Colored permanent antistatic PETG material applied to 3D printing

Abstract

The invention discloses a colored permanent antistatic PETG material applied to 3D printing. The colored permanent antistatic PETG material comprises the following components in parts by weight: 50-80 parts of a PETG material, 5-20 parts of a PC material, 10-30 parts of a permanent antistatic agent, 5-15 parts of a reinforcing agent, 1-5 parts of a lubricant, 1-5 parts of a compatilizer, 0.1-0.5 part of a coupling agent, 0.1-0.4 part of a hindered phenol antioxidant, 0.1-0.4 part of a phosphite antioxidant, 0.1-0.4 part of a plasticizer and 0.1-0.4 part of toner. The composite material has the beneficial effects that a PETG / PC alloy modification mode is used, so that the heat resistance, the mechanical property and the interlayer adhesive force of the PETG composite material are improved; the high-molecular permanent antistatic agent is used, so that the antistatic capacity of the material is improved under the condition that the color of PETG is not influenced, and the problem that a conventional carbon nanotube / conductive carbon black modified antistatic PETG material cannot be subjected to color matching is solved.

Description

Technical Field

[0001] This invention relates to the field of colored permanent antistatic PETG materials, and in particular to a colored permanent antistatic PETG material for 3D printing. Background Technology

[0002] In recent years, with the popularization of additive manufacturing 3D printing technology, fused deposition modeling (FDM) has gradually become an important part of the manufacturing process. FDM technology uses digital model files to complete the manufacturing model layer by layer, simplifying the manufacturing process and reducing production and R&D costs. It is gradually being applied to various industries. Polyethylene terephthalate-1,4-cyclohexanediethanol ester (PETG) is a non-crystalline green and environmentally friendly engineering plastic. Due to its high transparency, low shrinkage of amorphous materials, low price, and environmental friendliness, it has become one of the most widely used materials in the FDM field.

[0003] With the popularization of FDM technology, materials such as PETG are gradually being used in the fields of electronics, electrical appliances, and medical care. However, the surface resistance of PETG materials is usually between 10^14 and 10^16 Ω. The extremely high insulation will cause charge transfer due to friction. In an environment where the charge cannot be released, PETG materials with long-term accumulated charge will attract a large amount of dust. In severe cases, high voltage discharge will occur. Antistatic modification is extremely important for the application of PETG materials in the electronics and electrical appliance industries.

[0004] 3D-printed electronic and electrical products are typically used in various environments and have long service lives, making permanent antistatic materials (surface resistivity of 10^6 to 10^9 Ω) particularly important. Currently, permanent antistatic PETG materials are usually modified with multi-walled carbon nanotubes (CNTs). These permanent antistatic composite materials are typically black and virtually impossible to color match. In contrast, polymeric permanent antistatic agents are usually white and do not affect color matching, but they negatively impact the interlayer adhesion, strength, and modulus of PETG materials, thus limiting the application of permanent antistatic PETG materials in the field of 3D printing.

[0005] Therefore, this patent develops a colored permanent antistatic PETG material for 3D printing. It uses polymeric antistatic agents to improve the surface resistance of PETG materials, solves the problem of color matching in conventional carbon nanotube / conductive carbon black modified antistatic PETG materials, and improves the negative impact of permanent polymeric antistatic agents on interlayer adhesion of PETG materials. Summary of the Invention

[0006] To address the aforementioned technical problems, this invention provides a colored permanent antistatic PETG material for 3D printing, comprising the following components in parts by weight: 50-80 parts PETG material, 5-20 parts PC material, 10-30 parts permanent antistatic agent, 5-15 parts reinforcing agent, 1-5 parts lubricant, 1-5 parts compatibilizer, 0.1-0.5 parts coupling agent, 0.1-0.4 parts hindered phenolic antioxidant, 0.1-0.4 parts phosphite antioxidant, 0.1-0.4 parts plasticizer, and 0.1-0.4 parts pigment.

[0007] As a further supplement to this technical solution, the permanent antistatic agent is a polymeric permanent antistatic agent that does not affect the color matching of the material. It is one or more of the following: polyethylene oxide (PEO) and its copolymers, polyvinylpyrrolidone (PVP), polyethylene glycol (PEG) modified polymers, polystyrene sulfonate (PSS), quaternized polyacrylate, polymeric complexes containing metal salts, polyaniline (PANI), polypyrrole (PPy), polythiophene (PTh) and its derivatives.

[0008] As a further supplement to this technical solution, the reinforcing agent is one or more of nano-alumina, nano-silica, glass fiber (GF), cellulose nanofiber (CNF) and their modified derivatives, which reinforce the material without affecting the material's color matching.

[0009] As a further supplement to this technical solution, the lubricant is one or a combination of two of calcium stearate and organic wax lubricant.

[0010] As a further supplement to this technical solution, the compatibilizer is preferably one or more of PS-g-MAH, PS-co-GMA, POE-g-MAH, and SEBS-g-MAH copolymers.

[0011] As a further supplement to this technical solution, the coupling agent is one or more of silane coupling agents and aluminate coupling agents.

[0012] As a further supplement to this technical solution, the hindered phenolic antioxidant is one or more of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and 4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene.

[0013] As a further supplement to this technical solution, the phosphite antioxidant is one or more of bis(2,4-di-tert-butylphenol) pentaerythritol diphosphite, tris[2,4-di-tert-butylphenyl]phosphite, and poly(dipropylene glycol) phenyl phosphite.

[0014] As a further supplement to this technical solution, the plasticizer is one or more of paraffin oil, epoxidized soybean oil, polyethylene glycol, and citric acid fatty acid glycerol; the color powder is one or a combination of inorganic color powder and organic color powder.

[0015] A method for preparing a colored permanent antistatic PETG material for 3D printing includes the following steps:

[0016] Step 1: Dry PETG at 65-85℃ until the moisture content is no higher than 0.05%wt, then cool to room temperature for later use;

[0017] Step 2: Weigh the PETG raw material, PC material, permanent antistatic agent, reinforcing agent, lubricant, compatibilizer, coupling agent, hindered phenolic antioxidant, phosphite antioxidant, plasticizer and color powder according to the formula ratio, and stir the weighed components at a speed of 100-600 r / min for 5-20 min to obtain the pre-made raw material;

[0018] Step 3: Add the pre-made raw material into a twin-screw extruder for extrusion and granulation to obtain modified granules. The temperatures of each zone of the twin-screw extruder are set as follows: Zone 1 180-220℃, Zone 2 220-240℃, Zone 3 225-245℃, Zone 4 228-248℃, Zone 5 228-248℃, Zone 6 230-250℃, Zone 7 230-250℃, Zone 8 232-252℃, Zone 9 232-252℃, Zone 10 235-255℃, Zone 11 235-255℃, Die head 235-255℃, Main engine speed 200-500 r / min, Feeding frequency 5-15 r / min;

[0019] Step 4: Dry the modified granules at 65-85℃ until the moisture content does not exceed 0.05% to obtain dried granules. Then, add the dried granules to a single-screw extruder to extrude plastic melt. The heating zones of the single-screw extruder are set as follows: Zone 1 190-225℃, Zone 2 195-235℃, Zone 3 195-235℃, Zone 4 195-232℃, Zone 5 195-230℃, Zone 6 195-230℃, hot water temperature 55-70℃, cold water temperature 30-40℃. After the obtained wire is dried, it is then printed and tested.

[0020] Its beneficial effects are as follows: This patent uses PETG / PC alloy modification to improve the heat resistance, mechanical properties, and interlayer adhesion of PETG composite materials; this patent uses a polymeric permanent antistatic agent to enhance the antistatic ability of the material without affecting the color of PETG, solving the problem of color matching in conventional carbon nanotube / conductive carbon black modified antistatic PETG materials; this patent uses glass fiber, cellulose nanofiber, and their surface conductive modified derivatives as reinforcing agents to improve the strength, rigidity, and interlayer adhesion of PETG / polymeric antistatic agent composite materials, enabling the composite material performance to meet the requirements of 3D printing; this patent uses a lubricant to improve the flowability of PETG while solving the problem of PETG material sticking to the printing nozzle; this patent uses a compatibilizer to increase the compatibility between PETG, PC, polymeric permanent antistatic agent, and reinforcing agent, improving the interlayer adhesion of the material; this patent uses a coupling agent to bridge the compatibility between the reinforcing agent and the polymeric resin, improving the interlayer adhesion of the material. Detailed Implementation

[0021] To facilitate a clearer understanding of this technical solution by those skilled in the art, the technical solution of the present invention will be described in detail below with reference to embodiments:

[0022] Example 1

[0023] A colored permanent antistatic PETG material for 3D printing comprises the following components in parts by weight: 63 parts PETG material (grade S2008, manufactured by SK Corporation), 20 parts permanent antistatic agent (grade PELESTAT6500, manufactured by Sanyo Chemical Co., Ltd.), 10 parts glass fiber (GF), 3 parts lubricant, 3 parts compatibilizer, 0.2 parts coupling agent, 0.15 parts hindered phenolic antioxidant, 0.15 parts phosphite antioxidant, 0.2 parts plasticizer, and 0.3 parts blue pigment.

[0024] The above-mentioned method for preparing modified PETG materials for 3D printing includes the following steps:

[0025] Bake PETG at 65-85℃ until the moisture content is no higher than 0.05%wt, then cool to room temperature for later use.

[0026] Weigh out PETG raw materials, PC materials, permanent antistatic agents, reinforcing agents, lubricants, compatibilizers, coupling agents, hindered phenolic antioxidants, phosphite antioxidants, plasticizers, and color powders according to the formula ratio, and stir the weighed components at a speed of 100-600 r / min for 5-20 min to obtain the pre-made raw materials;

[0027] The pre-made raw materials are added to a twin-screw extruder for extrusion and granulation to obtain modified granules. The temperatures of each zone of the twin-screw extruder are set as follows: Zone 1 195℃, Zone 2 220℃, Zone 3 225℃, Zone 4 228℃, Zone 5 228℃, Zone 6 230℃, Zone 7 230℃, Zone 8 232℃, Zone 9 232℃, Zone 10 235℃, Zone 11 235℃, Die head 235℃, Main engine speed 350r / min, Feeding frequency 12r / min;

[0028] The modified granules are dried at 65-85℃ until the moisture content does not exceed 0.05%, resulting in dried granules. The dried granules are then added to a single-screw extruder to extrude plastic melt. The heating zones of the single-screw extruder are set as follows: Zone 1 190℃, Zone 2 220℃, Zone 3 225℃, Zone 4 225℃, Zone 5 225℃, Zone 6 225℃, hot water temperature 70℃, and cold water temperature 30℃. After the resulting wire is dried, it is then printed and tested.

[0029] Example 2

[0030] A colored permanent antistatic PETG material for 3D printing comprises the following components in parts by weight: 53 parts PETG material (brand name S2008, manufactured by SK Corporation), 10 parts PC material, 20 parts permanent antistatic agent (brand name PELESTAT6500, manufactured by Sanyo Chemical Co., Ltd.), 10 parts glass fiber (GF), 3 parts lubricant, 3 parts compatibilizer, 0.2 parts coupling agent, 0.15 parts hindered phenolic antioxidant, 0.15 parts phosphite antioxidant, 0.2 parts plasticizer, and 0.3 parts blue pigment.

[0031] The above-mentioned method for preparing modified PETG materials for 3D printing includes the following steps:

[0032] Bake PETG at 65-85℃ until the moisture content is no higher than 0.05%wt, then cool to room temperature for later use.

[0033] Weigh out PETG raw materials, PC materials, permanent antistatic agents, reinforcing agents, lubricants, compatibilizers, coupling agents, hindered phenolic antioxidants, phosphite antioxidants, plasticizers, and color powders according to the formula ratio, and stir the weighed components at a speed of 100-600 r / min for 5-20 min to obtain the pre-made raw materials;

[0034] The pre-made raw materials are added to a twin-screw extruder for extrusion and granulation to obtain modified granules. The temperatures of each zone of the twin-screw extruder are set as follows: Zone 1 195℃, Zone 2 220℃, Zone 3 225℃, Zone 4 228℃, Zone 5 228℃, Zone 6 230℃, Zone 7 230℃, Zone 8 232℃, Zone 9 232℃, Zone 10 235℃, Zone 11 235℃, Die head 235℃, Main engine speed 350r / min, Feeding frequency 12r / min;

[0035] The modified granules are dried at 65-85℃ until the moisture content does not exceed 0.05%, resulting in dried granules. The dried granules are then added to a single-screw extruder to extrude plastic melt. The heating zones of the single-screw extruder are set as follows: Zone 1 190℃, Zone 2 220℃, Zone 3 225℃, Zone 4 225℃, Zone 5 225℃, Zone 6 225℃, hot water temperature 70℃, and cold water temperature 30℃. After the resulting wire is dried, it is then printed and tested.

[0036] Example 3

[0037] A colored permanent antistatic PETG material for 3D printing comprises the following components in parts by weight: 58 parts PETG material (brand name S2008, manufactured by SK Corporation), 10 parts PC material, 20 parts permanent antistatic agent (brand name PELESTAT6500, manufactured by Sanyo Chemical Co., Ltd.), 5 parts cellulose nanofibers (CNF), 3 parts lubricant, 3 parts compatibilizer, 0.2 parts coupling agent, 0.15 parts hindered phenolic antioxidant, 0.15 parts phosphite antioxidant, 0.2 parts plasticizer, and 0.3 parts blue pigment.

[0038] The above-mentioned method for preparing modified PETG materials for 3D printing includes the following steps:

[0039] Bake PETG at 65-85℃ until the moisture content is no higher than 0.05%wt, then cool to room temperature for later use.

[0040] Weigh out PETG raw materials, PC materials, permanent antistatic agents, reinforcing agents, lubricants, compatibilizers, coupling agents, hindered phenolic antioxidants, phosphite antioxidants, plasticizers, and color powders according to the formula ratio, and stir the weighed components at a speed of 100-600 r / min for 5-20 min to obtain the pre-made raw materials;

[0041] The pre-made raw materials are added to a twin-screw extruder for extrusion and granulation to obtain modified granules. The temperatures of each zone of the twin-screw extruder are set as follows: Zone 1 195℃, Zone 2 220℃, Zone 3 225℃, Zone 4 228℃, Zone 5 228℃, Zone 6 230℃, Zone 7 230℃, Zone 8 232℃, Zone 9 232℃, Zone 10 235℃, Zone 11 235℃, Die head 235℃, Main engine speed 350r / min, Feeding frequency 12r / min;

[0042] The modified granules are dried at 65-85℃ until the moisture content does not exceed 0.05%, resulting in dried granules. The dried granules are then added to a single-screw extruder to extrude plastic melt. The heating zones of the single-screw extruder are set as follows: Zone 1 190℃, Zone 2 220℃, Zone 3 225℃, Zone 4 225℃, Zone 5 225℃, Zone 6 225℃, hot water temperature 70℃, and cold water temperature 30℃. After the resulting wire is dried, it is then printed and tested.

[0043] Example 4

[0044] A colored permanent antistatic PETG material for 3D printing comprises the following components in parts by weight: 53 parts PETG material (brand name S2008, manufactured by SK Corporation), 10 parts PC material, 20 parts permanent antistatic agent (brand name PELESTAT6500, manufactured by Sanyo Chemical Co., Ltd.), 5 parts glass fiber (GF), 5 parts cellulose nanofiber (CNF), 3 parts lubricant, 3 parts compatibilizer, 0.2 parts coupling agent, 0.15 parts hindered phenolic antioxidant, 0.15 parts phosphite antioxidant, 0.2 parts plasticizer, and 0.3 parts blue pigment.

[0045] The above-mentioned method for preparing modified PETG materials for 3D printing includes the following steps:

[0046] Bake PETG at 65-85℃ until the moisture content is no higher than 0.05%wt, then cool to room temperature for later use.

[0047] Weigh out PETG raw materials, PC materials, permanent antistatic agents, reinforcing agents, lubricants, compatibilizers, coupling agents, hindered phenolic antioxidants, phosphite antioxidants, plasticizers, and color powders according to the formula ratio, and stir the weighed components at a speed of 100-600 r / min for 5-20 min to obtain the pre-made raw materials;

[0048] The pre-made raw materials are added to a twin-screw extruder for extrusion and granulation to obtain modified granules. The temperatures of each zone of the twin-screw extruder are set as follows: Zone 1 195℃, Zone 2 220℃, Zone 3 225℃, Zone 4 228℃, Zone 5 228℃, Zone 6 230℃, Zone 7 230℃, Zone 8 232℃, Zone 9 232℃, Zone 10 235℃, Zone 11 235℃, Die head 235℃, Main engine speed 350r / min, Feeding frequency 12r / min;

[0049] The modified granules are dried at 65-85℃ until the moisture content does not exceed 0.05%, resulting in dried granules. The dried granules are then added to a single-screw extruder to extrude plastic melt. The heating zones of the single-screw extruder are set as follows: Zone 1 190℃, Zone 2 220℃, Zone 3 225℃, Zone 4 225℃, Zone 5 225℃, Zone 6 225℃, hot water temperature 70℃, and cold water temperature 30℃. After the resulting wire is dried, it is then printed and tested.

[0050] Comparative Example 1

[0051] A colored permanent antistatic PETG material for 3D printing comprises the following components in parts by weight: 78 parts PETG material (brand name S2008, manufactured by SK Corporation), 15 parts permanent antistatic agent (brand name PELESTAT6500, manufactured by Sanyo Chemical Co., Ltd.), 3 parts lubricant, 3 parts compatibilizer, 0.2 parts coupling agent, 0.15 parts hindered phenolic antioxidant, 0.15 parts phosphite antioxidant, 0.2 parts plasticizer, and 0.3 parts blue pigment.

[0052] The above-mentioned method for preparing modified PETG materials for 3D printing includes the following steps:

[0053] Bake PETG at 65-85℃ until the moisture content is no higher than 0.05%wt, then cool to room temperature for later use.

[0054] Weigh out PETG raw materials, PC materials, permanent antistatic agents, reinforcing agents, lubricants, compatibilizers, coupling agents, hindered phenolic antioxidants, phosphite antioxidants, plasticizers, and color powders according to the formula ratio, and stir the weighed components at a speed of 100-600 r / min for 5-20 min to obtain the pre-made raw materials;

[0055] The pre-made raw materials are added to a twin-screw extruder for extrusion and granulation to obtain modified granules. The temperatures of each zone of the twin-screw extruder are set as follows: Zone 1 195℃, Zone 2 220℃, Zone 3 225℃, Zone 4 228℃, Zone 5 228℃, Zone 6 230℃, Zone 7 230℃, Zone 8 232℃, Zone 9 232℃, Zone 10 235℃, Zone 11 235℃, Die head 235℃, Main engine speed 350r / min, Feeding frequency 12r / min;

[0056] The modified granules are dried at 65-85℃ until the moisture content does not exceed 0.05%, resulting in dried granules. The dried granules are then added to a single-screw extruder to extrude plastic melt. The heating zones of the single-screw extruder are set as follows: Zone 1 190℃, Zone 2 220℃, Zone 3 225℃, Zone 4 225℃, Zone 5 225℃, Zone 6 225℃, hot water temperature 70℃, and cold water temperature 30℃. After the resulting wire is dried, it is then printed and tested.

[0057] Comparative Example 2

[0058] A colored permanent antistatic PETG material for 3D printing comprises the following components in parts by weight: 68 parts PETG material (brand name S2008, manufactured by SK Corporation), 10 parts PC material, 15 parts permanent antistatic agent (brand name PELESTAT6500, manufactured by Sanyo Chemical Co., Ltd.), 3 parts lubricant, 3 parts compatibilizer, 0.2 parts coupling agent, 0.15 parts hindered phenolic antioxidant, 0.15 parts phosphite antioxidant, 0.2 parts plasticizer, and 0.3 parts blue pigment.

[0059] The above-mentioned method for preparing modified PETG materials for 3D printing includes the following steps:

[0060] Bake PETG at 65-85℃ until the moisture content is no higher than 0.05%wt, then cool to room temperature for later use.

[0061] Weigh out PETG raw materials, PC materials, permanent antistatic agents, reinforcing agents, lubricants, compatibilizers, coupling agents, hindered phenolic antioxidants, phosphite antioxidants, plasticizers, and color powders according to the formula ratio, and stir the weighed components at a speed of 100-600 r / min for 5-20 min to obtain the pre-made raw materials;

[0062] The pre-made raw materials are added to a twin-screw extruder for extrusion and granulation to obtain modified granules. The temperatures of each zone of the twin-screw extruder are set as follows: Zone 1 195℃, Zone 2 220℃, Zone 3 225℃, Zone 4 228℃, Zone 5 228℃, Zone 6 230℃, Zone 7 230℃, Zone 8 232℃, Zone 9 232℃, Zone 10 235℃, Zone 11 235℃, Die head 235℃, Main engine speed 350r / min, Feeding frequency 12r / min;

[0063] The modified granules are dried at 65-85℃ until the moisture content does not exceed 0.05%, resulting in dried granules. The dried granules are then added to a single-screw extruder to extrude plastic melt. The heating zones of the single-screw extruder are set as follows: Zone 1 190℃, Zone 2 220℃, Zone 3 225℃, Zone 4 225℃, Zone 5 225℃, Zone 6 225℃, hot water temperature 70℃, and cold water temperature 30℃. After the resulting wire is dried, it is then printed and tested.

[0064] Comparative Example 3

[0065] A colored permanent antistatic PETG material for 3D printing comprises the following components in parts by weight: 58 parts PETG material (brand name S2008, manufactured by SK Corporation), 10 parts PC material, 15 parts permanent antistatic agent (brand name PELESTAT6500, manufactured by Sanyo Chemical Co., Ltd.), 10 parts glass fiber (GF), 3 parts lubricant, 3 parts compatibilizer, 0.2 parts coupling agent, 0.15 parts hindered phenolic antioxidant, 0.15 parts phosphite antioxidant, 0.2 parts plasticizer, and 0.3 parts blue pigment.

[0066] The above-mentioned method for preparing modified PETG materials for 3D printing includes the following steps:

[0067] Bake PETG at 65-85℃ until the moisture content is no higher than 0.05%wt, then cool to room temperature for later use.

[0068] Weigh out PETG raw materials, PC materials, permanent antistatic agents, reinforcing agents, lubricants, compatibilizers, coupling agents, hindered phenolic antioxidants, phosphite antioxidants, plasticizers, and color powders according to the formula ratio, and stir the weighed components at a speed of 100-600 r / min for 5-20 min to obtain the pre-made raw materials;

[0069] The pre-made raw materials are added to a twin-screw extruder for extrusion and granulation to obtain modified granules. The temperatures of each zone of the twin-screw extruder are set as follows: Zone 1 195℃, Zone 2 220℃, Zone 3 225℃, Zone 4 228℃, Zone 5 228℃, Zone 6 230℃, Zone 7 230℃, Zone 8 232℃, Zone 9 232℃, Zone 10 235℃, Zone 11 235℃, Die head 235℃, Main engine speed 350r / min, Feeding frequency 12r / min;

[0070] The modified granules are dried at 65-85℃ until the moisture content does not exceed 0.05%, resulting in dried granules. The dried granules are then added to a single-screw extruder to extrude plastic melt. The heating zones of the single-screw extruder are set as follows: Zone 1 190℃, Zone 2 220℃, Zone 3 225℃, Zone 4 225℃, Zone 5 225℃, Zone 6 225℃, hot water temperature 70℃, and cold water temperature 30℃. After the resulting wire is dried, it is then printed and tested.

[0071] Comparative Example 4

[0072] A colored permanent antistatic PETG material for 3D printing comprises the following components in parts by weight: 63 parts PETG material (brand name S2008, manufactured by SK Corporation), 10 parts PC material, 15 parts permanent antistatic agent (brand name PELESTAT6500, manufactured by Sanyo Chemical Co., Ltd.), 5 parts cellulose nanofibers (CNF), 3 parts lubricant, 3 parts compatibilizer, 0.2 parts coupling agent, 0.15 parts hindered phenolic antioxidant, 0.15 parts phosphite antioxidant, 0.2 parts plasticizer, and 0.3 parts blue pigment.

[0073] The above-mentioned method for preparing modified PETG materials for 3D printing includes the following steps:

[0074] Bake PETG at 65-85℃ until the moisture content is no higher than 0.05%wt, then cool to room temperature for later use.

[0075] Weigh out PETG raw materials, PC materials, permanent antistatic agents, reinforcing agents, lubricants, compatibilizers, coupling agents, hindered phenolic antioxidants, phosphite antioxidants, plasticizers, and color powders according to the formula ratio, and stir the weighed components at a speed of 100-600 r / min for 5-20 min to obtain the pre-made raw materials;

[0076] The pre-made raw materials are added to a twin-screw extruder for extrusion and granulation to obtain modified granules. The temperatures of each zone of the twin-screw extruder are set as follows: Zone 1 195℃, Zone 2 220℃, Zone 3 225℃, Zone 4 228℃, Zone 5 228℃, Zone 6 230℃, Zone 7 230℃, Zone 8 232℃, Zone 9 232℃, Zone 10 235℃, Zone 11 235℃, Die head 235℃, Main engine speed 350r / min, Feeding frequency 12r / min;

[0077] The modified granules are dried at 65-85℃ until the moisture content does not exceed 0.05%, resulting in dried granules. The dried granules are then added to a single-screw extruder to extrude plastic melt. The heating zones of the single-screw extruder are set as follows: Zone 1 190℃, Zone 2 220℃, Zone 3 225℃, Zone 4 225℃, Zone 5 225℃, Zone 6 225℃, hot water temperature 70℃, and cold water temperature 30℃. After the resulting wire is dried, it is then printed and tested.

[0078] The testing method for the materials used in this invention includes the following steps:

[0079] The filaments from Examples 1-4 and Comparative Examples 1-4 were printed using an FDM 3D printer to test their surface resistivity, XZ tensile strength, and XY impact strength. Printing conditions included a printhead temperature of 255℃, a substrate temperature of 65-80℃, and the substrate being coated with Tri-Whe 190 varnish to increase adhesion between the substrate and the printed part. The printing speed was 100 mm / s. At a standard printing speed of 100 mm / s, dumbbell-shaped specimens were printed according to standard ISO 527 to test the XZ tensile strength, characterizing the interlayer adhesion. At a standard printing speed of 100 mm / s, specimens according to standard ISO 179 were printed to test the XY impact strength, characterizing the toughness. The test results are shown in Table 1.

[0080] Table 1. Effects and performance of wire printing in the examples and comparative examples.

[0081] <![CDATA[Tensile strength in the X-Z direction (KJ / m 2 )]]> <![CDATA[X-Y direction impact strength (KJ / m 2 )]]> Surface resistance Ω Example 1 16.5 60.5 4.2*10^8 Example 2 17 59.3 4.3*10^8 Example 3 15.5 61.2 1.2*10^8 Example 4 18 55 3.5*10^8 Comparative Example 1 9 66 3.5*10^8 Comparative Example 2 9.5 65.4 3.6*10^8 Comparative Example 3 19 52.6 4.1*10^10 Comparative Example 4 18.5 52.1 2.8*10^10

[0082] The filaments in Examples 1-4 of this invention are blue in color, have a surface resistivity that meets the antistatic range of 10^-10^9Ω, and have interlayer adhesion (tensile strength in the ZX direction) ≥14Mpa, which meets the requirements for 3D printed products in the electronics industry. This patent solves the problem of color matching for conventional carbon nanotube / conductive carbon black modified antistatic PETG materials and improves the negative impact of permanent polymer antistatic agents on interlayer adhesion of PETG materials.

[0083] As can be seen from the printing results of Examples 1 and 2, PC-modified PETG material, when added in an appropriate amount, does not affect the printing warpage and antistatic properties of the material, and can improve the interlayer adhesion strength of the material to a small extent.

[0084] The printing results of Examples 2, 3, and 4 show that cellulose nanofibers (CNF) have a relatively small addition amount of only 5% wt due to the surface aggregation effect. Compared with the 10% wt addition amount of glass fiber (GF), CNF has little effect on improving the material strength and interlayer adhesion. However, the combination of cellulose nanofibers (CNF) and glass fiber (GF) significantly increases the material strength and interlayer adhesion.

[0085] The printing results of Comparative Examples 1-2 and Examples 1-2 show that the composite material without added glass fiber (GF) has extremely high toughness and is relatively soft, but its strength, rigidity, and interlayer adhesion are extremely weak, which does not meet the conventional requirements of 3D printing materials.

[0086] The printing results of Comparative Examples 3-4 and Examples 2-3 show that adding glass fiber (GF) and cellulose nanofiber (CNF) to the composite material increases the material strength and interlayer adhesion. However, the insulating GF and CNF affect the conductivity of the material, making the antistatic effect of the material unsatisfactory. Therefore, it is necessary to increase the content of polymeric antistatic agent.

[0087] The above technical solutions only embody the preferred technical solutions of the present invention. Any modifications that may be made by those skilled in the art to certain parts thereof embody the principles of the present invention and fall within the protection scope of the present invention.

Claims

1. A colored permanent antistatic PETG material for 3D printing, characterized in that, It comprises the following components in parts by weight: 50-80 parts PETG material, 5-20 parts PC material, 10-30 parts permanent antistatic agent, 5-15 parts reinforcing agent, 1-5 parts lubricant, 1-5 parts compatibilizer, 0.1-0.5 parts coupling agent, 0.1-0.4 parts hindered phenolic antioxidant, 0.1-0.4 parts phosphite antioxidant, 0.1-0.4 parts plasticizer, and 0.1-0.4 parts colorant.

2. The colored permanent antistatic PETG material for 3D printing according to claim 1, characterized in that, The permanent antistatic agent is a polymeric permanent antistatic agent, which is one or more of the following: polyethylene oxide and its copolymers, polyvinylpyrrolidone, polyethylene glycol modified polymers, polystyrene sulfonate, quaternized polyacrylate, polymeric complexes containing metal salts, polyaniline, polypyrrole, polythiophene and its derivatives.

3. The colored permanent antistatic PETG material for 3D printing according to claim 2, characterized in that, The reinforcing agent is one or more of nano-alumina, nano-silica, glass fiber, cellulose nanofiber, and their modified derivatives.

4. The colored permanent antistatic PETG material for 3D printing according to claim 1, characterized in that, The lubricant is one or a combination of calcium stearate and organic wax lubricant.

5. A colored permanent antistatic PETG material for 3D printing according to claim 1, characterized in that, The compatibilizer is preferably one or more of PS-g-MAH, PS-co-GMA, POE-g-MAH, and SEBS-g-MAH copolymers.

6. A colored permanent antistatic PETG material for 3D printing according to claim 1, characterized in that, The coupling agent is one or more of silane coupling agents and aluminate coupling agents.

7. A colored permanent antistatic PETG material for 3D printing according to claim 1, characterized in that, The hindered phenolic antioxidant is one or more of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and 4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene.

8. A colored permanent antistatic PETG material for 3D printing according to claim 1, characterized in that, The phosphite antioxidant is one or more of pentaerythritol diphosphite (2,4-di-tert-butylphenol), tris[2,4-di-tert-butylphenyl]phosphite, and poly(dipropylene glycol) phenyl phosphite.

9. A colored permanent antistatic PETG material for 3D printing according to claim 1, characterized in that, The plasticizer is one or more of paraffin oil, epoxidized soybean oil, polyethylene glycol, and citric acid fatty acid glycerol; the color powder is one or a combination of inorganic and organic color powders.

10. A method for preparing a colored permanent antistatic PETG material for 3D printing according to claims 1-9, characterized in that, Includes the following steps: Step 1: Dry PETG at 65-85℃ until the moisture content is no higher than 0.05%wt, then cool to room temperature for later use; Step 2: Weigh the PETG raw material, PC material, permanent antistatic agent, reinforcing agent, lubricant, compatibilizer, coupling agent, hindered phenolic antioxidant, phosphite antioxidant, plasticizer and color powder according to the formula ratio, and stir the weighed components at a speed of 100-600 r / min for 5-20 min to obtain the pre-made raw material; Step 3: Add the pre-made raw material into a twin-screw extruder for extrusion and granulation to obtain modified granules. The temperatures of each zone of the twin-screw extruder are set as follows: Zone 1 180-220℃, Zone 2 220-240℃, Zone 3 225-245℃, Zone 4 228-248℃, Zone 5 228-248℃, Zone 6 230-250℃, Zone 7 230-250℃, Zone 8 232-252℃, Zone 9 232-252℃, Zone 10 235-255℃, Zone 11 235-255℃, Die head 235-255℃, Main engine speed 200-500 r / min, Feeding frequency 5-15 r / min; Step 4: Dry the modified granules at 65-85℃ until the moisture content does not exceed 0.05% to obtain dried granules. Then, add the dried granules to a single-screw extruder to extrude plastic melt. The heating zones of the single-screw extruder are set as follows: Zone 1 190-225℃, Zone 2 195-235℃, Zone 3 195-235℃, Zone 4 195-232℃, Zone 5 195-230℃, Zone 6 195-230℃, hot water temperature 55-70℃, cold water temperature 30-40℃. After the obtained wire is dried, it is then printed and tested.