KR102059777B1 - Conductive filaments for 3D printer and manufacturing method thereof - Google Patents

Abstract

The present invention relates to a conductive filament for a 3D printer and a manufacturing method thereof in which a filament is manufactured by adding iron-copper alloys to a carbon nanotube composite material so that the filament can replaces a heavy wire due to including a metal wire and can be used as a highly conductive and light wire, a polymer elastomer is added to enhance flexibility to improve extrusion efficiency, and a functional coolant is used to remove an odor peculiar to the filament. The present invention comprises carbon nanotubes, which have been surface-activated by using a surface active agent containing a metal salt reducing agent, iron-copper alloys, and polymer elastomers.

Description

Conductive filaments for 3D printer and manufacturing method thereof

The present invention is to produce a filament by adding the iron-copper alloy to the carbon nanotube composite material to replace the heavy wire, including the metal wire can be used as a high conductivity and light wire, and the addition of a polymer elastomer to increase the flexibility to increase the extrusion efficiency The present invention relates to a conductive filament for a 3D printer and a method for manufacturing the same, which can improve the odor and remove the odor peculiar to the filament with functional cooling water.

Recently, as the 3D printer capable of forming 3D objects is utilized in various industrial fields, the acceptance of the technology is increasing.

In particular, 3D printers of filament melting and laminating (FDM method) are advantageous for large-sized, and can be applied to various industrial fields, and are becoming increasingly popular for home and industrial use. Plastic materials such as ABS (Acrylonitrile Butadiene Styrene) and PLA (Poly Lactic Acid) are widely used as filament materials. Especially, PLA resin is preferred to ABS because of its easy output and eco-friendly properties, but its strength and durability are weak. Low conductivity is difficult to apply to various fields such as electrical / electronic components, bio.

Republic of Korea Patent No. 10-1712506

In order to solve the above problems, by adding an iron-copper alloy to the carbon nanotube composite material to produce a filament conductive filament for 3D printer and its use can be used as a high conductivity and light wire by replacing a heavy wire containing metal wire It is an object to provide a manufacturing method.

Another object of the present invention is to provide a conductive filament for a 3D printer and a method for manufacturing the same, which can improve extrusion efficiency by adding a polymer elastomer to enhance flexibility.

Another object of the present invention is to provide a conductive filament for a 3D printer and a method of manufacturing the same, which can remove the odor peculiar to filaments with functional cooling water.

As a means for achieving the above object, the configuration of the production method of the present invention, 1,000 parts by weight of distilled water, 0.1 to 10 parts by weight of activator, 5 to 20 parts by weight of metal salt reducing agent, 50 to 200 parts by weight of acid in order Preparing a surface activator by adding agitated at a rate of 50 to 1,000 RPM for 30 to 50 minutes; Injecting the carbon nanotubes in a weight ratio of 1: 1 to the prepared surface active agent and stirred for 60 minutes to surface-activate the carbon nanotubes; Based on 1,000 parts by weight of the activated carbon nanotubes, 950 parts by weight of the iron-copper alloy, 45 to 49 parts by weight of the polymer elastomer, 1.0 to 5.0 parts by weight of an antioxidant (in an order) to 160 ~ 300 ℃ temperature Primary melt mixing for 10 to 60 minutes at; After completion of the first melt mixing step, the second step is melt mixing for 60 minutes at a temperature of 160 ~ 300 ℃ by sequentially adding 0.1 ~ 5.0 parts by weight of the processing agent, 1 ~ 30 parts by weight of flame retardant (flame retardant) step; Extruding the filament with a diameter of 20-50 mm using a single screw or twin screw extruder; Transferring the extruded filaments to a cooler containing a cooling water containing bamboo charcoal powder and cooling the same at a speed of 0.1 to 100 m / min; Drying the cooled filaments; And a productive step of packaging the dried filaments.

The composition of the present invention, the step of preparing the surface activator, as a surface activator rhodium trichloride (rhodium trichloride), diamine palladium hydroxide (diamine palladium hydroxide), platinum chloride (platinum chloride), palladium chloride ( It is preferable to use at least one of palladium chloride and at least one of zinc chloride, cadmium chloride, and tin chloride as the metal salt reducing agent.

The composition of the present invention, the primary melt-mixing step, as a polymer elastomer, natural rubber, ethylene propylene rubber (ethylene propylene rubber, EPDM), silicone rubber (silicone rubber), nitrile butadiene rubber, NBR), or at least one of chloroprene rubber.Antioxidants play an antioxidant role in the processing of polymer composites, and 2,6-di-tert-butyl-4-methylphenol (2, 6-di-tert-butyl-4-methyl phenol), poly (1,2-dihydro-2,2,4-trimethylquinoline) [poly (1,2-dihydro-2,2,4-trimethylquinoline)] , Tetrakis [methylene (3,5-di-tert-butyl-4-hydrooxy-hydrocinnamate) methane] tetrakis [methylene (3,5-di-tert-butyl-4-hydroxy-hydrocinnamate)] methane] It is preferable to use at least one or more of tris (2,4-di-tert-butyl-phenyl) phosphite.

As a means for achieving the above object, the constitution of the present invention comprises a carbon nanotube, an alloy (90% by weight of iron, 10% by weight of copper), a polymer elastic body surface-treated with a surface active agent containing a metal salt reducing agent If antibacterial deodorization treatment is preferable.

The composition of the present invention, the polymer elastomer, natural rubber, ethylene propylene rubber (ethylene propylene rubber, EPDM), silicone rubber (silicone rubber), nitrile butadiene rubber (NBR), chloroprene rubber It is preferable to use at least one of (chloroprene rubber).

The present invention is to produce a filament by adding the iron-copper alloy to the carbon nanotube composite material to replace the heavy wire, including the metal wire can be used as a high conductivity and light wire, and the addition of a polymer elastomer to increase the flexibility to increase the extrusion efficiency Can be improved.

1 is a flowchart of a method of manufacturing a conductive filament for a 3D printer according to the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art may easily implement the present invention. Advantages, objects, and advantages of this invention will become more apparent from the description of the preferred embodiments.

For reference, the embodiments disclosed herein are only presented by selecting the most preferred embodiment in order to help those skilled in the art from understanding the possible examples, the technical spirit of the present invention is not necessarily limited or limited by the presented embodiments. However, various changes, additions, and changes, including equivalents or substitutes, may be made without departing from the spirit of the present invention.

In addition, the terms or words used in the specification and claims herein are defined on the basis of the principle that the inventor can appropriately define the concept of terms in order to best describe his or her invention in the best way. It should not be construed as limited to ordinary or dictionary meanings, but rather as meanings and concepts consistent with the technical spirit of this invention.

1 is a flowchart of a method of manufacturing a conductive filament for a 3D printer according to the present invention.

As shown in Figure 1, the configuration of the method for producing a conductive filament for 3D printer according to the present invention, 1,000 parts by weight of distilled water, 0.1 to 10 parts by weight of activator, 5 to 20 parts by weight of metal salt reducing agent, acid 50 Adding 200 parts by weight in sequence to stir at a rate of 50 to 1,000 RPM for 30 to 50 minutes to prepare a surface activator (S10); Injecting the carbon nanotubes in a weight ratio of 1: 1 to the prepared surface active agent and stirred for 60 minutes to surface-activate the carbon nanotubes (S20); Based on 1,000 parts by weight of the activated carbon nanotubes, 950 parts by weight of the iron-copper alloy, 45 to 49 parts by weight of the polymer elastomer, 1.0 to 5.0 parts by weight of an antioxidant (in an order) to 160 ~ 300 ℃ temperature Primary melt mixing for 10 to 60 minutes at step S30; After completion of the first melt mixing step, the second step is melt mixing for 60 minutes at a temperature of 160 ~ 300 ℃ by sequentially adding 0.1 ~ 5.0 parts by weight of the processing agent, 1 ~ 30 parts by weight of flame retardant (flame retardant) Step S40; Extruding into a filament having a diameter of 20 to 50 mm using a single screw or twin screw extruder (S50); Transferring the extruded filaments to a cooler containing a cooling water containing bamboo charcoal powder and cooling the same at a speed of 0.1 to 100 m / min (S60); Drying the cooled filaments (S70); And a commercialization step (S80) of packaging the dried filaments.

The step of preparing the surface activator (S10), rhodium trichloride (didium pchloride), diamine palladium hydroxide (diamine palladium hydroxide), platinum chloride (platinum chloride), palladium chloride (palladium chloride) as an activator Use at least one, and use at least one of zinc chloride, cadmium chloride, and tin chloride as the metal salt reducing agent.

The activator serves to activate the surface of the carbon nanotubes so that the iron-copper alloy is easily attached, when the addition amount is less than 0.1 parts by weight, the surface adhesion of the aggregated carbon nanotubes and the metal is lowered, more than 10 parts by weight There is a problem in that the cost increases if you add.

The metal salt reducing agent serves to reduce metal ions, and when the added amount is less than 5 parts by weight, the surface adhesion between the collected carbon nanotubes and the metal is lowered, and when 20 parts by weight or more are added, the cost increases. .

Surface active treatment of the carbon nanotubes (S20), the kneading property is most excellent when the weight ratio of the surface active agent and carbon nanotubes in a 1: 1 ratio. When the weight ratio of the surface active agent is increased, the viscosity decreases, and the workability is decreased in the following extrusion molding step (S40), and when the weight ratio of the surface active agent is decreased, the kneading property is lowered.

In the primary melt-mixing step (S30), the iron-copper alloy is made of 10 wt% copper and 90 wt% iron, and exhibits the best conductivity at this weight ratio.

A thermal conductivity of 76 W / m · K and a linear thermal expansion coefficient of 14.75E-6 / K are used.

The primary melt-mixing step (S30) is a natural polymer, natural rubber, ethylene propylene rubber (ethylene propylene rubber, EPDM), silicone rubber (silicone rubber), nitrile butadiene rubber (Ntrile butadiene rubber, NBR) ), At least one or more of chloroprene rubber, and antioxidants act as an antioxidant in the processing of polymeric elastomers, and 2,6-di-tert-butyl-4-methylphenol (2,6-di -tert-butyl-4-methyl phenol), poly (1,2-dihydro-2,2,4-trimethylquinoline) [poly (1,2-dihydro-2,2,4-trimethylquinoline)], tetrakis [Methylene (3,5-di-tert-butyl-4-hydrooxy-hydrocinnamate) methane [tetrakis [methylene (3,5-di-tert-butyl-4-hydroxy-hydrocinnamate)] methane] or tris ( Use at least one of 2,4-di-tert-butyl-phenyl) phosphite [tris (2,4-di-tert-butyl-phenyl) phosphite].

By adding the polymer elastomer, the flexibility in the step (S50) of the extrusion molding to the filament can be improved to increase the extrusion efficiency. If the amount of the polymer elastomer is greater than 49 parts by weight, the conductivity of the filament is lowered. If the amount of the polymer elastomer is less than 45 parts by weight, the filament cracking phenomenon occurs during the extrusion process.

When the amount of antioxidant added is less than 1.0 part by weight, the polymer is oxidized during the kneading step, and the cost increases when 5 parts by weight or more is added.

In the secondary melt-mixing step (S40), at least one of zinc stearate, magnesium stearate, and calcium stearate is used as a processing aid.

When the amount of the processing aid added is less than 0.1 part by weight, the dispersibility of the secondary melt mixture is lowered and the cost increases when 5 parts by weight or more is added.

In the second melt-mixing step (S40), the flame retardant imparts flame retardancy to the secondary melt mixture, when the amount of the flame retardant is less than 1 part by weight, the flame retardancy of the secondary melt mixture is lowered and kneading when 100 parts by weight or more is added The castle falls.

In the first melt mixing step (S30) and the second melt mixing step (S40), the mixing mixer uses a kneader, a banbury, a mill, or the like.

The cooling step (S60), the bamboo charcoal powder can be prepared by grinding the charcoal carbonized bamboo, is known to exhibit excellent antibacterial and deodorizing effect, by adding to the cooling water can remove the peculiar smell of filament .

Experimental Example 1

In order to confirm the thermal conductivity of the iron-copper alloy, an alloy (Example 1, Comparative Example 1, and Comparative Example 2) was prepared by varying the weight ratio of iron and copper, and thermal conductivity was measured. The results are shown in Table 1 below.

Example 1 Comparative Example 1 Comparative Example 2 Iron weight% 90 85 95 Copper weight% 10 15 5 Thermal Conductivity (W / mK) 76 36 40

As described above, the thermal conductivity of the iron-copper alloy having the weight ratio of Example 1 according to the present invention was the best. Therefore, using the iron-copper alloy of the present invention can be produced a filament with increased conductivity.

Experimental Example 2

In order to confirm the deodorizing power of the bamboo charcoal powder, the deodorization rate was measured through a gas detection tube method applying ASTM D1988-06.

First, a rubber stopper was inserted to seal the 500mL Erlenmeyer flask, and a hole was prepared to allow entrance and exit of the detection tube, and 1 μl of ammonia solution was injected into the flask to cause odor. After 30 minutes of odor generation, 1 mg of bamboo charcoal powder was injected, and the residual gas was compared and analyzed by using a gas detector in units of 30 minutes, 60 minutes, and 90 minutes. The experiment was carried out in a fume hood at 23 ° C., and the blank test was measured by injecting water. The results are shown in Table 2 below.

Deodorization rate (%) Blank Charcoal powder 30 minutes 12 50 60 minutes 15 53 90 minutes 19 57

As described above, it can be confirmed that the bamboo charcoal powder exhibits excellent deodorizing power, and by using the bamboo charcoal powder as a coolant additive, the odor peculiar to the extruded filaments can be removed.

Claims (5)

1,000 parts by weight of distilled water, 0.1 to 10 parts by weight of activator, 5 to 20 parts by weight of metal salt reducing agent, and 50 to 200 parts by weight of acid were added sequentially, followed by stirring at a speed of 50 to 1,000 RPM for 30 to 50 minutes. Preparing a;
Injecting the carbon nanotubes in a weight ratio of 1: 1 to the prepared surface active agent and stirred for 60 minutes to surface-activate the carbon nanotubes;
Based on 1,000 parts by weight of the activated carbon nanotubes, 950 parts by weight of the iron-copper alloy, 45 to 49 parts by weight of the polymer elastomer, 1.0 to 5.0 parts by weight of an antioxidant (in an order) to 160 ~ 300 ℃ temperature Primary melt mixing for 10 to 60 minutes at;
After completion of the first melt mixing step, the second step is melt mixing for 60 minutes at a temperature of 160 ~ 300 ℃ by sequentially adding 0.1 ~ 5.0 parts by weight of the processing agent, 1 ~ 30 parts by weight of flame retardant (flame retardant) step;
Extruding the filament with a diameter of 20-50 mm using a single screw or twin screw extruder;
Transferring the extruded filaments to a cooler containing a cooling water containing bamboo charcoal powder and cooling the same at a speed of 0.1 to 100 m / min;
Drying the cooled filaments;
A method of manufacturing a conductive filament for a 3D printer comprising a; commercialization step of packaging the dried filament. The method of claim 1,
Preparing the surface activator,
As an activator, at least one of rhodium trichloride, diamine palladium hydroxide, platinum chloride, and palladium chloride is used. Method for producing a conductive filament for 3D printer, characterized in that at least one of zinc chloride), cadmium chloride, tin chloride (tin chloride) is used. The method of claim 1,
The first melt mixing step,
Polymer elastomer, at least one of natural rubber, ethylene propylene rubber (EPDM), silicone rubber, nitrile butadiene rubber (NBR), and chloroprene rubber Antioxidants play an antioxidant role in the processing of polymer composites, 2,6-di-tert-butyl-4-methylphenol, poly (1,2-dihydro-2,2,4-trimethylquinoline) [poly (1,2-dihydro-2,2,4-trimethylquinoline)], tetrakis [methylene (3,5-di-tert-butyl 4-hydrooxy-hydrocinnamate) methane [tetrakis [methylene (3,5-di-tert-butyl-4-hydroxy-hydrocinnamate)] methane] or tris (2,4-di-tert-butyl-phenyl) A method for producing a conductive filament for a 3D printer, characterized by using at least one of phosphite [tris (2,4-di-tert-butyl-phenyl) phosphite]. Alloy (iron 90% by weight, copper) 10% by weight) 950 parts by weight, 45-49 parts by weight of the polymer elastomer, 1.0-5.0 parts by weight of antioxidant, 0.1-5.0 parts by weight of processing agent, 1-30 parts by weight of flame retardant And antibacterial deodorant treatment.
As the active agent, at least one of rhodium trichloride, diamine palladium hydroxide, platinum chloride, palladium chloride is used,
As the metal salt reducing agent, at least one of zinc chloride, cadmium chloride, and tin chloride is used,
As the antioxidant, 2,6-di-tert-butyl-4-methylphenol, poly (1,2-dihydro-2,2,4 -Trimethylquinoline) [poly (1,2-dihydro-2,2,4-trimethylquinoline)], tetrakis [methylene (3,5-di-tert-butyl-4-hydrooxy-hydrocinnamate) methane [tetrakis [methylene (3,5-di-tert-butyl-4-hydroxy-hydrocinnamate)] methane] or tris (2,4-di-tert-butyl-phenyl) phosphite [tris (2,4-di-tert- butyl-phenyl) phosphite] at least
The polymer elastomer may include at least one of natural rubber, ethylene propylene rubber (EPDM), silicone rubber, nitrile butadiene rubber (NBR), and chloroprene rubber. Use more than one,
The alloy is a conductive filament for 3D printer, characterized in that the thermal conductivity is 76 W / m · K, the thermal expansion coefficient is 14.75E-6 / K.
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