KR20180027271A - Complex filament composition for manufacturing water purifying filter - Google Patents

Abstract

The present invention relates to a complex filament composition for water purification, a manufacturing method thereof, and a water purifying filter manufactured by the composition. The complex filament composition contains a polymer resin and at least one purification function material selected from a group made of iron oxide (III), titanium oxide (II), magnesium oxide, silver iodide, silver, akaganeite, keto acid, and CNT.

Description

COMPOUND FILAMENT COMPOSITION FOR MANUFACTURING WATER PURIFYING FILTER

The present invention relates to water-functional materials, particularly iron oxide (III), titanium oxide (II), magnesium oxide, silver iodide, silver, akaganeite, chitosan and CNT , A method for producing a composite filament, and a composite filament and a water filter manufactured from the composite filament composition.

3D printing technology refers to a technique of designing and outputting a three-dimensional structure to be produced using CAD. 3D printing technology is largely divided into FDM method and SLA method depending on manufacturing method and material. Among them, the FDM (Fused Deposition Modeling) method uses a thermoplastic resin. The resin is melted by applying a temperature equal to or higher than the melting point of the resin to the nozzle end of the printer, and the resin is jetted along a predetermined path, It is a method of making a structure of a desired shape. The material used for the 3D printing of the FDM method is called a filament, and the 3D printing filament is made of a long wire having a certain size of a cross-section of a thermoplastic resin and is easily manufactured into a 3D printer.

Hot Melt Extrusion (HME) technology is used to fabricate functional 3D printing filaments. Basically, high-temperature melt injection technology has been studied since the 1930s to develop polymer materials for medical applications. Polymer and raw material drugs are mixed in a cylinder, heated, mixed and injected through small-diameter holes . Thus, the drug substance is uniformly dispersed in the polymer, and the polymer has the characteristics of the drug substance. By applying such high-temperature melt injection technology, various other functional polymers can be obtained, which are directly connected to functional 3D printing filaments.

Structures made from functional 3D printing filaments must be directly in contact with the source of contamination to cause adsorption on the surface. Adsorption refers to the phenomenon that, when two phases are in contact with each other, the constituent components forming the phase are concentrated on the contact surface. Such adsorbable materials are called adsorbents and various metal oxides are well known as adsorbents. In order to adsorb and remove other contaminants, high efficiency can be obtained when the adsorbent corresponding to the contaminant source is used. In order to increase the adsorption efficiency, the surface area per unit volume must be increased. In particular, in the case of the 3D printing filament, the amount of the adsorbed contaminant increases as the mass of the adsorbent per unit mass increases.

However, if the mass of the material used as the adsorbent in the filament is increased, the physical properties of the filament are also changed. The filament is a thermoplastic resin, and the melting point and viscosity of the filament are increased as a foreign matter is basically added. This can serve as a variable to change the quality of the 3D printing structure. Therefore, the amount of the adsorbent can not be increased indefinitely in order to increase the adsorption efficiency.

Arsenic (As), one of the heavy metals, accumulates in the body and weakly causes headache, dizziness, vomiting and diarrhea. When exposed to arsenic in the long term, serious arthritis such as vascular damage, metabolic disorder, It is known to cause disease. Bangladesh, Vietnam and Cambodia have been contaminated by drinking water sources by natural arsenic, and these countries are making efforts to remove arsenic in drinking water.

Among the substances that react with arsenic, iron oxide is known as a substance for removing arsenic. The most simple method to remove arsenic using iron oxide is to rust the nod into water after a certain period of time. This is because the iron oxide present on the surface of the rust nail reacts with arsenic. However, this method has a disadvantage that it is difficult to control the water purification efficiency, and the iron oxide separated from the rusty nail surface acts as another contaminant.

In order to overcome the disadvantages of existing methods for removing arsenic contaminants, a method of combining with 3D printing has been devised as a new method using a known material as a contaminant removing material.

Korean Patent Publication No. 10-2015-0098142 Korean Patent Publication No. 10-2009-0079834

The present invention provides a composite filament composition for a water filter, a method for producing a composite filament for a water filter, and a water filter, which can more easily produce a water filter capable of easily and effectively removing water pollutants.

One aspect of the present invention is a process for producing a water-soluble polymer comprising at least one water-functional material selected from the group consisting of iron oxide (III), titanium dioxide (II), magnesium oxide, silver iodide, silver, acacanate, chitosan and CNT, A composite filament composition for a water filter is provided.

According to an embodiment of the present invention, the water-purifying functional material may be contained in an amount of 1 to 20% by weight based on the total weight of the filament composition.

According to one embodiment of the present invention, the polymer resin is a thermoplastic resin, specifically, acrylonitrile butadiene styrene (ABS) polymer, polylactic acid polymer, polycaprolactone (PCL) Polymers may be selected from the group consisting of polyvinyl alcohol (PVA) polymers, polycarbonate (PC) polymers, and high-density polyethylene (HDPE) polymers.

One aspect of the present invention relates to a method for producing a polymer resin pellet comprising the steps of: (a) adding oil to a polymer resin pellet to coat the surface of the polymer resin particle with the oil; (b) adding an aqueous functional material powder to the oil-coated polymer resin pellets and attaching them; And (C) extruding the resultant product of step (b), wherein the water-soluble functional material powder comprises iron oxide (III), titanium oxide (II), magnesium oxide, , Silver, at least one water-functional material selected from the group consisting of acacanate, chitosan and CNT.

According to an embodiment of the present invention, the water-containing functional material may be added in an amount of 1 to 20% by weight based on the total weight of the composite filament.

According to one embodiment of the present invention, the polymeric resin pellets are prepared from the group consisting of acrylonitrile butadiene styrene polymer, polylactic acid polymer, polycaprolactone polymer, polyvinyl alcohol polymer, polycarbonate polymer and high density polyethylene polymer Can be selected.

One aspect of the present invention provides a composite filament for a water filter manufactured by the above method.

One aspect of the present invention provides a water purification filter manufactured by 3D printing the composite filament.

The composite filament composition for a water filter according to the present invention can be used to manufacture and use a water filter having the same specifications as currently commercialized water filters, . The water filter using the complex filament composition for water purification according to the present invention can be used for a long period of time, even if it is impossible to use a high cost and high efficiency other purification method, It can be effectively used when it is necessary to remove pollutants.

Fig. 1 shows (a) thermogravimetric analysis (TGA) data of general ABS pellets, (b) thermogravimetric analysis data in the case where the ABS pellets contain 1.834% iron oxide according to the present invention, and (c) Shows the thermogravimetric analysis data when the ABS pellets contain 2.377% of iron oxide.
2 is a graph showing the degree of removal of arsenic in water according to the weight of the composite filament for a water filter according to an embodiment of the present invention.
FIG. 3 shows Sorption Efficiency according to iron oxide content of the composite filament for a water filter according to the present invention.

As used herein, the term "filament" means a filament for a 3D printer, specifically a 3D printer in FDM format. As used herein, the term "composite filament" means that an additional component for imparting a specific function to a pure polymer material is added.

As used herein, the term " water-functional material "means a material exhibiting a water-purifying function. Specific examples of the functional materials used in this specification are as follows.

As used herein, "iron oxide (III)" refers to the removal of arsenic, "titanium oxide (II)" refers to the removal of organic or inorganic contaminants, "magnesium oxide", "silver iodide" In the removal of biological contaminants such as bacteria, "acarganate" exerts a specific effect on the removal of chromium (VI), "chitosan" on the removal of lead (II) and "CNT" on the removal of water-soluble dyes.

According to an embodiment of the present invention, the water-purifying functional material may be contained in an amount of 1 to 20 wt% based on the total weight of the composite filament composition. If the content of the water-soluble functional material exceeds 20% by weight based on the total weight of the composite filament composition, the strength of the filament is lowered. Therefore, the filament is bent or broken without passing through a predetermined path during the injection process for printing, It is not preferable to apply it. When the content of the water-soluble functional material is increased, the content of the polymer resin in the composite filament composition is reduced, so that the stiffness of the filament is decreased. If the water-soluble functional material is included in a critical mass or more, a pressure overcoming the viscosity I can not stand it.

As used herein, the term "polymer resin" refers to a thermoplastic resin, specifically, an acrylonitrile butadiene styrene polymer, a polylactic acid polymer, a polycaprolactone polymer, a polyvinyl alcohol polymer, a polycarbonate polymer, and a high density polyethylene polymer But are not limited thereto.

As used herein, "oil" may be selected from the group consisting of paraffin oil, silicone oil and cooking oil, but is not limited thereto, and paraffin oil is preferred. When the oil is added in an amount of 1% by weight or less based on the total weight of the composite filament composition, the oil can be most efficiently adhered to the water.

 In step (c) of the method for manufacturing a composite filament for a water filter according to the present invention, the resultant product of step (b) is extruded through, for example, an extruder to melt the polymeric resin pellets in the extruder Dispersed and then passed through a nozzle and extruded in the form of a composite filament.

3D printers are equipment that processes materials according to design data and stacks them in a layer-by-layer manner to produce three-dimensional objects, which can be classified into various types according to the lamination method and materials to be used. The lamination method can be classified into extrusion, inkjet spraying, photo-curing, powder sintering, drawing, sheet joining, etc. The usable materials include resin, metal, paper, wood and food.

According to one aspect of the present invention, a composite filament made by the above method and having a diameter of 1.75 mm is provided for a water filter.

A water filter can be manufactured by 3D printing the composite filament for a water filter of the present invention. A water filter can be manufactured by using an extrusion type 3D printer. Since a composite filament can be melted and output in a nozzle to produce an article in a desired shape and size, a water filter having a desired shape and size can be manufactured .

According to an embodiment of the present invention, there is provided a method for producing a composite filament, comprising the steps of: preparing a composite filament comprising two species selected from the group consisting of iron oxide (III), titanium oxide (II), magnesium oxide, silver iodide, silver, Or more of water functional materials can be used in combination, and a water filter can be manufactured by using a composite filament comprising two or more kinds of water-functional materials, and a liquid to be purified can be passed therethrough to remove one or more kinds of contaminants have. Alternatively, it is also possible to produce several kinds of composite filaments containing a single-component water-purifying functional material, fabricate several kinds of water filters from the respective composite filaments, laminate various filters in one place, One or more contaminants can be removed at one time.

The shape of the water filter manufactured from the composite filament of the present invention may be a rectangular plate shape, a triangle plate shape, a disk shape, a hexahedral shape, a triangular columnar shape, a cylindrical shape, or a polygonal pyramid shape, but is not limited thereto.

Hereinafter, the present invention will be described in more detail with reference to one or more embodiments. However, these embodiments are illustrative of one or more embodiments, and the scope of the present invention is not limited to these embodiments.

Example  1. Preparation of composite filaments containing iron oxide powder 1

19 g of pellets of acrylonitrile butadiene styrene (ABS, purchased from Filabot) were added to a 50 mL centrifuge tube and 10 μL of paraffin oil (purchased from Sigma-aldrich) Was added. The centrifuge tube was vibrated using a stirrer for 5 minutes to completely coat the surface of the ABS pellet with paraffin oil. After the paraffin oil coating was completed, 1 g of iron oxide (III) powder (purchased from cnvision) was added and stirred again to be attached to the ABS surface.

The ABS pellets having the surface of the iron oxide powder adhered to the surface thereof were put in an extruder (Noztek), and the composite filaments were injected at an injection temperature of 210 ° C, an injection speed of 60 rpm and a nozzle size of 1.75 mm. During the melting of the pellets inside the injection machine, the iron oxide powders were dispersed and mixed with ABS, then injected in the form of filaments through the nozzles.

Example  2 to 10. Preparation of various composite filaments

Composite filaments were prepared in the same manner as described in Example 1, except that the compounds shown in Table 1 were used.

Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 ABS pellet 19.7 g 19.5g 19g 19g 19g 19g 19g 19g 19g Paraffin oil 10 μL 10 μL 10 μL 10 μL 10 μL 10 μL 10 μL 10 μL 10 μL Iron oxide (III)
powder 0.3 g 0.5 g - - - - - - - Titanium oxide (II)
powder - - 1g - - - - - - Magnesium oxide powder - - - 1g - - - - - Iodide
powder - - - - 1g - - - - Silver powder - - - - - 1g - - - - Agargate powder - - - - - - 1g - - Chitosan powder - - - - - - - 1g - CNT powder - - - - - - - - 1g

Test Example  1. Composite Filament Thermogravimetry

The thermogravimetric analysis of each composition was measured using a thermogravimetric analyzer (TGAQ50, TA Instruments-Waters L.L.C.) for the composite filaments prepared in Examples 2 and 3 among the composite filaments according to the present invention.

As a result of the experiment, it was confirmed that the composite filaments according to the present invention, specifically the composite filaments according to Examples 2 and 3, contained iron oxide as a water-soluble functional material through data change in the range of 400 to 700 ° C ).

Test Example  2. Composite filaments containing iron oxide powder Arsenic detection  And removal effects

Arsenic kit (purchased from Industrial Test Systems), which is an arsenic detection kit, was used to confirm whether arsenic adsorption of the composite filament for a water filter according to the present invention was caused.

0.5 g, 1 g, and 2 g of the composite filaments prepared in Example 1 were immersed in 50 mL of a 1.35x10 ^-4 M arsenic solution prepared as a standard solution, and the resulting solution was allowed to stand for 4 hours, The arsenic adsorption capacity of the composite filament was confirmed. As a result of the experiment, it was confirmed that the concentration of arsenic in the solution containing the composite filament of the present invention was reduced, and further, the greater the mass of the composite filament used, the greater the removal effect of arsenic (see FIG.

Test Example  3. Check whether the composite filament is normal output

In order to confirm whether the composite filaments prepared in Examples 1 to 10 were normal output, they were output using a Replicator 2X 3D printer (MakerBot). As a result, the filament was normally injected into the nozzle of the 3D printer, and it was confirmed that the filament was normally output at a nozzle temperature of 230 ° C.

Test Example  4. Output power  Confirm proper contents of functional materials in related composite filaments

Examples 11 to 13 and Comparative Examples 1 and 2 were carried out in different amounts of the iron (III) powder in addition to Examples 1 to 3 in order to confirm the proper content of the functional material in the composite filament for normal output . Composite filaments were prepared in the same manner as described in Example 1, except that the compounds shown in Table 2 were used.

Example 1 Example 2 Example 3 Example 11 Example 12 Example 13 Comparative Example 1 Comparative Example 2 ABS pellet 19g 19.7 g 19.5g 18g 17g 16g 15.5g 15g Paraffin oil 10 μL 10 μL 10 μL 10 μL 10 μL 10 μL 10 μL 10 μL Iron oxide (III) powder 1g 0.3 g 0.5 g 2g 3g 4g 4.5 g 5g The ratio of the content of the iron (III) powder to the total weight of the composite filament produced 5 wt% 1.9 wt% 2.4 wt% 10 wt% 15 wt% 20 wt% 22.5 wt% 25 wt% Normal output ○ ○ ○ ○ ○ ○ △ △

As a result of further checking whether the composite filaments prepared in Examples 11 to 13 and Comparative Examples 1 and 2 were properly output, if the amount of the iron oxide (III) powder was more than 20% by weight based on the total weight of the composite filament (Comparative Examples 1 and 2), it was confirmed that the minimum stiffness required for 3D printing was lost and the output was not normally output.

Test Example  5. Confirm proper content of functional materials in functional related composite filaments

Examples 14 to 23 were carried out by varying the content of the iron (III) powder in order to confirm the proper content of the functional material in the composite filament for the purpose of performing the water purification function. Composite filaments were prepared in the same manner as described in Example 1, except that the compounds shown in Table 3 were used.

Example 14 Example 15 Example 16 Example 17 Example 18 Example 19 Example 20 Example 21 Example 22 Example 23 ABS pellet 14.86 g 14.71 g 17.28 g 17.15 g 17.72 g 17.81 g 18.00 g 19.57 g 20.68 g 19.07 g Paraffin oil 10 μL 10 μL 10 μL 10 μL 10 μL 10 μL 10 μL 10 μL 10 μL 10 μL Iron oxide (III) powder 0.277 g 0.608 g 1.321 g 2.603 g 2.950 g 3.377 g 3.571 g 4.395g 5.281 g 5.492 g The ratio of the content of the iron (III) powder to the total weight of the composite filament produced 1.83
weight% 3.97
weight% 7.10
weight% 13.18
weight% 14.27
weight% 15.94
weight% 16.55
weight% 18.34
weight% 20.34
weight% 22.36
weight% Normal output ○ ○ ○ ○ ○ ○ ○ ○ △ △

The amounts of arsenic removed in water of the composite filaments prepared in Examples 14 to 21 were confirmed. The removal of arsenic in water was calculated in the following manner:

(q _e : the amount (mg / g) of metal removed by the adsorbent,

c _i, c _e : initial concentration and later concentration (mg / ml),

V: volume (ml) of assay solution,

W: mass of adsorbent used (g))

It was confirmed that the amount of arsenic absorbed per unit mass of filament converges to a specific value as the content of iron oxide (III) approaches 20 wt% (see Fig. 3).

The present invention has been described with reference to the preferred embodiments. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. Therefore, the disclosed embodiments should be considered in an illustrative rather than a restrictive sense. The scope of the present invention is defined by the appended claims rather than the foregoing description, and all changes or modifications derived from the meaning and scope of the claims and equivalents thereof are included in the scope of the present invention. .

Claims (8)

At least one water-soluble functional material selected from the group consisting of iron oxide (III), titanium oxide (II), magnesium oxide, silver iodide, silver, akaganeite, chitosan and CNT, Composite filament composition.
The method according to claim 1,
Wherein the water-soluble functional material is contained in an amount of 1 to 20% by weight based on the total weight of the composite filament composition.
The method according to claim 1,
The polymeric resin may be an acrylonitrile butadiene styrene (ABS) polymer, a polylactic acid polymer, a polycaprolactone (PCL) polymer, a polyvinyl alcohol (PVA) polymer, a polycarbonate polycarbonate (PC) polymer, and high-density polyethylene (HDPE) polymer.
(a) coating the surface of the polymer resin pellet with the oil by adding oil to the polymer resin pellet;
(b) adding an aqueous functional material powder to the oil-coated polymer resin pellets and attaching them; And
(C) extruding the result of step (b)
The method comprising the steps of:
Wherein the water-purifying functional material powder is at least one water-soluble functional material selected from the group consisting of iron oxide (III), titanium oxide (II), magnesium oxide, silver iodide, silver, acacanate, chitosan and CNT Filament.
5. The method of claim 4,
Wherein the water-soluble functional material is added in an amount of 1 to 20% by weight based on the total weight of the composite filament.
5. The method of claim 4,
Wherein the polymer resin is at least one selected from the group consisting of an acrylonitrile butadiene styrene polymer, a polylactic acid polymer, a polycaprolactone polymer, a polyvinyl alcohol polymer, a polycarbonate polymer and a high-density polyethylene polymer A method for producing a composite filament.
A composite filament for a water filter produced by the method according to any one of claims 4 to 6.
A water purification filter manufactured by 3D printing the composite filament according to claim 7.

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