanghai MacLean Biochemical Technology Co., Ltd.; Starch, CAS No. 9005-84-9, was purchased from Sinopharm Chemical Reagent Co., Ltd.; Trisodium citrate, CAS No. 68-04-2, was purchased from Sinopharm Chemical Reagent Co., Ltd. Dopamine hydrochloride, CAS No. 62-31-7, was purchased from Shanghai MacLean Biochemical Technology Co., Ltd.; Acrylic acid, CAS No. 79-10-7, was purchased from Sinopharm Chemical Reagent Co., Ltd.

[0032] Example 1 This embodiment provides a method for preparing a conductive UV inkjet ink containing nanosilver wires, comprising the following steps: In parts by weight, 50 parts of composite modified carbon nanotubes, 8 parts of modified nano silver wires, 6 parts of polyester acrylate resin, 4 parts of pentaerythritol triacrylate, 2 parts of photoinitiator diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide and 70 parts of solvent n-butanol were mixed, stirred at 76° C. for 50 minutes, and then transferred to a grinder and ground for 120 minutes to obtain a conductive UV inkjet ink containing nano silver wires.

[0033] The modified silver nanowires are prepared as follows: 1.6 parts of graphene oxide are added to 500 parts of ethylene glycol for ultrasonic dispersion, and 100 parts of silver nitrate are added and stirred to dissolve to obtain liquid A; 0.8 parts of ferric chloride are added to 500 parts of ethylene glycol for thorough dissolution to obtain a ferric chloride solution, 16 parts of polyvinyl pyrrolidone are added to 500 parts of ethylene glycol for stirring to dissolve, and then 20 parts of the ferric chloride solution are added and stirred to obtain liquid B; 240 parts of liquid A are added to 500 parts of liquid B for high-temperature reaction at 170°C for 3 hours, cooled, centrifuged and washed with acetone and anhydrous ethanol in sequence, and dried to obtain the modified silver nanowires.

[0034] Preparation of the composite modified carbon nanotubes: 8 parts by weight of commercially available carbon nanotubes are added to a mixture of 100 parts of nitric acid and 300 parts of sulfuric acid, acidified at 110° C. for 60 minutes, filtered, washed with water, centrifuged, dried, and then added to 600 parts of deionized water for ultrasonic dispersion to obtain a carbon nanotube dispersion; 60 parts of 0.1 mol / L silver nitrate solution and 20 parts of 0.2 mol / L glucose solution are mixed, and then 0.8 parts of starch and 0.8 parts of trisodium citrate are added and stirred uniformly to obtain a mixed solution; 80 parts of the mixed solution are added dropwise to 600 parts of the carbon nanotube dispersion for stirring and reaction, and ultrasonic mixing is performed for 6 minutes. 0min, then heating to 70°C, stirring at a speed of 100r / min for 2h, high-speed centrifugal separation, water washing, and drying to obtain silver-loaded carbon nanotubes; 8 parts of the silver-loaded carbon nanotubes are added to 600 parts of anhydrous ethanol and dispersed evenly, then 4 parts of dopamine hydrochloride are added for self-polymerization, the pH is adjusted to 8.4, stirred at room temperature for 4h, centrifuged, washed with water to obtain modified carbon nanotubes; 8 parts of the modified carbon nanotubes are added to 100 parts of deionized water, and then 30 parts of acrylic acid are added for grafting treatment, placed in a nitrogen atmosphere, and reacted at a constant temperature of 60°C for 20min, filtered, washed with water, and dried to obtain composite modified carbon nanotubes.

[0035] Example 2 This embodiment provides a method for preparing a conductive UV inkjet ink containing nanosilver wires, comprising the following steps: In parts by weight, 40 parts of composite modified carbon nanotubes, 4 parts of modified nano silver wires, 2 parts of polyester acrylate resin, 2 parts of pentaerythritol triacrylate, 1 part of photoinitiator 2,4-diethylthioxanthone and 50 parts of solvent tert-butanol were mixed, stirred at 70° C. for 60 minutes, and then transferred to a grinder and ground for 120 minutes to obtain a conductive UV inkjet ink containing nano silver wires.

[0036] The modified silver nanowires are prepared as follows: 1.2 parts of graphene oxide are added to 400 parts of ethylene glycol for ultrasonic dispersion, and 80 parts of silver nitrate are added and stirred to dissolve to obtain liquid A; 0.6 parts of ferric chloride are added to 400 parts of ethylene glycol and fully dissolved to obtain a ferric chloride solution; 10 parts of polyvinyl pyrrolidone are added to 400 parts of ethylene glycol and stirred to dissolve; then 10 parts of the ferric chloride solution are added and stirred to obtain liquid B; 200 parts of liquid A are added to 400 parts of liquid B for high-temperature reaction at 160° C. for 5 hours, cooled, centrifuged and washed with acetone and anhydrous ethanol in sequence, and dried to obtain the modified silver nanowires.

[0037] Preparation of the composite modified carbon nanotubes: 4 parts by weight of commercially available carbon nanotubes are added to a mixture of 120 parts of nitric acid and 280 parts of sulfuric acid, acidified at 100°C for 80 minutes, filtered, washed with water, centrifuged, dried, and then added to 400 parts of deionized water for ultrasonic dispersion to obtain a carbon nanotube dispersion; 40 parts of 0.1 mol / L silver nitrate solution and 10 parts of 0.2 mol / L glucose solution are mixed, and then 0.4 parts of starch and 0.6 parts of trisodium citrate are added and stirred uniformly to obtain a mixed solution; 50 parts of the mixed solution are added dropwise to 400 parts of the carbon nanotube dispersion for stirring reaction, and ultrasonic mixing is performed first. 50min, then heating to 60°C, stirring at a speed of 80r / min for 4h, high-speed centrifugal separation, water washing, and drying to obtain silver-loaded carbon nanotubes; 4 parts of the silver-loaded carbon nanotubes were added to 500 parts of anhydrous ethanol and dispersed evenly, and then 2 parts of dopamine hydrochloride were added for self-polymerization, the pH was adjusted to 8.2, stirred at room temperature for 2h, centrifuged, and washed with water to obtain modified carbon nanotubes; 4 parts of the modified carbon nanotubes were added to 80 parts of deionized water, and then 20 parts of acrylic acid were added for grafting treatment, placed in a nitrogen atmosphere, and reacted at a constant temperature of 58°C for 30min, filtered, washed with water, and dried to obtain composite modified carbon nanotubes.

[0038] Example 3 This embodiment provides a method for preparing a conductive UV inkjet ink containing nanosilver wires, comprising the following steps: In parts by weight, 45 parts of composite modified carbon nanotubes, 6 parts of modified nanosilver wires, 4 parts of polyester acrylate resin, 3 parts of pentaerythritol triacrylate, 1.5 parts of photoinitiator 2-isopropylthioxanthone and 50-70 parts of solvent isopropyl alcohol were mixed, stirred at 72° C. for 55 minutes, and then transferred to a grinder and ground for 110 minutes to obtain a conductive UV inkjet ink containing nanosilver wires.

[0039] The modified silver nanowires are prepared as follows: by weight, 1.4 parts of graphene oxide are added to 450 parts of ethylene glycol for ultrasonic dispersion, and then 90 parts of silver nitrate are added and stirred to dissolve to obtain liquid A; 0.7 parts of ferric chloride are added to 450 parts of ethylene glycol for thorough dissolution to obtain a ferric chloride solution, 14 parts of polyvinyl pyrrolidone are added to 450 parts of ethylene glycol for stirring and dissolving, and then 15 parts of the ferric chloride solution are added and stirred uniformly to obtain liquid B; 220 parts of liquid A are added to 450 parts of liquid B for high-temperature reaction at 165° C. for 4 hours, cooled, centrifuged and washed with acetone and anhydrous ethanol in sequence, and dried to obtain the modified silver nanowires.

[0040] Preparation of the composite modified carbon nanotubes: 6 parts by weight of commercially available carbon nanotubes are added to a mixture of 110 parts of nitric acid and 290 parts of sulfuric acid, acidified at 105°C for 70 minutes, filtered, washed with water, centrifuged, dried, and then added to 500 parts of deionized water for ultrasonic dispersion to obtain a carbon nanotube dispersion; 50 parts of 0.1 mol / L silver nitrate solution and 15 parts of 0.2 mol / L glucose solution are mixed, and then 0.6 parts of starch and 0.7 parts of trisodium citrate are added and stirred uniformly to obtain a mixed solution; 60 parts of the mixed solution are added dropwise to 500 parts of the carbon nanotube dispersion for stirring and reaction, and ultrasonic mixing is performed first. 55min, then heated to 68°C, stirred at 90r / min for 3h, high-speed centrifuged, washed with water, and dried to obtain silver-loaded carbon nanotubes; 6 parts of the silver-loaded carbon nanotubes were added to 550 parts of anhydrous ethanol and dispersed evenly, and then 3 parts of dopamine hydrochloride were added for self-polymerization, the pH was adjusted to 8.3, stirred at room temperature for 3h, centrifuged, washed with water, and modified carbon nanotubes were obtained; 6 parts of the modified carbon nanotubes were added to 90 parts of deionized water, and then 25 parts of acrylic acid were added for grafting treatment, placed in a nitrogen atmosphere, and reacted at a constant temperature of 59°C for 28min, filtered, washed with water, and dried to obtain composite modified carbon nanotubes.

[0041] Comparative Example 1 This comparative example provides a method for preparing a UV inkjet ink, comprising the following steps: In parts by weight, 50 parts of hydroxylated carbon nanotubes, 6 parts of polyester acrylate resin, 4 parts of pentaerythritol triacrylate, 2 parts of photoinitiator diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide and 70 parts of solvent n-butanol were mixed, stirred at 76° C. for 50 minutes, and then transferred to a grinder and ground for 120 minutes to obtain a conductive UV inkjet ink containing nanosilver wires.

[0042] Comparative Example 2 This comparative example provides a method for preparing a UV inkjet ink, comprising the following steps: In parts by weight, 50 parts of nanosilver, 6 parts of polyester acrylate resin, 4 parts of pentaerythritol triacrylate, 2 parts of photoinitiator diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide and 70 parts of solvent n-butanol were mixed, stirred at 76° C. for 50 minutes, and then transferred to a grinder and ground for 120 minutes to obtain a conductive UV inkjet ink containing nanosilver wires.

[0043] The performance of the UV inkjet ink provided in the above embodiments and comparative examples was tested using the following test methods: (1) Conductivity test: Conduct the test in accordance with the requirements of BS EN 16813 2016.

[0044] (2) Stability test: The prepared ink was sealed and stored at 80°C for 4 days to observe the dispersion.

[0045] The above performance test data is shown in Table 1.

[0046] Table 1 Performance test results ; As can be seen from the above content, the present invention uses composite modified carbon nanotubes and modified nanosilver wires, and uses ester acrylate resin, pentaerythritol triacrylate and photoinitiator together to prepare conductive UV inkjet inks containing nanosilver wires (Examples 1 to 3). The inks have high conductivity and good stability.

[0047] Compared with Example 1, when 50 parts of hydroxylated carbon nanotubes (Article No. 100311) were used to replace 50 parts of composite modified carbon nanotubes, and 8 parts of modified nanosilver wires were not added, the conductivity decreased and the ink stability was poor (Comparative Example 1). Compared with Example 1, when 50 parts of nanosilver (Article No. 100422) were used to replace 50 parts of composite modified carbon nanotubes, and 8 parts of modified nanosilver wires were not added, the ink stability was poor (Comparative Example 2).

[0048] In summary, the present invention performs composite modification on carbon nanotubes, first achieving silver loading through a heating reduction method, and then obtaining photocuring properties through the grafting of dopamine and acrylic acid. The modified nano silver wires are used together to prepare a conductive UV inkjet ink containing nano silver wires, which effectively improves the conductivity while ensuring that the ink is dispersed stably and does not precipitate.

Claims

1. A conductive UV inkjet ink containing nano silver wires, characterized in that: In parts by weight, it comprises the following components: 40-50 parts of carbon nanotubes, 4-8 parts of modified silver nanowires, 2-6 parts of polyester acrylate resin, 2-4 parts of pentaerythritol triacrylate, 1-2 parts of photoinitiator and 50-70 parts of solvent; The modified silver nanowire preparation method comprises: adding 1.2 to 1.6 parts of graphene oxide to 400 to 500 parts of ethylene glycol by weight and ultrasonically dispersing the mixture; then adding 80 to 100 parts of silver nitrate and stirring to dissolve the mixture to obtain a solution A; adding 0.6 to 0.8 parts of ferric chloride to 400 to 500 parts of ethylene glycol and fully dissolving the mixture to obtain a ferric chloride solution; adding 10 to 16 parts of polyvinyl pyrrolidone to 400 to 500 parts of ethylene glycol and stirring to dissolve the mixture; and then adding 10 to 20 parts of the ferric chloride solution and stirring to obtain a solution B; 200-240 parts of liquid A are added to 400-500 parts of liquid B for high temperature reaction to obtain modified nano silver wires.

2. The conductive UV inkjet ink containing nano silver wires according to claim 1, characterized in that: The conditions of the high temperature reaction include: reacting at 160-170° C. for 3-5 hours, cooling, centrifugally washing with acetone and anhydrous ethanol in sequence, and drying.

3. The conductive UV inkjet ink containing nano silver wires according to claim 1, characterized in that: The photoinitiator is selected from at least one of diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, 2,4-diethylthioxanthone, and 2-isopropylthioxanthone.

4. The conductive UV inkjet ink containing nano silver wires according to claim 1, characterized in that: The solvent is selected from at least one of n-butanol, tert-butanol, and isopropanol.

5. The conductive UV inkjet ink containing nano silver wires according to claim 1, characterized in that: The carbon nanotubes are composite modified carbon nanotubes; The preparation method of the composite modified carbon nanotubes comprises: firstly subjecting 4 to 8 parts of multi-walled carbon nanotubes to acid treatment, and then adding them to 400 to 600 parts of deionized water for ultrasonic dispersion to obtain a carbon nanotube dispersion; 40-60 parts of a 0.1 mol / L silver nitrate solution and 10-20 parts of a 0.2 mol / L glucose solution are mixed, and then 0.4-0.8 parts of starch and 0.6-0.8 parts of trisodium citrate are added and stirred uniformly to obtain a mixed solution; 50-80 parts of the mixed solution are dropwise added into 400-600 parts of the carbon nanotube dispersion to carry out stirring reaction to obtain silver-loaded carbon nanotubes; 4-8 parts of the silver-loaded carbon nanotubes are added into 500-600 parts of anhydrous ethanol to be dispersed uniformly, and then 2-4 parts of dopamine hydrochloride are added to carry out self-polymerization to obtain modified carbon nanotubes; 4-8 parts of the modified carbon nanotubes are added into 80-100 parts of deionized water, and then 20-30 parts of acrylic acid are added to carry out grafting treatment to obtain composite modified carbon nanotubes.

6. The conductive UV inkjet ink containing nano silver wires according to claim 5, characterized in that: The acidification treatment step includes: adding 4 to 8 parts by weight of commercially available carbon nanotubes to a mixture of 100 to 120 parts of nitric acid and 280 to 300 parts of sulfuric acid, acidifying at 100 to 110° C. for 60 to 80 minutes, filtering, washing with water, centrifuging, and drying.

7. The conductive UV inkjet ink containing nano silver wires according to claim 5, characterized in that: The stirring reaction conditions include: first ultrasonic mixing for 50-60 minutes, then heating to 60-70° C., stirring at a speed of 80-100 r / min for 2-4 hours, high-speed centrifugal separation, water washing, and drying.

8. The conductive UV inkjet ink containing nano silver wires according to claim 5, characterized in that: The self-polymerization conditions include: adjusting the pH to 8.2-8.4, stirring at room temperature for 2-4 hours, centrifuging, and washing with water.

9. The conductive UV inkjet ink containing nano silver wires according to claim 5, characterized in that: The grafting treatment conditions include: placing in a nitrogen atmosphere, reacting at a constant temperature of 58-60° C. for 20-30 minutes, filtering, washing with water, and drying.

10. A method for preparing the conductive UV inkjet ink containing nano silver wires according to any one of claims 1 to 9, characterized in that: The following steps are involved: In parts by weight, 40-50 parts of carbon nanotubes, 4-8 parts of modified nanosilver wires, 2-6 parts of polyester acrylate resin, 2-4 parts of pentaerythritol triacrylate, 1-2 parts of photoinitiator and 50-70 parts of solvent are mixed, stirred at 70-76° C. for 50-60 minutes, and then transferred to a grinder for grinding for 100-120 minutes to obtain a conductive UV inkjet ink containing nanosilver wires.