KR102411285B1 - Masterbatch composition for adjusting physical properties of 3d printed output - Google Patents

Abstract

The present invention is 20 to 40% by weight of carbon fiber; And it relates to a masterbatch composition for controlling the physical properties of a 3D printer output, comprising 60 to 80% by weight of a thermoplastic polymer resin. In addition, the present invention provides a 3D printer output including the composition, and a method for producing the masterbatch. According to the present invention, by providing a masterbatch composition, the mixing ratio of the masterbatch and the polymer resin can be easily adjusted during printing using a 3D printer, and thus, the physical properties can be adjusted according to the design and use of the output.

Description

MASTERBATCH COMPOSITION FOR ADJUSTING PHYSICAL PROPERTIES OF 3D PRINTED OUTPUT}

The present invention relates to a masterbatch composition for controlling the physical properties of a 3D printer output.

3D printers have a 3D printing mechanism that is configured to form physical objects in 3D. As a material for 3D printing that allows the 3D printer to form a physical object in 3D, research related to a resin composition for 3D printing is continuing.

The advantage of 3D printing is that even if only one product is produced, the production cost is relatively low, and products of any shape can be freely created. In the existing model manufacturing technology, the cost of making one product is very high because the product is produced using the mold after making a mold, but 3D printing technology produces products by stacking raw materials one by one without a mold. It is very suitable for small quantity production of various kinds.

In addition, according to the 3D printing technology, it can be said that the types of products that can be produced using the 3D printing technology are virtually limitless because even complex shapes can be simply produced. As a result, 3D printing technology is expected to lead industrial innovation by changing the technological paradigm in various fields such as manufacturing, medical, and IT fields.

However, although 3D printing technology has the advantage that it can be applied in a variety of fields, research on a method for adjusting the physical properties of 3D printing output according to various uses and designs has been somewhat insufficient.

A method of manufacturing the resin used for this purpose to fit the 3D printer has been proposed (Korean Patent Application Laid-Open No. 2017-0055857), but there was a limit that could not be applied when other polymer resins had to be used.

An object of the present invention for solving the above technical needs is to provide a method for easily adjusting the physical properties of a 3D printer output according to a use, and the present invention is to develop a masterbatch composition for controlling the physical properties of a 3D printer output for that purpose

However, the technical problem to be achieved by the present invention is not limited to the above-mentioned problems, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

Accordingly, the present invention as a first preferred embodiment, 20 to 40% by weight of carbon fibers; And to provide a masterbatch composition for controlling the physical properties of a 3D printer output, comprising 60 to 80% by weight of a thermoplastic polymer resin.

In one embodiment of the present invention, the carbon fiber is characterized in that the surface is treated with a thermoplastic resin.

In another embodiment of the present invention, the thermoplastic resin is a polar thermoplastic resin or a non-polar thermoplastic resin.

In another embodiment of the present invention, the polar thermoplastic resin is a polyamide (PA)-based resin.

In another embodiment of the present invention, the non-polar thermoplastic resin is a polyethylene (PE), polypropylene (PP) or acrylonitrile butadiene styrene (ABS)-based resin.

In another embodiment of the present invention, the carbon fiber is characterized in that it has a length of 0.1 to 2 mm.

In another embodiment of the present invention, the carbon fiber, when the melt flow index of the thermoplastic polymer resin to be mixed is 10 or less, it will be 0.1 to 0.7 mm, and the melt flow index of the thermoplastic polymer resin to be mixed is greater than 10 case, it is characterized in that it is 0.7 to 2 mm.

In addition, the present invention provides a 3D printer output comprising the composition.

In an embodiment of the present invention, the 3D printer output includes the masterbatch composition and the polymer resin, wherein the composition and the polymer resin are mixed in a weight ratio of 1:0.5 to 1:10.

In addition, the present invention comprises the steps of impregnating the carbon fiber in a sizing agent solution to prepare a sized carbon fiber (S1);

Cutting the carbon fiber sized in the step S1 (S2);

mixing and kneading the carbon fiber cut in step S2 with a thermoplastic polymer resin (S3); and

When the kneading is completed, it provides a method for producing a master batch for controlling the physical properties of a 3D printer output, comprising the step (S4) of extruding the master batch in the form of pellets.

In one embodiment of the present invention, before being impregnated in the sizing agent solution, the carbon fiber of step S1 is passed through a nitrogen atmosphere carbonization furnace to remove the epoxy sizing agent.

The present invention is to provide a masterbatch composition for controlling the physical properties of a 3D printer output, provided in the form of a masterbatch, to easily control the mixing ratio with a polymer material during 3D printing, and to adjust the physical properties according to the characteristics of the output to be manufactured It has the advantage of being adjustable.

1 is a photograph showing the appearance of the masterbatch prepared in the present invention.
Figure 2 shows the results of measuring the tensile strength of the master batch (ABS 95%, CF 5%) prepared in Examples of the present invention.
Figure 3 shows the results of measuring the tensile strength of the master batch (ABS 70%, CF 30%) prepared in Examples of the present invention.

The present invention relates to a method for controlling the physical properties of a 3D printer output, and more particularly, to a masterbatch composition for controlling the physical properties of a 3D printer output.

In general, 3D printing output takes several hours to several tens of hours, and materials must be continuously supplied during printing. In order to control the physical properties of 3D printing output, reinforcing materials have been added to the polymer material used for printing, and mainly aramid, Kevlar, xylon, metal fiber, carbon fiber, glass fiber, basalt fiber, etc. have been used.

However, the reinforcing material has been generally provided in the form of a filament, and the filament-type material is not uniformly dispersed with the polymer material or has a limitation in that the content ratio cannot be accurately adjusted.

Accordingly, an object of the present invention is to provide a masterbatch composition for controlling the physical properties of a 3D printer output and a method for preparing the masterbatch, which are manufactured in the form of pellets.

In this way, when the material in the form of pellets, not filaments, is continuously supplied to the 3D printer through an appropriate material supply device. Depending on the content ratio of the polymer material used and the masterbatch, the physical properties of the printout can be variously adjusted. In addition, it is possible to prevent fine dust generated during manufacturing in the form of powder or filament or material loss caused by this, and the quality of the output can be maintained constant.

Masterbatch technology is used to improve the dispersibility of polymer materials and additives in the mixing process of raw materials for manufacturing injection moldings such as plastics, but masterbatch-related technology specialized in 3D printers is still minimal. Accordingly, an object of the present invention is to provide a masterbatch capable of easily controlling the physical properties of a 3D printer output.

In order to achieve the above technical object, the present invention is carbon fiber 20 to 40% by weight; And it provides a masterbatch composition for controlling the physical properties of a 3D printer output, comprising 60 to 80% by weight of a thermoplastic polymer resin. In addition, a 3D printing output including the composition may be provided.

In addition, the present invention comprises the steps of impregnating the carbon fiber in a sizing agent solution to prepare a sized carbon fiber (S1);

Cutting the carbon fiber sized in the step S1 (S2);

mixing and kneading the carbon fiber cut in step S2 with a thermoplastic polymer resin (S3); and

When the kneading is completed, it is possible to provide a method for producing a master batch for controlling the physical properties of a 3D printer output, comprising the step (S4) of extruding the master batch in the form of pellets.

Hereinafter, the present invention will be described in more detail.

In the present invention, the carbon fiber is characterized in that the surface is treated with a thermoplastic resin. By the surface treatment, the thermoplastic resin is treated on the surface of the carbon fiber to increase the interfacial bonding strength with the thermoplastic resin, so that the thermoplastic resin forming the masterbatch and the carbon resin can be firmly bonded.

The thermoplastic resin included in the composition of the present invention is ABS (acrylonitrile butadiene styrene copolymer, acrylonitrile butadiene styrene copolymer), PC (polycarbonate, polycarbonate), PU (poly urethane, polyurethane), PA (poly amide, polyamide) ), PET (polyethylene terephthalate), PBT (polybutylene terephthalate, polybutylene terephthalate), PP (polypropylene, polypropylene), PLA (polylactic acid, polylactic acid), PPS (polyphenylene sulfide, polyphenylene sulfide) , PE (polyethylene, polyethylene), PEEK (polyetheretherketone, polyether ether ketone), and PEI (polyetherimide, polyetherimide) may be at least one resin selected from the group consisting of. According to the type of the resin, a thermoplastic resin to be treated on the surface of the carbon fiber may be freely selected and used.

The resin to be treated on the surface of the carbon fiber may be a polar thermoplastic resin or a non-polar thermoplastic resin, the polar thermoplastic resin may be a PA-based resin, and the non-polar thermoplastic resin may be a PE, PP or ABS-based resin.

Before the surface of the carbon fiber is treated with a thermoplastic resin, the carbon fiber may be desizing through the step of removing the epoxy sizing. Since general carbon fibers have been subjected to epoxy sizing treatment, in the case of carbon fibers treated with epoxy sizing, in a carbonization furnace at 800 to 1200 ° C (preferably 900 ° C) in a nitrogen atmosphere at a speed of 1 to 2 m/min. The desizing treatment can be performed through the step of passing through to remove the epoxy sizing agent.

In the step (S1) of producing sized carbon fibers by impregnating the carbon fibers with a sizing agent solution, 1 to 5 wt% of a sizing agent made of a polar thermoplastic resin or a non-polar thermoplastic resin is contained in a water tank containing carbon. After impregnation by passing the fiber, it can be carried out by drying at 130 ~ 150 ℃ in a 1m section. This process is continuous and proceeds at a speed of 0.5 to 2 m/min.

In the present invention, the step (S2) of cutting the carbon fiber sized in step S1 is a step of adjusting the length of the carbon fiber according to the use of the output to be manufactured by cutting the carbon fiber that has been sized.

In the present invention, the length of the carbon fiber is adjusted to 0.1 to 0.7 mm when the melt flow index of the thermoplastic polymer resin to be mixed is 10 or less, and when the melt flow index of the thermoplastic polymer resin to be mixed is greater than 10, 0.7 to 3 mm. The melt flow index is measured with a melt flow index meter (MFI), and the melt flow index means a value measured at 220° C., 10 kg, g/10 min_ condition by ASTM D1238 method.

In the present invention, step S3 is a step of mixing and kneading the carbon fiber cut in step S2 with a thermoplastic polymer resin. There is no limitation on the method of kneading, but carbon fibers cut in 60-80 wt% weight ratio of thermoplastic polymer resins such as ABS, PC, PU, PA, PET, PBT, PP, PLA, PPS, PE, PEEK, PEI 20- 40% by weight is melt mixed. At this time, the resin melting is carried out at 230 ~ 330 ℃ using a twin extruder, the twin extruder has 2 to 10 temperature sections. When mixing the thermoplastic polymer resin and carbon fiber, the fiber content is adjusted in the range of 20 to 40% according to the melt flow index of the thermoplastic polymer resin.

When the kneading is completed, the masterbatch in the form of pellets can be prepared by extruding in step S4.

The present invention can provide a 3D printer output manufactured using the masterbatch and the polymer resin. The type of the polymer resin is not limited. The composition and the polymer resin may be mixed in a weight ratio of 1:0.5 to 1:10, but may be mixed by adjusting the weight ratio according to the design and use of the output to be produced.

For example, if a masterbatch containing 40% carbon fiber (ABS 60%, CF 40%) is used, when using a 1:1 mixture of the masterbatch and ABS polymer resin, finally ABS with 20% carbon fiber content Polymer material 3D printer output can be obtained.

If it is necessary to obtain an output with lower physical properties than carbon fiber with a content of 20%, so if you want to print with carbon fiber with a content of 10%, you can use a 1:3 mixture of masterbatch and ABS polymer. In the same way, if you want to print with carbon fiber with a content of 5%, use a 1:7 mixture of masterbatch and ABS.

In this way, in 3D printing, the physical properties can be adjusted according to the design and use of the output.

Hereinafter, the present invention will be described in more detail through examples. These examples are only for illustrating the present invention in more detail, and it will be apparent to those of ordinary skill in the art to which the present invention pertains that the scope of the present invention is not limited by these examples.

[Example]

Example 1. Preparation of carbon fiber

Common carbon fibers are epoxy sizing, so a de-sizing process is required. Therefore, the epoxy sizing agent was removed by passing the carbon fiber through a carbonization furnace at 900° C. in a nitrogen atmosphere at a speed of 1 to 2 m/min.

Example 2. Plastic resin resizing

In order to increase the interfacial bonding strength of carbon fibers with ABS plastic resins, carbon fibers in which plastic resins such as phenoxy, urethane, and nylon are sized were prepared.

First, the carbon fiber was impregnated by passing it through a solution containing 3 wt% of ABS as a sizing agent, and then dried at a temperature of 130 to 150 °C in a 1m section. This process was carried out continuously and proceeded at a speed of 1 m/min.

Example 3. Carbon Fiber Cutting

The sized carbon fibers were uniformly cut to a length of 0.5 mm. At this time, in order to uniformly control the mixing conditions of the fiber and the resin according to the viscosity deviation in the molten state of the plastic polymer resin, the length deviation of the cut carbon fibers was made to be within 0.1 mm.

Example 4. Mixing with Thermoplastic Polymer Resin

In the ABS plastic resin 60% weight ratio, 40% of the cut carbon fiber prepared in Example 3 was melt-mixed. At this time, the resin melting was performed at 250° C. using a twin extruder, and a twin extruder having 6 temperature sections was used.

Thereafter, a master batch in the form of pellets was prepared to have a length of about 5 mm and a diameter of 3 mm through extrusion.

Example 5 Mixing with Thermoplastic Polymer Resin

In the ABS plastic resin 60% weight ratio, 40% of the cut carbon fiber prepared in Example 3 was melt-mixed. At this time, the resin melting was performed at 250° C. using a twin extruder, and a twin extruder having 6 temperature sections was used.

Thereafter, a master batch in the form of pellets was prepared to have a length of about 5 mm and a diameter of 3 mm through extrusion (FIG. 1).

Example 6. Confirmation of tensile strength of masterbatch

In the same manner as in the manufacturing method of Example 5, a master batch prepared by mixing 95 wt% of a plastic resin and 5 wt% of carbon fiber, and a master batch prepared by mixing 70 wt% of a plastic resin and 30 wt% of carbon fiber, respectively prepared.

The tensile strength according to the tensile strain of the master batch was measured and shown in FIG. 2 (ABS 95%, CF 5%) and FIG. 3 (ABS 70%, CF 30%). As a result, when 30% of CF was included, the result was about 40 MPa or more, and when 5% of CF was included, the tensile strain was high as about 3%, but the tensile strength was about 30 MPa.

As the specific parts of the present invention have been described in detail above, for those of ordinary skill in the art, it is clear that these specific descriptions are only preferred embodiments, and the scope of the present invention is not limited thereby. will be. Accordingly, it is intended that the substantial scope of the present invention be defined by the appended claims and their equivalents.

Claims (15)

delete delete delete delete delete delete delete delete delete Impregnating the carbon fiber in a sizing agent solution to prepare a sized carbon fiber (S1);
Cutting the carbon fiber sized in the step S1 (S2);
mixing and kneading the carbon fiber cut in step S2 with a thermoplastic polymer resin (S3); and
When the kneading is completed, it comprises a step (S4) of extruding to prepare a master batch in the form of pellets,
The carbon fiber of step S1 is passed through a nitrogen atmosphere carbonization furnace before being impregnated with the sizing agent solution to remove the epoxy sizing agent.
delete 11. The method of claim 10,
The sizing agent solution of step S1 is a method of manufacturing a masterbatch for controlling the physical properties of a 3D printer output, characterized in that it contains a polar thermoplastic resin or a non-polar thermoplastic resin.
13. The method of claim 12,
The polar thermoplastic resin is a polyamide (PA)-based resin, characterized in that the manufacturing method of the masterbatch for controlling the physical properties of the 3D printer output.
13. The method of claim 12,
The non-polar thermoplastic resin is polyethylene (PE), polypropylene (PP) or acrylonitrile butadiene styrene (ABS)-based resin, characterized in that, the method of manufacturing a masterbatch for controlling the physical properties of a 3D printer output.
11. The method of claim 10,
The length of the carbon fiber is,
When the melt flow index of the thermoplastic polymer resin to be mixed is 10 or less, it is 0.1 to 0.7 mm,
When the melt flow index of the thermoplastic polymer resin to be mixed is greater than 10, it is characterized in that 0.7 to 2 mm, a method of manufacturing a masterbatch for controlling the physical properties of a 3D printer output.

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