An environmentally friendly antistatic LED-UV curing ink functional agent

Abstract

The present invention relates to the field of ink additives, specifically an environmentally friendly antistatic LED-UV curing ink functional agent. The functional agent solves the problem of static electricity accumulation during long-term printing, and reduced ink adhesion caused by excessive addition of antistatic agents to UV inks when combating large amounts of static electricity, resulting in poor scratch resistance of the ink after curing, blurred printed layers, and reduced image quality. The functional agent comprises, by weight, 10-30 parts of a composite conductive nanomaterial, 6-12 parts of a resin, 20-40 parts of a silicone oil, 1-5 parts of a surfactant, and 10-20 parts of water. The composite conductive nanomaterial is prepared by stabilizing carbon nanotubes and iodinated polyacetylene by filling them with carbon nanotubes at a weight ratio of 1:1-1.2. The functional agent fills the carbon nanotubes with polyacetylene molecular chains, maintaining the function and structure of the long polyacetylene chains unaffected, thereby enhancing the antistatic agent's ability to derive static charges. This protects the ink from the effects of static electricity during long-term printing, thereby improving printing effects.

Description

Technical Field

[0001] The present invention relates to the technical field of ink additives, and in particular to an environmentally friendly antistatic LED-UV curing ink functional agent. Background Art

[0002] LED-UV ink is an ink that cures instantly after being irradiated with light of 395nm wavelength. It includes photoinitiators, monomers, diluents, thickeners, and auxiliary additives. The light energy is absorbed by the photoinitiator in the ink, generating active fragments, which polymerize oligomers or monomers containing double bonds to form a cross-linked network, ultimately achieving ink curing. However, due to the printing substrate, during the fast printing process, the rapid rotation and movement of the printing substrate causes frictional electrification, which generates a large amount of static electricity on the substrate surface. When the UV ink is transferred to the substrate surface by roller coating, the existence of the charge causes the ink and the substrate to repel each other, resulting in roller slippage and uneven roller coating. After the ink molecules are charged, not only will the adhesion between the ink and the substrate be reduced during the curing process, but the ink will also be unevenly distributed on the substrate surface, resulting in white leakage.

[0003] The existing solution to the problem of static electricity is mainly to add antistatic agents to the ink. For example, substances containing ether bonds such as polyoxyethylene castor oil, polyoxyethylene laurate, and polyethylene glycol combine with water to form a conductive path, thereby conducting away excess charge and reducing static electricity. However, the antistatic agent in this method is unevenly distributed in the resin. Excessive use can result in low ink adhesion and scratch resistance. It can also cause oily substances to seep out of the paint film surface, reducing the appearance of the packaging material. Another method is to treat the substrate surface with a surfactant before curing. The lipophilic groups on the substrate surface increase adhesion, while the hydrophilic groups combine with water to form a conductive layer, thereby conducting away the surface charge of the substrate and eliminating the effects of static electricity. However, this method does not effectively remove static electricity carried by the UV ink itself. After long-term printing, the charge accumulates in the ink storage box, resulting in ink flying, blurring the printed image, and reducing print quality. Summary of the Invention

[0004] In order to solve the problem of static electricity accumulation during long-term printing, excessive addition of antistatic agents to UV inks to combat large amounts of static electricity leads to reduced ink adhesion, resulting in poor scratch resistance after ink curing, blurred printed layers, and reduced image quality, the present invention provides an environmentally friendly antistatic LED-UV curing ink functional agent, including the following specific components:

[0005] The composition is as follows:

[0006] Composite conductive nanomaterial: 10-30 parts, resin: 6-12 parts, silicone oil: 20-40 parts, surfactant: 1-5 parts and water: 10-20 parts.

[0007] The composite conductive nanomaterial is prepared by filling carbon nanotubes and iodinated polyacetylene in a weight ratio of 1:1-1.2 and then stabilizing the mixture.

[0008] The preparation method of the composite conductive nanomaterial is as follows:

[0009] S1. Treat the carbon nanotubes with concentrated nitric acid, dry them, and then perform plasma etching to obtain uncapped carbon nanotubes. Place the uncapped carbon nanotubes in water, pressurize and heat them, and dry them to obtain carbon nanotubes with an inner diameter of 20-50 nm.

[0010] S2. Place polyacetylene in iodine vapor for reaction to obtain iodinated polyacetylene.

[0011] S3, self-assembly of iodinated polyacetylene and carbon nanotubes, dissolving iodinated polyacetylene in a solvent, adding a surfactant, then adding carbon nanotubes and stirring to react, and evaporating the solvent to obtain composite conductive nanotubes.

[0012] S4. The composite conductive nanotubes are placed in chloroform, iron powder is added thereto for ultrasonic mixing, and then a stabilized composite conductive nanomaterial is obtained through thermal reaction.

[0013] The technical solution adopted in this application not only uses a surfactant, but also adopts a composite conductive nanomaterial with better charge extraction performance. Iodinated polyacetylene is used in combination with carbon nanotubes to enhance the ability of charge extraction and flow. In the face of a large amount of charge accumulation, the ability to carry charge can be effectively maintained. Filling iodinated polyacetylene into carbon nanotubes can slow down the disappearance of the polyacetylene π electron cloud and avoid the loss of conjugated structure. Therefore, this functional agent can produce strong electrical conductivity during the ink roller coating process and the UV curing process, avoid uneven application of ink due to charge, and enhance the printing quality of the layer.

[0014] The iodinated polyacetylene and carbon nanotubes used in this application are filled in a weight ratio of 1-1.2:1, which can effectively position part of the polyacetylene molecular chains outside the carbon nanotubes. These external polyacetylene molecular chains, due to their carbon-carbon double bonds, can effectively connect with the resin monomer and the cross-linking curing agent to form a strong grid structure, thereby enhancing adhesion to the substrate surface without affecting the conjugated structure of the remaining polyacetylene chains in the carbon nanotubes, thereby maintaining strong antistatic capabilities.

[0015] This application also uses silicone oil in the functional agent. The addition of silicone oil reduces the viscosity of the ink and increases the fluidity of the UV ink, so that the composite conductive nanomaterial in the functional agent can be better suspended. After being added to the ink, it can be dispersed more evenly, thereby enhancing the overall resistance of the ink to electric charge and achieving better printing effects.

[0016] Furthermore, the carbon nanotubes in S1 are multi-walled carbon nanotubes, the diameter of the multi-walled carbon nanotubes is 30-80 nm, the ratio of the carbon nanotubes to water is 1:2, the treatment pressure is 1.5-3.0 MPa, the treatment temperature is 140-220°C, and the pressurized and heated treatment is followed by ultrasonic treatment, the ultrasonic power is 200-300w, and the ultrasonic treatment time is 20-30min.

[0017] This application uses multi-walled carbon nanotubes, which have the advantage of a larger inner diameter than single-walled carbon nanotubes, making it easier for polyacetylene to pass through. High-pressure treatment is used to form water clusters inside the carbon nanotubes, making it easier for polyacetylene to fill the carbon nanotubes.

[0018] Furthermore, the S3 solvent is one of n-octane, chloroform, chloroform or tetrahydrofuran, and the solid-liquid ratio of the iodinated polyacetylene to the solvent is 1g:100-120ml.

[0019] Furthermore, the surfactant in S3 is one of sodium lauryl sulfate, sodium lauryl sulfonate, sodium tetrapropylene sulfonate or sodium dioctyl sulfosuccinate.

[0020] The present application adds a small amount of surfactant to achieve better contact between carbon nanotubes and iodinated polyacetylene, thereby promoting the filling of the polyacetylene structure.

[0021] Furthermore, the added volume ratio of the surfactant to the solvent in S3 is 2-10:100.

[0022] Furthermore, the solid-liquid ratio of the carbon nanotubes in S1 treated with concentrated nitric acid is 1g:10ml, the treatment temperature is 140-200°C, and the reaction time is 24-48h.

[0023] Furthermore, the plasma excitation power of the plasma etching in S1 is 100-2000W, the etching environment pressure is 1000Pa, and the impact gas of the plasma etching is one of oxygen, air, nitrogen or argon.

[0024] Furthermore, the usage amount of the functional agent is 3-15% of the LED-UV curing ink.

[0025] The environmentally friendly antistatic LED-UV curing ink functional agent prepared by the present invention can be used in relevant inks.

[0026] This application has at least the following beneficial effects:

[0027] 1. In the process of preparing the functional agent for curing ink, the present application uses multi-walled carbon nanotubes and polyacetylene to form a structure for exporting charges. This structure not only has good conductivity and avoids charge accumulation, but also can increase the degree of cross-linking, enhance the connection strength between the functional agent and the ink, and indirectly strengthen the adhesion between the ink and the substrate, making it more scratch-resistant.

[0028] 2. In the present application, a certain gap is opened on the surface or end of the carbon nanotube through plasma etching to facilitate the filling of polyacetylene into the interior of the carbon nanotube. After the polyacetylene is filled into the carbon nanotube, the filled carbon nanotube is treated with chloroform and iron powder to facilitate the removal of polyacetylene or other impurities on the outer wall of the carbon nanotube that are not fixedly connected, thereby reducing the oxygen barrier distance and making the effective composite conductive nanomaterial more pure. The connection strength between the polyacetylene inside the carbon nanotube and the inner wall of the carbon nanotube is enhanced through thermal reaction. Therefore, after being added to UV ink, it can maintain a strong ability to extract charge, and remove charge through the water layer in the functional agent, thereby enhancing the uniformity of the ink pattern, forming a more regular layer, and strengthening the printing effect.

[0029] 3. The functional agent of the present application is not only antistatic before curing and reduces the surface tension of the ink, but also maintains a strong ability to prevent static electricity accumulation after curing and forming a film, avoiding the adsorption of dust. The carbon nanotubes effectively protect the conjugated structure of polyacetylene. Compared with the unprotected polyacetylene, the double bonds are opened and cross-linked during curing. The polyacetylene protected by the carbon nanotubes will not cross-link with the photoinitiator and resin monomer inside the carbon nanotubes, and can protect the film layer for a long time. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 Schematic diagram of the resistivity of the surface of UV ink films of various embodiments of the present invention and various comparative examples at different addition ratios. DETAILED DESCRIPTION

[0031] The following will refer to the attached Figure 1 The embodiments of the present invention are described in detail. It should be understood by those skilled in the art that these embodiments are only used to explain the technical principles of the present invention and are not intended to limit the scope of protection of the present invention.

[0032] Preparation Example 1

[0033] Preparation of composite conductive nanomaterials, the specific preparation steps are as follows:

[0034] S1. By weight, 10 parts of multi-walled carbon nanotubes are placed in 100 parts of concentrated nitric acid for immersion treatment at a treatment temperature of 180°C and a reaction time of 24 hours, and are washed with water, heated and dried, and then placed in an etching chamber for plasma etching. The working gas for plasma etching is air, the plasma excitation power is 1000W, and the etching environment pressure is 1000Pa to obtain uncapped carbon nanotubes. The uncapped carbon nanotubes are placed in 20 parts of water, pressurized to 2.0MPa, heated to 180°C, and then ultrasonically treated with an ultrasonic power of 300W and an ultrasonic treatment time of 25min. After surface drying, carbon nanotubes are obtained, and the inner diameter of the carbon nanotubes is 30-50nm.

[0035] S2. 11 parts of polyacetylene are placed on a mesh in a reactor, and iodine vapor is input into the lower part of the reactor for reaction. The mass ratio of polyacetylene to iodine vapor is 1:2.5, and the reaction temperature is 200° C. to obtain iodinated polyacetylene.

[0036] S3. Dissolve iodinated polyacetylene in n-octane with a solid-liquid ratio of iodinated polyacetylene to n-octane of 1 g:110 ml, and add sodium lauryl sulfate with a volume that is 5% of the volume of n-octane. Then add carbon nanotubes and stir to react. After heating to evaporate the n-octane, composite conductive nanotubes are obtained.

[0037] S4. Place the composite conductive nanotubes in chloroform, add iron powder and perform ultrasonic mixing treatment. The ultrasonic treatment power is 120W, and the amount of iron powder added is 10% of the weight of the composite conductive nanotubes. Heat the chloroform to react for 20 minutes to obtain a stabilized composite conductive nanomaterial.

[0038] Preparation Example 2

[0039] Preparation of composite conductive nanomaterials, the specific preparation steps are as follows:

[0040] S1. By weight, 10 parts of multi-walled carbon nanotubes are placed in 100 parts of concentrated nitric acid for soaking treatment at a treatment temperature of 140°C and a reaction time of 24 hours, and are washed with water, heated and dried, and then placed in an etching chamber for plasma etching. The working gas for plasma etching is oxygen, the plasma excitation power is 100W, and the etching environment pressure is 1000Pa to obtain uncapped carbon nanotubes. The uncapped carbon nanotubes are placed in 20 parts of water, pressurized to 1.5MPa, heated to 140°C, and then ultrasonically treated with an ultrasonic power of 200W and an ultrasonic treatment time of 20min. After surface drying, carbon nanotubes are obtained, and the inner diameter of the carbon nanotubes is 20-40nm.

[0041] S2. Place 10 parts of polyacetylene on a mesh in a reactor, input iodine vapor into the lower part of the reactor for reaction, the mass ratio of polyacetylene to iodine vapor is 1:2, the reaction temperature is 190°C, and iodinated polyacetylene is obtained.

[0042] S3. Dissolve iodinated polyacetylene in chloroform with a solid-liquid ratio of iodinated polyacetylene to chloroform of 1 g:100 ml, and add sodium dodecyl sulfate in a volume that is 2% of the volume of chloroform. Then add carbon nanotubes and stir to react. After heating to evaporate the chloroform, composite conductive nanotubes are obtained.

[0043] S4. Place the composite conductive nanotubes in chloroform, add iron powder and perform ultrasonic mixing treatment. The ultrasonic treatment power is 120W, and the amount of iron powder added is 10% of the weight of the composite conductive nanotubes. Heat the chloroform to react for 20 minutes to obtain a stabilized composite conductive nanomaterial.

[0044] Preparation Example 3

[0045] Preparation of composite conductive nanomaterials, the specific preparation steps are as follows:

[0046] S1. By weight, 10 parts of multi-walled carbon nanotubes are placed in 100 parts of concentrated nitric acid for immersion treatment at a treatment temperature of 200°C and a reaction time of 48 hours, and are washed with water, heated and dried, and then placed in an etching chamber for plasma etching. The working gas for plasma etching is nitrogen, the plasma excitation power is 2000W, and the etching environment pressure is 1000Pa to obtain uncapped carbon nanotubes. The uncapped carbon nanotubes are placed in 20 parts of water, pressurized to 13.0MPa, heated to 220°C, and then ultrasonically treated with an ultrasonic power of 300W and an ultrasonic treatment time of 30min. After surface drying, carbon nanotubes are obtained, and the inner diameter of the carbon nanotubes is 30-50nm.

[0047] S2. Place 12 parts of polyacetylene on a mesh in a reactor, input iodine vapor into the lower part of the reactor for reaction, the mass ratio of polyacetylene to iodine vapor is 1:3, the reaction temperature is 220°C, and iodinated polyacetylene is obtained.

[0048] S3. Dissolve iodinated polyacetylene in tetrahydrofuran at a solid-liquid ratio of 1 g to 120 ml, add sodium dioctyl sulfosuccinate in a volume of 10% of tetrahydrofuran, add carbon nanotubes, stir and react, heat and evaporate the tetrahydrofuran to obtain composite conductive nanotubes.

[0049] S4. Place the composite conductive nanotubes in chloroform, add iron powder and perform ultrasonic mixing treatment. The ultrasonic treatment power is 120W, and the amount of iron powder added is 10% of the weight of the composite conductive nanotubes. Heat the chloroform to react for 20 minutes to obtain a stabilized composite conductive nanomaterial.

[0050] Preparation Example 4

[0051] Preparation of composite conductive nanomaterials, the specific preparation steps are as follows:

[0052] S1. By weight, 10 parts of multi-walled carbon nanotubes are placed in 100 parts of concentrated nitric acid for immersion treatment at a treatment temperature of 160°C and a reaction time of 32 hours, and are washed with water, heated and dried, and then placed in an etching chamber for plasma etching. The working gas for plasma etching is argon, the plasma excitation power is 1400W, and the etching environment pressure is 1000Pa to obtain uncapped carbon nanotubes. The uncapped carbon nanotubes are placed in 20 parts of water, pressurized to 2.3MPa, heated to 160°C, and then ultrasonically treated with an ultrasonic power of 240W and an ultrasonic treatment time of 240min. After surface drying, carbon nanotubes are obtained, and the inner diameter of the carbon nanotubes is 30-50nm.

[0053] S2. 12 parts of polyacetylene are placed on a mesh in a reactor, and iodine vapor is introduced into the lower part of the reactor for reaction. The mass ratio of polyacetylene to iodine vapor is 1:2.6, and the reaction temperature is 210° C. to obtain iodinated polyacetylene.

[0054] S3. Dissolve iodinated polyacetylene in chloroform with a solid-liquid ratio of iodinated polyacetylene to chloroform of 1 g:110 ml, and add sodium tetrapropylene benzene sulfonate in an amount of 3% by volume of the solvent. Then add carbon nanotubes and stir to react. After heating to evaporate the chloroform, composite conductive nanotubes are obtained.

[0055] S4. Place the composite conductive nanotubes in chloroform, add iron powder and perform ultrasonic mixing treatment. The ultrasonic treatment power is 120W, and the amount of iron powder added is 10% of the weight of the composite conductive nanotubes. Heat the chloroform to react for 20 minutes to obtain a stabilized composite conductive nanomaterial.

[0056] Preparation Example 5: No plasma etching

[0057] Preparation of composite conductive nanomaterials, the specific preparation steps are as follows:

[0058] S1. By weight, 10 parts of multi-walled carbon nanotubes were immersed in 100 parts of concentrated nitric acid at a treatment temperature of 180°C for 24 hours, washed with water, heated and dried, then placed in 20 parts of water, pressurized to 2.0 MPa, heated to 180°C, and then ultrasonically treated at an ultrasonic power of 300W for 25 minutes. After surface drying, carbon nanotubes were obtained, and the inner diameter of the carbon nanotubes was 30-50 nm.

[0059] S2. 11 parts of polyacetylene are placed on a mesh in a reactor, and iodine vapor is input into the lower part of the reactor for reaction. The mass ratio of polyacetylene to iodine vapor is 1:2.5, and the reaction temperature is 200° C. to obtain iodinated polyacetylene.

[0060] S3. Dissolve iodinated polyacetylene in n-octane with a solid-liquid ratio of iodinated polyacetylene to n-octane of 1 g:110 ml, and add sodium lauryl sulfate with a volume that is 5% of the volume of n-octane. Then add carbon nanotubes and stir to react. After heating to evaporate the n-octane, composite conductive nanotubes are obtained.

[0061] S4. Place the composite conductive nanotubes in chloroform, add iron powder and perform ultrasonic mixing treatment. The ultrasonic treatment power is 120W, and the amount of iron powder added is 10% of the weight of the composite conductive nanotubes. Heat the chloroform to react for 20 minutes to obtain a stabilized composite conductive nanomaterial.

[0062] Preparation Example 6: No pressurization, heating, or ultrasonic treatment

[0063] Preparation of composite conductive nanomaterials, the specific preparation steps are as follows:

[0064] S1. By weight, 10 parts of multi-walled carbon nanotubes are immersed in 100 parts of concentrated nitric acid at a treatment temperature of 180°C for a reaction time of 24 hours, and are washed with water, heated and dried. Then, the multi-walled carbon nanotubes are placed in an etching chamber for plasma etching. The working gas for plasma etching is air, the plasma excitation power is 1000W, and the etching environment pressure is 1000Pa to obtain uncapped carbon nanotubes with an inner diameter of 30-50nm.

[0065] S2. 11 parts of polyacetylene are placed on a mesh in a reactor, and iodine vapor is input into the lower part of the reactor for reaction. The mass ratio of polyacetylene to iodine vapor is 1:2.5, and the reaction temperature is 200° C. to obtain iodinated polyacetylene.

[0066] S3. Dissolve iodinated polyacetylene in n-octane with a solid-liquid ratio of iodinated polyacetylene to n-octane of 1 g:110 ml, and add sodium lauryl sulfate with a volume that is 5% of the volume of n-octane. Then add carbon nanotubes and stir to react. After heating to evaporate the n-octane, composite conductive nanotubes are obtained.

[0067] S4. Place the composite conductive nanotubes in chloroform, add iron powder and perform ultrasonic mixing treatment. The ultrasonic treatment power is 120W, and the amount of iron powder added is 10% of the weight of the composite conductive nanotubes. Heat the chloroform to react for 20 minutes to obtain a stabilized composite conductive nanomaterial.

[0068] Preparation Example 7: The amount of iodinated polyacetylene used is less than that of carbon nanotubes

[0069] Preparation of composite conductive nanomaterials, the specific preparation steps are as follows:

[0070] S1. By weight, 10 parts of multi-walled carbon nanotubes are placed in 100 parts of concentrated nitric acid for immersion treatment at a treatment temperature of 180°C and a reaction time of 24 hours, and are washed with water, heated and dried, and then placed in an etching chamber for plasma etching. The working gas for plasma etching is air, the plasma excitation power is 1000W, and the etching environment pressure is 1000Pa to obtain uncapped carbon nanotubes. The uncapped carbon nanotubes are placed in 20 parts of water, pressurized to 2.0MPa, heated to 180°C, and then ultrasonically treated with an ultrasonic power of 300W and an ultrasonic treatment time of 25min. After surface drying, carbon nanotubes are obtained, and the inner diameter of the carbon nanotubes is 30-50nm.

[0071] S2. 8 parts of polyacetylene are placed on a mesh in a reactor, and iodine vapor is input into the lower part of the reactor for reaction. The mass ratio of polyacetylene to iodine vapor is 1:2.5, and the reaction temperature is 200° C. to obtain iodinated polyacetylene.

[0072] S3. Dissolve iodinated polyacetylene in n-octane with a solid-liquid ratio of iodinated polyacetylene to n-octane of 1 g:110 ml, and add sodium lauryl sulfate with a volume that is 5% of the volume of n-octane. Then add carbon nanotubes and stir to react. After heating to evaporate the n-octane, composite conductive nanotubes are obtained.

[0073] S4. Place the composite conductive nanotubes in chloroform, add iron powder and perform ultrasonic mixing treatment. The ultrasonic treatment power is 120W, and the amount of iron powder added is 10% of the weight of the composite conductive nanotubes. Heat the chloroform to react for 20 minutes to obtain a stabilized composite conductive nanomaterial.

[0074] Preparation Example 8: Using single-walled carbon nanotubes

[0075] Preparation of composite conductive nanomaterials, the specific preparation steps are as follows:

[0076] S1. By weight, 10 parts of single-arm carbon nanotubes are placed in 100 parts of concentrated nitric acid for immersion treatment at a treatment temperature of 180°C and a reaction time of 24 hours, and are washed with water, heated and dried, and then placed in an etching chamber for plasma etching. The working gas for plasma etching is air, the plasma excitation power is 1000W, and the etching environment pressure is 1000Pa to obtain uncapped carbon nanotubes. The uncapped carbon nanotubes are placed in 20 parts of water, pressurized to 2.0MPa, heated to 180°C, and then ultrasonically treated with an ultrasonic power of 300W and an ultrasonic treatment time of 25min. After surface drying, carbon nanotubes are obtained, and the inner diameter of the carbon nanotubes is 0.5-5nm.

[0077] S2. 11 parts of polyacetylene are placed on a mesh in a reactor, and iodine vapor is input into the lower part of the reactor for reaction. The mass ratio of polyacetylene to iodine vapor is 1:2.5, and the reaction temperature is 200° C. to obtain iodinated polyacetylene.

[0078] S3. Dissolve iodinated polyacetylene in n-octane with a solid-liquid ratio of iodinated polyacetylene to n-octane of 1 g:110 ml, and add sodium lauryl sulfate with a volume that is 5% of the volume of n-octane. Then add carbon nanotubes and stir to react. After heating to evaporate the n-octane, composite conductive nanotubes are obtained.

[0079] S4. Place the composite conductive nanotubes in chloroform, add iron powder and perform ultrasonic mixing treatment. The ultrasonic treatment power is 120W, and the amount of iron powder added is 10% of the weight of the composite conductive nanotubes. Heat the chloroform to react for 20 minutes to obtain a stabilized composite conductive nanomaterial.

[0080] Preparation Example 9: Polyacetylene without iodination

[0081] Preparation of composite conductive nanomaterials, the specific preparation steps are as follows:

[0082] S1. By weight, 10 parts of multi-walled carbon nanotubes are placed in 100 parts of concentrated nitric acid for immersion treatment at a treatment temperature of 180°C and a reaction time of 24 hours, and are washed with water, heated and dried, and then placed in an etching chamber for plasma etching. The working gas for plasma etching is air, the plasma excitation power is 1000W, and the etching environment pressure is 1000Pa to obtain uncapped carbon nanotubes. The uncapped carbon nanotubes are placed in 20 parts of water, pressurized to 2.0MPa, heated to 180°C, and then ultrasonically treated with an ultrasonic power of 300W and an ultrasonic treatment time of 25min. After surface drying, carbon nanotubes are obtained, and the inner diameter of the carbon nanotubes is 30-50nm.

[0083] S2. Dissolve 11 parts of polyacetylene in n-octane with a solid-liquid ratio of polyacetylene to n-octane of 1 g:110 ml, and add sodium lauryl sulfate with a volume that is 5% of the volume of n-octane. Then add carbon nanotubes and stir to react. After heating to evaporate the n-octane, composite conductive nanotubes are obtained.

[0084] S3. Place the composite conductive nanotubes in chloroform, add iron powder and perform ultrasonic mixing treatment. The ultrasonic treatment power is 120W, and the amount of iron powder added is 10% of the weight of the composite conductive nanotubes. Heat the chloroform to react for 20 minutes to obtain a stabilized composite conductive nanomaterial. Example 1

[0085] The preparation of an environmentally friendly antistatic LED-UV curing ink functional agent comprises the following specific steps:

[0086] Weigh 20 parts of the composite conductive nanomaterial in Preparation Example 1, 8 parts of acrylic resin, 30 parts of silicone oil, 3 parts of surfactant polyethylene glycol, and 15 parts of water, place the composite conductive nanomaterial in the silicone oil, add the surfactant and resin, stir slowly, add water during the stirring process, and mix evenly to obtain a curing ink functional agent. Example 2

[0087] The preparation of an environmentally friendly antistatic LED-UV curing ink functional agent comprises the following specific steps:

[0088] Weigh 10 parts of the composite conductive nanomaterial in Preparation Example 2, 10 parts of acrylic resin, 20 parts of silicone oil, 1 part of surfactant polyethylene glycol, and 10 parts of water, place the composite conductive nanomaterial in the silicone oil, add the surfactant and resin, stir slowly, add water during the stirring process, and mix evenly to obtain a curing ink functional agent. Example 3

[0089] The preparation of an environmentally friendly antistatic LED-UV curing ink functional agent comprises the following specific steps:

[0090] Weigh 30 parts of the composite conductive nanomaterial in Preparation Example 3, 6 parts of acrylic resin, 40 parts of silicone oil, 5 parts of surfactant polyethylene glycol, and 20 parts of water, place the composite conductive nanomaterial in the silicone oil, add the surfactant and resin, stir slowly, add water during the stirring process, and mix evenly to obtain a curing ink functional agent. Example 4

[0091] The preparation of an environmentally friendly antistatic LED-UV curing ink functional agent comprises the following specific steps:

[0092] Weigh 20 parts of the composite conductive nanomaterial in Preparation Example 4, 12 parts of acrylic resin, 30 parts of silicone oil, 3 parts of surfactant polyethylene glycol, and 12 parts of water, place the composite conductive nanomaterial in the silicone oil, add the surfactant and resin, stir slowly, add water during the stirring process, and mix evenly to obtain a curing ink functional agent.

[0093] Comparative Example 1

[0094] The preparation of an environmentally friendly antistatic LED-UV curing ink functional agent comprises the following specific steps:

[0095] Weigh 20 parts of the composite conductive nanomaterial in Preparation Example 5, 12 parts of acrylic resin, 30 parts of silicone oil, 3 parts of surfactant polyethylene glycol, and 12 parts of water, place the composite conductive nanomaterial in the silicone oil, add the surfactant and resin, stir slowly, add water during the stirring process, and mix evenly to obtain a curing ink functional agent.

[0096] Comparative Example 2

[0097] The preparation of an environmentally friendly antistatic LED-UV curing ink functional agent comprises the following specific steps:

[0098] Weigh 20 parts of the composite conductive nanomaterial in Preparation Example 6, 12 parts of acrylic resin, 30 parts of silicone oil, 3 parts of surfactant polyethylene glycol, and 12 parts of water, place the composite conductive nanomaterial in the silicone oil, add the surfactant and resin, stir slowly, add water during the stirring process, and mix evenly to obtain a curing ink functional agent.

[0099] Comparative Example 3

[0100] The preparation of an environmentally friendly antistatic LED-UV curing ink functional agent comprises the following specific steps:

[0101] Weigh 20 parts of the composite conductive nanomaterial in Preparation Example 7, 12 parts of acrylic resin, 30 parts of silicone oil, 3 parts of surfactant polyethylene glycol, and 12 parts of water, place the composite conductive nanomaterial in the silicone oil, add the surfactant and resin, stir slowly, add water during the stirring process, and mix evenly to obtain a curing ink functional agent.

[0102] Comparative Example 4

[0103] The preparation of an environmentally friendly antistatic LED-UV curing ink functional agent comprises the following specific steps:

[0104] Weigh 20 parts of the composite conductive nanomaterial in Preparation Example 8, 12 parts of acrylic resin, 30 parts of silicone oil, 3 parts of surfactant polyethylene glycol, and 12 parts of water, place the composite conductive nanomaterial in the silicone oil, add the surfactant and resin, stir slowly, add water during the stirring process, and mix evenly to obtain a curing ink functional agent.

[0105] Comparative Example 5

[0106] The preparation of an environmentally friendly antistatic LED-UV curing ink functional agent comprises the following specific steps:

[0107] Weigh 20 parts of the composite conductive nanomaterial in Preparation Example 9, 12 parts of acrylic resin, 30 parts of silicone oil, 3 parts of surfactant polyethylene glycol, and 12 parts of water, place the composite conductive nanomaterial in the silicone oil, add the surfactant and resin, stir slowly, add water during the stirring process, and mix evenly to obtain a curing ink functional agent.

[0108] The environmentally friendly antistatic LED-UV curing ink functional agents prepared in the above examples and comparative examples were added to conventional UV inks for testing. The antistatic ability, adhesion, and pattern printing effect of each ink were tested. The usage of the functional agents in each example and comparative example was 3-15% of the LED-UV curing ink.

[0109] The formula of this conventional UV ink is as follows:

[0110] 20 parts of epoxy acrylic resin monomer, 10 parts of polyester acrylic resin, 5 parts of silica, 1 part of defoaming agent, 5 parts of pentaerythritol, 20 parts of tripropylene glycol diacrylate, 5 parts of benzophenone and the environmentally friendly antistatic LED-UV curing ink functional agent in this application. The amount of the environmentally friendly antistatic LED-UV curing ink functional agent is shown in Tables 1 and 2 below.

[0111] Experiments and data

[0112] The test method is as follows:

[0113] The antistatic ability is tested according to the standard of GB1410-2006.

[0114] Adhesion was tested according to ASTM D3359-B.

[0115] The pattern printing effect is checked visually, with the standard being whether the pattern is clear and the color is uniform.

[0116] The test data of the embodiment are shown in Table 1 below:

[0117]

[0118] The test data of the comparative example are shown in Table 2 below:

[0119]

[0120] The surface resistivity of each embodiment and each comparative example is plotted as a bar graph. Figure 1 As shown, Figure 1 The value of the vertical axis is the surface resistivity 10 x The value of x in .

[0121] analyze

[0122] From Table 1 and Figure 1 The data show that the antistatic LED-UV curing ink functional agent prepared in Examples 1 to 4 has a good improvement on the surface resistivity, adhesion and printing effect of UV ink.

[0123] The antistatic LED-UV curing ink functional agent of Preparation Example 5 was used in the ink of Comparative Example 1. The carbon nanotubes of the functional agent were not plasma etched, and the remaining steps were the same as those of Preparation Example 1. According to the data in Tables 1 and 2, the surface resistivity of the oil film of Comparative Example 1 was lower than that of Example 1, and the adhesion and printing effect decreased significantly after the usage increased, indicating that etching the carbon nanotubes can effectively improve the adhesion of the ink on the substrate surface and the pattern printing effect.

[0124] The antistatic LED-UV curable ink functional agent of Comparative Example 2 did not subject the carbon nanotubes to pressurized, heated, and ultrasonic treatment, and no water clusters were formed in the carbon nanotubes. The remaining steps were basically the same as those in Preparation Example 1. According to the data in Tables 1 and 2, the surface resistivity, adhesion, and printing effect of the oil film of Comparative Example 2 were not as good as those of Example 1, indicating that the presence of water clusters can better improve the performance of the combination of polyacetylene and carbon nanotubes, and can enhance the problem of decreased antistatic ability of high-concentration functional agents.

[0125] The amount of iodinated polyacetylene used in the antistatic LED-UV curing ink functional agent of Comparative Example 3 is less than that of carbon nanotubes. According to the data in Tables 1 and 2, the surface resistivity of Comparative Example 3 is higher and the printing effect is better, but the adhesion is lower, indicating that the conjugated structure of polyacetylene is more preserved and not destroyed, and has a stronger antistatic ability.

[0126] Single-arm carbon nanotubes are used in the antistatic LED-UV curing ink functional agent of Comparative Example 4. According to the data in Tables 1 and 2, the surface resistivity of this comparative example is slightly improved, but its adhesion and printing effect decrease significantly with the increase in usage, indicating that multi-walled carbon nanotubes with a larger inner diameter can improve ink adhesion and printing effect, and reduce the impact of using more antistatic agents.

[0127] The polyacetylene in the antistatic LED-UV curing ink functional agent of Comparative Example 5 was not iodized, and the conductivity of the polyacetylene was not improved. The conductivity was improved only by combining polyacetylene with carbon nanotubes. According to the data in Tables 1 and 2, the surface resistance and printing effect of Comparative Example 5 were poor, but the adhesion was very good, indicating that the conductive properties of polyacetylene itself have a greater impact on the antistatic properties of the functional agent of this application, and can improve the antistatic ability of the ink.

[0128] Thus far, the technical solutions of the present invention have been described in conjunction with the preferred embodiments shown in the accompanying drawings. However, it will be readily understood by those skilled in the art that the scope of protection of the present invention is obviously not limited to these specific embodiments. Without departing from the principles of the present invention, those skilled in the art may make equivalent changes or substitutions to the relevant technical features, and the technical solutions after such changes or substitutions will fall within the scope of protection of the present invention.

Claims

1. An environmentally friendly antistatic LED-UV curing ink functional agent, characterized in that: The composition is as follows by weight: Composite conductive nanomaterial: 10-30 parts, resin: 6-12 parts, silicone oil: 20-40 parts, surfactant: 1-5 parts and water: 10-20 parts; The composite conductive nanomaterial is prepared by filling carbon nanotubes and iodinated polyacetylene in a weight ratio of 1:1-1.2 and then stabilizing the mixture. The preparation method of the composite conductive nanomaterial is as follows: S1. Treating the carbon nanotubes with concentrated nitric acid, drying them, and then plasma etching them to obtain uncapped carbon nanotubes. Placing the uncapped carbon nanotubes in water, applying pressure and heating, and surface drying them to obtain carbon nanotubes having an inner diameter of 20-50 nm. S2, placing polyacetylene in iodine vapor for reaction to obtain iodinated polyacetylene; S3, self-assembly of iodinated polyacetylene and carbon nanotubes, dissolving iodinated polyacetylene in a solvent, adding a surfactant, then adding carbon nanotubes and stirring to react, and evaporating the solvent to obtain composite conductive nanotubes; S4, placing the composite conductive nanotubes in chloroform, adding iron powder, performing ultrasonic mixing, and then performing a thermal reaction to obtain a stabilized composite conductive nanomaterial; The carbon nanotubes in S1 are multi-walled carbon nanotubes, the diameter of the multi-walled carbon nanotubes is 30-80 nm, the ratio of the carbon nanotubes to water is 1:2, the treatment pressure is 1.5-3.0 MPa, the treatment temperature is 140-220° C., and the pressurized and heated treatment is followed by ultrasonic treatment, the ultrasonic power is 200-300 W, and the ultrasonic treatment time is 20-30 min; The mass ratio of the polyacetylene to iodine vapor is 1:2-3, and the reaction temperature is 190-220°C.

2. The environmentally friendly antistatic LED-UV curing ink functional agent according to claim 1, characterized in that: The S3 solvent is one of n-octane, chloroform, chloroform or tetrahydrofuran, and the solid-liquid ratio of the iodinated polyacetylene to the solvent is 1g:100-120ml.

3. The environmentally friendly antistatic LED-UV curing ink functional agent according to claim 1, characterized in that: The surfactant in S3 is one of sodium lauryl sulfate, sodium lauryl sulfonate, sodium tetrapropylene sulfonate or sodium dioctyl sulfosuccinate.

4. The environmentally friendly antistatic LED-UV curing ink functional agent according to claim 1, characterized in that: The added volume ratio of the surfactant to the solvent in the S3 is 2-10:

100.

5. The environmentally friendly antistatic LED-UV curing ink functional agent according to claim 1, characterized in that: The solid-liquid ratio of the carbon nanotubes in S1 treated with concentrated nitric acid is 1g:10ml, the treatment temperature is 140-200°C, and the reaction time is 24-48h.

6. The environmentally friendly antistatic LED-UV curing ink functional agent according to claim 1, characterized in that: The plasma excitation power of the plasma etching in S1 is 100-2000W, the etching environment pressure is 1000Pa, and the impact gas of the plasma etching is one of oxygen, air, nitrogen or argon.

7. The environmentally friendly antistatic LED-UV curing ink functional agent according to claim 1, characterized in that: The usage of the functional agent is 3-15% of the LED-UV curing ink.

8. Use of the environmentally friendly antistatic LED-UV curing ink functional agent according to any one of claims 1 to 7 in ink.

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