Patent Grant
11835535
This application is a national phase entry under 35 U.S.C. § 371 of International Application No. PCT/KR2018/012732, filed on Oct. 25, 2018, which claims priority from Korean Patent Application No. 10-2017-0154395, filed on Nov. 20, 2017, and Korean Patent Application No. 10-2018-0053637, filed on May 10, 2018, the disclosures of which are hereby incorporated herein by reference.
The present invention relates to a device and a method for qualitative analysis and quantitative analysis of heavy metals and, more particularly, to a device and a method for qualitative analysis and quantitative analysis of heavy metals using a rotatable disk system.
In general, the most widely used method for detecting heavy metals is spectroscopic analysis such as inductively coupled plasma mass spectrometry or atomic absorption/emission spectrometry. Mass spectrometry and spectroscopy based heavy metal detection methods are accurate and have high detection limits, but they are expensive and require skilled analytical techniques, making it difficult to perform a heavy metal analysis in the field quickly and simply.
It is required to develop economical and cost-effective color development based heavy metal analysis system for replacing expensive mass spectrometry and spectroscopy based heavy metal analysis equipment, and development of miniaturized analysis system that can be conveniently applied in the field is required. In addition, it is required to develop a system capable of quantitative analysis as well as qualitative analysis of heavy metals while shortening analysis time by performing simultaneous detection of multiple heavy metals.
In addition, when a fluid sample containing heavy metals is developed in a detection unit and quantitative analysis is performed according to a development distance, a method for performing a more accurate quantitative analysis is required.
The present invention pertains to a device for qualitative analysis and quantitative analysis comprising a rotatable platform and a plurality of microfluidic structures disposed radially and symmetrically on the rotatable platform. Each of the plurality of the microfluidic structures comprises a sample injection unit into which a fluid sample containing heavy metals is injected; a microfluidic channel (a siphon channel) which is a passage through which the sample can be moved to a detection unit and connects the sample injection unit to the one end of the detection unit; the detection unit coated with an organic substance capable of causing the color development reaction with the heavy metals of the sample; and a ruler for measuring the color developed distance. Each of the plurality of the microfluidic structures may receive different kinds of samples. The rotation of the device is controlled so that the sample moves from the sample injection unit to the microfluidic channel and then to the detection unit, and the qualitative analysis through the color development reaction of the heavy metals in the detection unit and the quantitative analysis through the measurement of the color developed distance may be possible.
Further, in the device for qualitative analysis and quantitative analysis according to the present invention, the detection unit comprises a development area coated with an organic substance capable of causing the color development reaction with the heavy metals of the fluid sample so that the fluid sample can be developed and a reservoir area where the organic material is not coated. The reservoir area is provided in one end of the detection unit and the microfluidic channel may be connected to the side of the reservoir area of the detection unit.
Further, in the device for qualitative analysis and quantitative analysis according to the present invention, the sample injection unit may include a space capable of receiving the sample and an opening through which the sample can be injected.
Further, in the device for qualitative analysis and quantitative analysis according to the present invention, the control of the rotation of the device can be accomplished by rotating the device firstly and then stopping so that the sample injected into the sample injection unit is moved to the microfluidic channel; rotating the device secondarily so that the sample moved to the microfluidic channel is moved to the reservoir area; and stopping the device so that sample moved to the reservoir area is developed in the detection unit.
Further, in the device for qualitative analysis and quantitative analysis according to the present invention, the microfluidic channel may include a portion of a “U” shaped tube so that the sample can be received within the microfluidic channel after the first rotation and before the second rotation of the device.
Also, in the device for qualitative analysis and quantitative analysis according to the present invention, the first rotation may be performed at 2000 to 4000 RPM for 5 to 20 seconds and the second rotation may be performed at 4000 to 6000 RPM for 3 to 10 seconds.
Further, in the device for qualitative analysis and quantitative analysis according to the present invention, the rotatable platform is a circular disk and may have a diameter of 12 cm to 20 cm.
Further, in the device for qualitative analysis and quantitative analysis according to the present invention, the detection unit may be made of paper.
Further, in the device for qualitative analysis and quantitative analysis according to the present invention, the heavy metals that may be included in the sample may comprise Fe2+, Zn2+, Hg2+, Cr6+, Ni2+, or Cu2+.
Further, in the device for qualitative analysis and quantitative analysis according to the present invention, the organic material previously applied to the detection unit may comprise dimethylglyoxime, bathophenanthroline, dithiooxamide, dithizone, diphenylcarbazide, or 1-(2-pyridylazo)-2-naphthol.
Further, the present invention pertains to an analytic method of a fluid sample containing heavy metals by using the qualitative analysis and quantitative analysis device according to the present invention. The analytic method comprises: (S1) injecting the sample into the sample injection unit; (S2) controlling the rotation of the device; and (S3) performing at least one of qualitative analysis and quantitative analysis of the sample developed in the detection unit.
Further, in the analytic method of a fluid sample containing heavy metals according to the present invention, the injection of the sample into the sample injection unit of the step (S1) may comprise injecting the fluid sample containing different kinds of the heavy metals into each of the plurality of microfluidic structures, or injecting the fluid sample containing same kinds of the heavy metals of varying concentrations into each of the plurality of microfluidic structures.
Further, in the analytic method of a fluid sample containing heavy metals according to the present invention, the controlling of the rotation of the device of the step (S2) may comprise (S2-1) rotating the device firstly and then stopping so that the sample injected into the sample injection unit is moved to the microfluidic channel; (S2-2) rotating the device secondarily so that the sample moved to the microfluidic channel is moved to the reservoir area; and (S2-3) stopping the rotation of the device so that the sample moved to the reservoir area is developed in the detection unit.
Further, in the analytic method of a fluid sample containing heavy metals according to the present invention, the performance of at least one of qualitative analysis and quantitative analysis of the sample of the step (S3) may comprise performing at least one of (S3-1) qualitative analysis through the color development reaction of the sample developed in the detection unit and (S3-2) the quantitative analysis through the measurement of the color developed distance.
According to the device for qualitative analysis and quantitative analysis (1, 1′) and the analysis method of the sample using the same (2) according to one embodiment of the present invention, the increase of the detection limit of heavy metals through the control of the automated fluidic control and the control of the torque and capillary force is possible. It is possible to improve the detection limit of heavy metal ions by the torque control. That is, it is possible to improve the detection limit by controlling the color development reaction time and the colored area via adjustment of the centrifugal force and the capillary force by control of the rotation of the device.
According to the device for qualitative analysis and quantitative analysis (1, 1′) and the analysis method of the sample using the same (2) according to one embodiment of the present invention, qualitative analysis and quantitative analysis of several heavy metals can be performed with one device (1, 1′).
According to the present invention, economical and rapid multi-metal qualitative/quantitative analysis is possible. It is more economical than conventional expensive spectroscopy or mass spectrometry based heavy metal detector and can shorten analysis time. In addition, the configurations for qualitative analysis and quantitative analysis can be integrated into one miniaturized device (1, 1′), and can be applied quickly and conveniently in the field where qualitative/quantitative analysis of heavy metals is required.
In addition, since the channel (a microfluidic channel) and the detection unit are all patterned in one device, the fabrication of the device for qualitative analysis and quantitative analysis (1, 1′) is simple.
In the device for qualitative analysis and quantitative analysis comprising a rotatable platform and a plurality of microfluidic structures disposed radially and symmetrically on the rotatable platform according to present invention, each of the plurality of microfluidic structures comprises a sample injection unit into which a fluid sample containing heavy metals is injected; a microfluidic channel which is a passage through which the sample can be moved to a detection unit and connects the sample injection unit to the one end of the detection unit; the detection unit coated with an organic substance capable of causing the color development reaction with the heavy metals of the sample; and a ruler for measuring the color developed distance. Each of the plurality of microfluidic structures may receive different kinds of samples. The rotation of the device is controlled so that the sample moves from the sample injection unit to the microfluidic channel and then to the detection unit, and the qualitative analysis through the color development reaction of the heavy metals in the detection unit and the quantitative analysis through the measurement of the color developed distance may be possible.
Further, in the device for qualitative analysis and quantitative analysis according to the present invention, the detection unit comprises a development area coated with an organic substance capable of causing the color development reaction with the heavy metals of the fluid sample so that the fluid sample can be developed and a reservoir area where the organic material is not coated. The reservoir area is provided in one end of the detection unit and the microfluidic channel may be connected to the side of the reservoir area of the detection unit.
Further, in the device for qualitative analysis and quantitative analysis according to the present invention, the sample injection unit may include a space capable of receiving the sample and an opening through which the sample can be injected.
Further, in the device for qualitative analysis and quantitative analysis according to the present invention, the control of the rotation of the device can be accomplished by rotating the device firstly and then stopping so that the sample injected into the sample injection unit is moved to the microfluidic channel; rotating the device secondarily so that the sample moved to the microfluidic channel is moved to the reservoir area; and stopping the device so that sample moved to the reservoir area is developed in the detection unit.
Further, in the device for qualitative analysis and quantitative analysis according to the present invention, the microfluidic channel may include a portion of a “U” shaped tube so that the sample may be received within the microfluidic channel after the first rotation and before the second rotation of the device.
Also, in the device for qualitative analysis and quantitative analysis according to the present invention, the first rotation may be performed at 2000 to less than 4000 RPM for 5 to 20 seconds and the second rotation may be performed at 4000 to 6000 RPM for 3 to 10 seconds.
Further, in the device for qualitative analysis and quantitative analysis according to the present invention, the rotatable platform is a circular disk and may have a diameter of 12 cm to 20 cm.
Further, in the device for qualitative analysis and quantitative analysis according to the present invention, the detection unit may be made of paper.
Further, in the device for qualitative analysis and quantitative analysis according to the present invention, the heavy metals that may be included in the sample may be Fe2+, Zn2+, Hg2+, Cr6+, Ni2+, or Cu2+.
Further, in the device for qualitative analysis and quantitative analysis according to the present invention, the organic material previously applied to the detection unit may comprise dimethylglyoxime, bathophenanthroline, dithiooxamide, dithizone, diphenylcarbazide, or 1-(2-pyridylazo)-2-naphthol.
Further, in the analytic method of a fluid sample containing heavy metals by using the qualitative analysis and quantitative analysis device according to the present invention, the method comprises: (S1) injecting the sample into the sample injection unit; (S2) controlling the rotation of the device; and (S3) performing at least one of qualitative analysis and quantitative analysis of the sample developed in the detection unit.
Further, in the analytic method of a fluid sample containing heavy metals according to the present invention, the injection of the sample into the sample injection unit of the step (S1) may comprise injecting fluid sample containing different kinds of the heavy metals into each of the plurality of microfluidic structures, or injecting fluid sample containing same kinds of the heavy metals of varying concentrations into each of the plurality of microfluidic structures.
Further, in the analytic method of a fluid sample containing heavy metals according to the present invention, the controlling of the rotation of the device of the step (S2) may comprise (S2-1) rotating the device firstly and then stopping so that the sample injected into the sample injection unit is moved to the microfluidic channel; (S2-2) rotating the device secondarily so that the sample moved to the microfluidic channel is moved to the reservoir area; and (S2-3) stopping the rotation of the device so that the sample moved to the reservoir area is developed in the detection unit.
Further, in the analytic method of a fluid sample containing heavy metals according to the present invention, the performance of at least one of qualitative analysis and quantitative analysis of the sample of the step (S3) may comprise performing at least one of (S3-1) qualitative analysis through the color development reaction developed in the detection unit and (S3-2) the quantitative analysis through the measurement of the color developed distance.
Hereinafter, the device and the method for qualitative analysis and quantitative analysis of heavy metals using a rotatable disk system according to the present invention will be described in detail. The accompanying drawings, which are included to provide a further understanding of the invention, illustrate embodiments of the present invention and the technical scope of the present invention is not limited thereto.
In addition, the same or corresponding components are denoted by the same reference numbers regardless of the figures, and redundant description thereof will be omitted. For convenience of explanation, the size and shape of each constituent member shown may be exaggerated or reduced.
First, referring
The rotatable platform (10) includes the plurality of microfluidic structures (20) which are positioned radially and symmetrically on the rotatable platform (10). For example, the plurality of microfluidic structures (20) may comprise two, four, six, eight, ten, or twelve of the structures. In
Referring to
Each microfluidic structure (20) of the plurality of the microfluidic structures (20) may receive the fluid sample containing different kinds of the heavy metals. The heavy metals that may be included in the fluid sample may include, for example, Fe2+, Zn2+, Hg2+, Cr6+, Ni2+, or Cu2+.
The sample injection unit (100) includes a space for accommodating a fluid sample containing the heavy metals and an opening (100a) through which the fluid sample can be injected into the space. The sample injection unit (100) and one end of the detection unit (120) may be connected to the microfluidic channel (110). Further, the sample injection unit (100) may include a blocking unit (100b) which prevents the sample injected through the opening (100a) from flowing directly into the microfluidic channel (110) and stores the sample in the inner space of the sample injection unit (100) by using drop of the channel. Since the vicinity of the rear end portion (100c) of the sample injection unit (100) where the microfluidic channel (110) is connected to each other in the sample injection unit (100) has, for example, a streamlined shape, when the fluid sample injected into the injection unit (100) moves to the microfluidic channel (110), the resistance of the fluid sample is minimized and all of the fluid sample injected into the sample injection unit (100) is moved to the microfluidic channel (110).
The microfluidic channel (110) may have a width of 1 mm and a depth of 100 μm. The microfluidic channel (110) may comprise, for example, a portion of a “U” shaped tube. As will be described below, the fluid sample including heavy metals after the first rotation and before the second rotation of the device for qualitative analysis and quantitative analysis (1) has the passage through which the fluid sample moves due to the hydrophilicity of the microfluidic channel (110), and as a result, the fluid sample can be accommodated in the microfluidic channel (110).
The detection unit (120) may be made of a porous hydrophilic material, for example, paper, nitrocellulose, cotton, silica based sol-gel matrix, etc., and may be preferably made of paper. In addition, the detection unit (120) may include a development area (120a), which are coated with an organic material (organic ligand) capable of causing the color development reaction with the heavy metals of the fluid sample so that the fluid sample can be developed, and a reservoir area (120b) connecting the microfluidic channel (110) to development area (120a). The reservoir area (120b) may or may not be coated with an organic material. The microfluidic channel (110) is connected to the side of the reservoir area (120b) of the detection unit (120). The fluid sample moved from the sample injection unit (100) to the microfluidic channel (110) during the first rotation of the rotatable platform (10) is moved from the microfluidic channel (110) to the reservoir area (120b) of the detection unit (120) connected to the microfluidic channel (110) during the secondary rotation of the rotatable platform (10). At this time, the fluid sample remains in the reservoir area (120b) without being developed into the development area (120a) of the detection unit (120) by the centrifugal force due to the rotation. When the secondary rotation of the rotatable platform (10) is stopped, the fluid sample is developed from the reservoir area (120b) to the development area (120a). A more detailed description thereof will be given below with reference to
The ruler (130) is positioned alongside of the detection unit (120) in the vicinity of the detection unit (120). The ruler (130) may be, for example, scaled in millimeters (mm). Alternatively, it may be scaled in units of concentration such as ppm, ppb, etc., in addition to the length unit such as mm in the scale unit (130). In the case where the scale is expressed in terms of the concentration unit in the ruler (130), it may be expressed in terms of a concentration unit obtained by substituting the development distance of the heavy metals into a calibration curve (see
Meanwhile, the device for qualitative analysis and quantitative analysis (1′) of
Further, in the device for qualitative analysis and quantitative analysis (1′) of
In the device for qualitative analysis and quantitative analysis (1′) of
The sample injection unit (100) and the microfluidic channel (110) are provided within the top layer, and the sample injection unit (100) and the microfluidic channel (110) can be formed through a patterning process using micro-milling. The lower surface of the top layer where the detection unit (120′) are positioned may be variously modified and changed so that the detection unit (120′) can be inserted, including a concave portion in conformity with the shape of the detection unit (120′). Also, the depth of the concave portion can be variously modified and changed according to the environment in which the present invention is actually implemented. A hydrophilic material is coated on the inside of the microfluidic channel (110) to receive the fluid sample containing the heavy metals. A space in which the detection unit (120′) can be inserted is provided in the bottom layer and the lower surface of the top layer may include a concave portion in conformity with the shape of the detection unit (120′). The ruler (130) is patterned in the bottom layer. The PSA layer is an adhesive layer serving to bond the top layer and the bottom layer, and can be formed into, for example, an acryl based double-sided adhesive tape. In a tape or a plate having an adhesive component corresponding to the size of the rotatable platform (10), the region corresponding to the sample injection unit (100) and the microfluidic channel (110) in the top layer, and the region corresponding to the detection unit (120′) in the bottom layer may be removed by cutting or the like, as shown in
However, the present invention is not limited to the above-described embodiments, and various modifications and changes are possible, for example, the ruler (130) may be patterned on the top layer.
According to the device for qualitative analysis and quantitative analysis (1, 1′) of the present invention, the rotation of the device for qualitative analysis and quantitative analysis (1) is controlled so that the fluid sample containing the heavy metals moves from the sample injecting unit (100) into the microfluidic channel (110), and then moves to the detection unit (120, 120′). For example, after the fluid sample containing heavy metals is injected into the sample injection unit (100), when the device for qualitative analysis and quantitative analysis (1, 1′) is first rotated for 10 seconds at 3000 RPM and then stopped, the fluid sample containing the heavy metals moves to the microfluidic channel (110). When the device for qualitative analysis and quantitative analysis (1, 1′) is secondarily rotated at 5,000 RPM for 5 seconds, the fluid sample containing the heavy metals in the microfluidic channel (110) of the top layer is injected to the reservoir area (120b, 150) inserted in the bottom layer by the centrifugal force. When the rotation of the device for qualitative analysis and quantitative analysis (1, 1′) is stopped, the fluid sample containing the heavy metals is developed on the detection units (120, 120′) by the capillary force.
The fluid sample including the heavy metals developed on the detection unit (120, 120′) reacts with the reagents previously coated on the detection unit (120, 120′) to indicate colors related to the heavy metals. As an organic substance that can be previously applied to the detection unit (120, 120′), for example, an organic chelating agent may be used. In one embodiment, organic substances based on a reaction list between heavy metal ions and the organic chelating agents as shown in Table 1 below may be used.
The device for qualitative analysis and quantitative analysis (1, 1′) according to the present invention can provide a simultaneous qualitative analysis up to a level of 25 ppm for a plurality of heavy metals such as Fe2+, Zn2+, Hg2+, Cr6+, Ni2+, or Cu2+ within 15 minutes.
The qualitative analysis can be performed on heavy metals contained in the fluid sample with the hue according to the color development reaction on the detection unit (120, 120′). For example, when the hue according to the color development reaction is observed with the naked eyes, the types of the heavy metals contained in the fluid sample can be identified. In this regard,
In addition, the degree of development of the fluid sample including the heavy metals on the detection unit (120, 120′) can be quantitatively analyzed by using the ruler (130) of
Hereinafter, with reference to
Step 1: Injecting a fluid sample into the sample injection unit (100) of the device for qualitative analysis and quantitative analysis (1, 1′) (S1); Step 2: Controlling the rotation of the device for qualitative analysis and quantitative analysis (1, 1′) (S2); and Step 3: Performing at least one of qualitative analysis and quantitative analysis (S3).
Step 1: Injecting a Fluid Sample into the Sample Injection Unit (100) of the Device for Qualitative Analysis and Quantitative Analysis (1, 1′) (S1)
The fluid sample is injected into each sample injection unit (100) of the plurality of microfluidic structures (20) of the device for qualitative analysis and quantitative analysis (1, 1′). For example, about 40 μl of the fluid sample each can be injected into each sample injection unit (100). However, the present invention is not limited to this embodiment, and the amount of the injection can be variously adjusted according to various environments in which the present invention is implemented. The fluid sample containing different kinds of the heavy metals is respectively injected into each of the plurality of the microfluidic structures (20, 20′) (S1-1) to perform qualitative analysis and/or quantitative analysis as described below, the fluid sample containing the same kind of the heavy metals of varying concentrations are respectively injected into each of the microfluidic structures (20, 20′) (S1-2) to perform qualitative analysis and/or quantitative analysis as described below.
Step 2: Controlling the Rotation of the Device for Qualitative Analysis and Quantitative Analysis (1, 1′) (S2)
The device for qualitative analysis and quantitative analysis (1, 1′) is mounted on a system for qualitative analysis and quantitative analysis (3) capable of rotating the device for qualitative analysis and quantitative analysis (1, 1′), for example, a rotatable system for qualitative analysis and quantitative analysis (3) as shown in
Step 2-1: The device for qualitative analysis and quantitative analysis (1, 1′) is initially rotated at 2000 to less than 4000 RPM for 5 to 20 seconds and then is stopped to move the fluid sample including heavy metals injected into the sample injection unit (100) located at the top layer of the microfluidic structure (20, 20′) to the microfluidic channel (110) (S2-1).
Step 2-2: The device for qualitative analysis and quantitative analysis (1, 1′) is secondarily rotated at 4000 to 6000 RPM for 3 to 10 seconds to flow the fluid sample including heavy metals transferred to the microfluidic channel (110) at step 2-1 into the reservoir region (120b, 150) of the microfluidic structures (20, 20′) (S2-2).
Step 2-3: The rotation of the device for qualitative analysis and quantitative analysis (1, 1′) is stopped so that the fluid sample including the heavy metals are guided by the capillary force from the reservoir region (120b, 150) to the development area (120a) of the detection unit (120)/one end of the detection unit (120′) to be developed on the detection unit (120, 120′) (S2-3).
Step 3: Performing at Least One of Qualitative Analysis and Quantitative Analysis (S3)
A qualitative analysis can be performed on the fluid sample developed on the detection unit (120, 120′) by a method of analyzing the color development reaction on the detection unit (120, 120′) with the naked eyes (S3-1), or a quantitative analysis can be performed by measuring the degree of development of the fluid sample developed on the detection unit (120, 120′) by using a ruler (130) and then substituting the measured values to the calibration curves of the corresponding heavy metals developed on the scale (S3-2), or both of the quantitative analysis and the quantitative analysis can be performed (S3-1 and S3-2). Examples related to this are described above with reference to
In summary, the device for qualitative analysis and quantitative analysis (1, 1′) according to an embodiment of the present invention includes the microfluidic structures (20) having the same structure that can detect a plurality of types (for example, six kinds) of heavy metals on a rotatable platform (10) (for example, a circular disk), wherein each microfluidic structure (20) is arranged radially and symmetrically along the rotational direction of the rotatable platform (10) and comprises the detection unit (120, 120′) coated with an organic substance that can cause a color development reaction with the heavy metals.
According to the device for qualitative analysis and quantitative analysis (1, 1′) and the method of analyzing the sample using the same (2) according to the embodiment of the present invention, the centrifugal force generated upon rotation of the device for qualitative analysis and quantitative analysis (1, 1′) can move the fluid sample containing the heavy metals to the detection unit (120, 120′) and the qualitative analysis can be performed through the color development reaction. Further, the fluid can be developed by the paper capillary force when the rotation of the device stops and the quantification may be performed by identifying the color developed distance with the ruler (130) patterned on the device for qualitative analysis and quantitative analysis (1, 1′). It is possible to increase the detection limit of heavy metals through automatic fluid control and control of torque and capillary force. It is possible to improve the detection limit of heavy metal ions by the torque control. That is, by adjusting the centrifugal force and the capillary force by the rotation control, it is possible to improve the detection limit by controlling the reaction time of color development and the colored area. Specifically, when the development speed of the sample containing heavy metals due to the capillary force becomes faster than the speed at which the heavy metals and the organic chelating agent react with each other on the detection unit, the sample containing the heavy metals fails to sufficiently react with the organic chelating agent and develops on the entire detection unit. In the case of a heavy metal sample having a high concentration, there is no problem in detection because of the color appears, but there is a possibility that the quantitative property is lowered. In the case of a heavy metal sample of low concentration, there is a possibility that the color development does not occur due to insufficient reaction with the organic chelating agent of the detection unit, and the detection sensitivity and limitations may be lowered. However, according to the present invention, since the centrifugal force acts on the opposite side of the capillary force, the centrifugal force is applied to control the solution development speed by the capillary force so that the color development reaction can be sufficiently performed on the detection unit to improve the detection limitations.
Further, according to the device for qualitative analysis and quantitative analysis (1, 1′) and the method of analyzing the sample using the same (2) according to the embodiment of the present invention, it is economical and quick in the qualitative/quantitative analysis of multiple heavy metals. It is more economical than conventional expensive spectroscopy or mass spectrometry based heavy metal detector and can shorten analysis time. Thus, it can be applied quickly and conveniently in the field where the qualitative/quantitative analysis of heavy metals is required.
The technical constitution of the present invention as described above 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. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. In addition, the scope of the present invention is indicated by the appended claims rather than the detailed description of the invention. Also, all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being included within the scope of the present invention.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2017-0154395 | Nov 2017 | KR | national |
| 10-2018-0053637 | May 2018 | KR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/KR2018/012732 | 10/25/2018 | WO |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2019/098561 | 5/23/2019 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 5075215 | Dreyer | Dec 1991 | A |
| 7723120 | Xiao et al. | May 2010 | B2 |
| 8191715 | Cho et al. | Jun 2012 | B2 |
| 8470588 | Boehm et al. | Jun 2013 | B2 |
| 9737889 | Moon et al. | Aug 2017 | B2 |
| 9737890 | Lin et al. | Aug 2017 | B2 |
| 20010001060 | Kellogg et al. | May 2001 | A1 |
| 20030203495 | Rupp | Oct 2003 | A1 |
| 20040161365 | Siu Yu | Aug 2004 | A1 |
| 20050059165 | Davis | Mar 2005 | A9 |
| 20050087479 | Okada | Apr 2005 | A1 |
| 20050250218 | Andrelczyk et al. | Nov 2005 | A1 |
| 20080227217 | Yamamoto et al. | Sep 2008 | A1 |
| 20080280365 | Grumann et al. | Nov 2008 | A1 |
| 20090191643 | Boehm et al. | Jul 2009 | A1 |
| 20100120173 | Zhou et al. | May 2010 | A1 |
| 20100297659 | Yoo | Nov 2010 | A1 |
| 20120178182 | Kim et al. | Jul 2012 | A1 |
| 20120282707 | Borch | Nov 2012 | A1 |
| 20140017806 | Lee | Jan 2014 | A1 |
| 20140178978 | Cate | Jun 2014 | A1 |
| 20140186935 | Yoo | Jul 2014 | A1 |
| 20140199776 | Kim et al. | Jul 2014 | A1 |
| 20140370502 | Brennan et al. | Dec 2014 | A1 |
| 20150064774 | Moon et al. | Mar 2015 | A1 |
| 20150254845 | Tsai et al. | Sep 2015 | A1 |
| 20150321192 | Lee | Nov 2015 | A1 |
| 20160051986 | Lin et al. | Feb 2016 | A1 |
| 20170023465 | Zehler et al. | Jan 2017 | A1 |
| 20170209863 | Qin et al. | Jul 2017 | A1 |
| 20180369812 | Boehm et al. | Dec 2018 | A1 |
| 20190004043 | Araoz et al. | Jan 2019 | A1 |
| 20200141962 | Park et al. | May 2020 | A1 |
| Number | Date | Country |
|---|---|---|
| 101748204 | Jun 2010 | CN |
| 102580644 | Jul 2012 | CN |
| 103537329 | Jan 2014 | CN |
| 103917638 | Jul 2014 | CN |
| 104360068 | Feb 2015 | CN |
| 104937415 | Sep 2015 | CN |
| 105445449 | Mar 2016 | CN |
| 107192709 | Sep 2017 | CN |
| 2026072 | Feb 2009 | EP |
| 3173149 | May 2017 | EP |
| 3715852 | Sep 2020 | EP |
| 3715853 | Sep 2020 | EP |
| 2386331 | Sep 2003 | GB |
| 2003028883 | Jan 2003 | JP |
| 2004021112 | Jan 2004 | JP |
| 2007078676 | Mar 2007 | JP |
| 2007278741 | Oct 2007 | JP |
| 2007052647 | Apr 2009 | JP |
| 2010505096 | Feb 2010 | JP |
| 2013156070 | Aug 2013 | JP |
| 2015531494 | Nov 2015 | JP |
| 2019513977 | May 2019 | JP |
| 2019513977 | May 2019 | JP |
| 2020522704 | Jul 2020 | JP |
| 2020522705 | Jul 2020 | JP |
| 20030046315 | Jun 2003 | KR |
| 20080047409 | May 2008 | KR |
| 100846516 | Jul 2008 | KR |
| 20080069209 | Jul 2008 | KR |
| 20110079570 | Jul 2011 | KR |
| 20120132477 | Dec 2012 | KR |
| 2013000009 | Jan 2013 | KR |
| 20130000009 | Jan 2013 | KR |
| 20130000009 | Jan 2013 | KR |
| 101256474 | Apr 2013 | KR |
| 20130107069 | Oct 2013 | KR |
| 20140008976 | Jan 2014 | KR |
| 101375752 | Mar 2014 | KR |
| 20150027939 | Mar 2015 | KR |
| 20160022751 | Mar 2016 | KR |
| 20160105729 | Sep 2016 | KR |
| 20160119425 | Oct 2016 | KR |
| 20170024274 | Mar 2017 | KR |
| 2017108582 | Jun 2017 | WO |
| Entry |
|---|
| European Search Report for Application No. EP18878488.8, dated Nov. 4, 2020, 10 pages. |
| European Search Report for Application No. EP18879636.1, dated Nov. 9, 2020, 10 pages. |
| Extended European Search Report including Written Opinion for EP18878218.9, dated Nov. 4, 2020, 10 pages. |
| International Search Report from Application No. PCT/KR2018/012724, dated Feb. 11, 2019, 2 pages. |
| International Search Report from Application No. PCT/KR2018/012732 dated Feb. 11, 2019, 2 pages. |
| International Search Report from Application No. PCT/KR2018/012736 dated Feb. 11, 2019, 2 pages. |
| International Search Report from Application No. PCT/KR2018/012738 dated Feb. 11, 2019, 3 pages. |
| Extended European Search Report including Written Opinion for EP18877790.8 dated Oct. 5, 2020; 9 pages. |
| Search Report dated Aug. 10, 2022 from the Office Action for Chinese Application No. 201880037193.4 dated Aug. 17, 2022, 3 pages. |
| Search Report dated Aug. 17, 2022 from the Office Action for Chinese Application No. 201880036885.7 dated Aug. 24, 2022, 3 pages. |
| Search Report dated Aug. 17, 2022 from the Office Action for Chinese Application No. 201880037187.9 dated Aug. 23, 2022, 3 pages. |
| Search Report dated Aug. 19, 2022 from the Office Action for Chinese Application No. 201880036599.0 dated Aug. 26, 2022, 3 pages. |
| Number | Date | Country | |
|---|---|---|---|
| 20200141962 A1 | May 2020 | US |
