Patent Application
20160002749
The present invention relates to a high purity manganese (Mn) manufactured from a commercially available electrolytic manganese (Mn) and a manufacturing method thereof.
A method for manufacturing a commercially available metal Mn is an electrolytic process in an ammonium sulfate electrolytic bath. In a commercially available electrolytic Mn obtained by this method, contained are about 100 to 3000 ppm of sulfur (S) and several hundred ppm of carbon (C). Several hundred ppm of chlorine (CI) is also contained, and about several thousand ppm of oxygen (O) is further contained as it is an electrodeposit out of an aqueous solution.
As a method for removing S, O from the above electrolytic Mn, the sublimation purification method is well known among conventional technologies. However, the sublimation purification method has disadvantages such as very expensive instrumentation and very poor yield. Further, even though the sublimation purification method can reduce S and O, a metal Mn obtained from the purification method will be subject to contamination due to the material of a heater, the material of a condenser and the like in a sublimation purification apparatus. For this reason, disadvantageously, it is not suitable as a raw material for electronic devices.
As a prior art, the following Patent Literature 1 describes a method for removing S in metal Mn in which, at a melting temperature of an Mn oxide compound such as MnO, Mn3O4 and MnO2 and/or metal Mn, a material to be converted into such an Mn oxide, for example Mn carbonate, is added, and metal Mn to which an Mn compound has been added is melted under an inert atmosphere, and maintained in a molten state preferably for 30 to 60 minutes to give a sulfur content of 0.002%.
However, Literature 1 does not contain any description about the contents of oxygen (O), nitrogen (N), carbon (C) and chlorine (CI), and does not provide a solution for a problem that is caused when these materials are contained.
The following Patent Literature 2 describes a method for electrowinning metal Mn, and a method for electrowinning metal Mn characterized in that used is an electrolytic solution prepared by dissolving an excess amount of a high purity metal Mn in hydrochloric acid, filtering out undissolved materials to obtain a solution, neutralizing the solution by the addition of an oxidizing agent, filtering out the resulting precipitates, and then adding a buffering agent. It also describes a more preferable method for electrowinning metal Mn with the use of an electrolytic solution prepared by further adding metal Mn to a hydrochloric acid solution of a metal Mn, filtering out undissolved materials to obtain a solution, adding hydrogen peroxide and aqueous ammonia to the solution, filtering out precipitates formed under weakly acidic or neutral pH, and then adding a buffering agent.
However, although Literature 2 describes that S in a high purity Mn is reduced to 1 ppm, it does not have any description about the contents of oxygen (O), nitrogen (N), carbon (C) and chlorine (Cl), and does not provide a solution for a problem that is caused when these materials are contained.
The following Patent Literature 3 describes a method for manufacturing a high purity Mn, and a method in which an ion-exchange purification method using a chelating resin is applied to an aqueous Mn chloride, and then the resulting purified aqueous Mn chloride is highly purified by the electrowinning method. It is described that in a dry process, a high purity Mn can be obtained from solid phase Mn by the vacuum sublimation purification method (Mn vapor obtained by sublimation of solid phase Mn is selectively condensed and deposited as a purified material at a cooling unit due to the difference in vapor pressures).
Further, Literature 3 describes that the total concentration of sulfur (S), oxygen (O), nitrogen (N) and carbon (C) is 10 ppm or less.
However, Literature 3 does not contain any description about the content of chlorine (Cl) which has a deleterious effect on the manufacture of semiconductor components. Mn chloride is used as a raw material, and therefore, disadvantageously, chlorine may be contained at a high concentration.
The following Patent Literature 4 describes a method for manufacturing a low-oxygen Mn material in which an Mn material with oxygen reduced to 100 ppm or less can be obtained by performing induction skull melting to an Mn raw material under an inert gas atmosphere, and the Mn raw material is preferably subjected to an acid wash before induction skull melting in view of further reducing oxygen. However, although Literature 4 has a description about the reduction of oxygen (O), sulfur (S) and nitrogen (N) in a high purity Mn, it does not have any description about the content of the other impurities, and does not provide a solution for a problem caused when these materials are contained.
The following Patent Literature 5 describes an Mn alloy material for magnetic materials, an Mn alloy sputtering target, and a magnetic thin film. Also described is that the content of oxygen (O) is 500 ppm or less, the content of sulfur (S) is 100 ppm or less, and further, the total content of impurities (elements other than Mn and alloy components) is preferably 1000 ppm or less. Further, the Literature describes a method for removing oxygen (O) and sulfur (S) by adding, as deoxidizing/desulfurizing agents, Ca, Mg, La and the like to a commercially available electrolytic Mn and then performing high frequency melting. It also describes that vacuum distillation is performed after preliminary melting for being highly purified.
With regard to the above Mn raw material, it is described that in Example 3, a deoxidizing/desulfurizing agent is added, and then high frequency melting is performed to give an oxygen content of 50 ppm and a sulfur content of 10 ppm (Table 3). In Example 7, vacuum distillation is performed after preliminary melting to give an oxygen content of 30 ppm and a sulfur content of 10 ppm (Table 7). Moreover, in these Examples, about 10 to 20 ppm of Si and about 10 to 30 ppm of Pb are contained.
However, the purity of Mn manufactured according to the following Patent Literature 5 is at a 3N level, and a high purity Mn, such as that obtained from the present invention, could not be obtained. Further, in Example 3 of the following Patent Literature 5, high frequency melting is performed after adding a deoxidizing/desulfurizing agent. Therefore, disadvantageously, a deoxidizing/desulfurizing agent may contaminate Mn to reduce the purity. In the case of Example 7, vacuum distillation is performed after preliminary melting. Therefore, disadvantageously, a manufacturing cost is high because 99% or more of dissolved Mn is subject to volatilization.
The following Patent Literature 6 describes a method for manufacturing a high purity Mn material and a high purity Mn material for forming a thin film. In this case, it is described that preliminary melting of crude Mn is performed at 1250 to 1500° C., and then vacuum distillation is performed at 1100 to 1500° C. to obtain a high purity Mn material. The degree of vacuum when performing vacuum distillation is preferably 5×10−5 to 10 Torr.
The total impurity content in a high purity Mn obtained as described above is 100 ppm or less: Oxygen (O): 200 ppm or less, Nitrogen (N): 50 ppm or less, Sulfur (S): 50 ppm or less and Carbon (C): 100 ppm or less. This is followed by examples in which the oxygen content is 30 ppm, and other elements are contained less than 10 ppm in Example 2 (Table 2). However, even in this case, the impurity level has not reached the intended level.
In addition, the following Patent Literature 7 describes a sputtering target comprising a high purity Mn alloy. Patent Literature 8 describes a method for recovering Mn using sulfuric acid. Patent Literature 9 describes a method for manufacturing metal Mn in which Mn oxide is subjected to heat reduction. However, none of the above describes desulfurization in particular.
In view of the above, the present inventors have proposed a method for manufacturing a high purity Mn, comprising leaching an Mn raw material in acid, filtering out residues and using the filtrate for the cathode side in electrolysis; the above method for manufacturing a high purity Mn, further comprising degassing the above electrolytic Mn to reduce the CI content in the above electrolytic Mn to 100 ppm or less; and the method for manufacturing a high purity Mn, further comprising degassing the above electrolytic Mn material, and performing melting under an inert atmosphere to manufacture Mn where Cl≦10 ppm, C≦50 ppm, S<50 ppm, and O<30 ppm (see Patent Literature 10).
This method is effective for producing a high purity Mn. An object of the present invention is to provide a manufacturing method capable of achieving a higher purity and reducing cost. Another object is to provide a high purity Mn.
An object of the present invention is to provide a high purity Mn manufactured from a commercially available electrolytic Mn and a manufacturing method thereof. In particular, the present invention aims to provide a high purity Mn that has a significantly lower impurity content and is manufactured at a lower cost as compared with the conventional technology.
The present invention solves the above problems, and provides the following invention.
1) A method for manufacturing a high purity Mn, the method comprising: placing an Mn raw material in a magnesia crucible to perform melting with the use of a vacuum induction melting furnace (VIM furnace) at a melting temperature of 1240 to 1400° C. under an inert atmosphere of 500 Torr or less; then adding calcium (Ca) in a range between 0.5 and 2.0% of the weight of Mn to perform deoxidation and desulfurization; casting the resultant in an iron mold after the completion of the deoxidation and desulfurization to manufacture an ingot; then placing the Mn ingot in a magnesia crucible to perform melting with the use of a vacuum induction melting furnace (VIM furnace) at a melting temperature, which is adjusted to 1200 to 1450° C. and maintained for 10 to 60 minutes, under an inert atmosphere of 200 Torr or less; casting the resultant in an iron mold to manufacture an ingot; then placing the metal Mn ingot in an alumina crucible; reducing pressure to 0.01 to 1 Torr with a vacuum pump; and then heating to develop a sublimation and distillation reaction for obtaining a high purity Mn.
2) The method for manufacturing a high purity Mn according to 1), comprising, when performing the sublimation and distillation, placing the metal Mn ingot in a cylindrical alumina crucible and vertically aligning a similarly-shaped alumina cylinder (a cooling cylinder) on top of the above cylindrical crucible to develop a sublimation and distillation reaction so that Mn deposits inside the upper alumina cylinder.
3) The method for manufacturing a high purity Mn according to 1) or 2), comprising attaching a carbon heater to the outside of the cylindrical alumina crucible into which the above metal Mn ingot is placed, and performing heating.
4) The method for manufacturing a high purity Mn according to any one of 1) to 3), comprising performing sublimation and distillation purification at 1100 to 1250° C. and a sublimation rate of 20 to 184 g/h.
5) The method for manufacturing a high purity Mn according to any one of 1) to 4), comprising, when the deposited amount of sublimated/distilled Mn reaches 70% of the weight of the metal Mn ingot charged into the alumina crucible during the sublimation/distillation step, stopping the sublimation/distillation step.
6) A high purity Mn having a purity of 4N5 (99.995%) or more except for gas components, wherein the total amount of impurity elements B, Mg, Al, Si, S, Ca, Cr, Fe and Ni is 50 ppm or less. Note that the gas component elements in the present invention mean hydrogen (H), oxygen (O), nitrogen (N), and carbon (C). The same hereinafter.
7) A high purity Mn having a purity of 5N (99.999%) or more except for gas components, wherein the total amount of impurity elements B, Mg, Al, Si, S, Ca, Cr, Fe and Ni is 10 ppm or less.
8) A high purity Mn having a purity of 4N5 (99.995%) or more except for gas components, wherein O and N as the gas components are less than 10 ppm respectively, and the total amount of impurity elements B, Mg, Al, Si, S, Ca, Cr, Fe and Ni is 50 ppm or less.
9) A high purity Mn having a purity of 5N (99.999%) or more except for gas components, wherein O and N as the gas components are less than 10 ppm respectively, and the total amount of impurity elements B, Mg, Al, Si, S, Ca, Cr, Fe and Ni is 10 ppm or less.
Note that each instance of the unit “ppm” used herein means “wtppm”. Except for nitrogen (N) and oxygen (O) which are gas component elements, analytical values for the concentration of each element were analyzed with the GDMS (Glow Discharge Mass Spectrometry) method. Moreover, gas component elements were analyzed using an oxygen/nitrogen analyzer from LECO Corporation.
The present invention provides the following effects.
(1) A high purity Mn, which has a purity of 4N5 (99.995%) or more except for gas components, and in which the total amount of impurity elements B, Mg, Al, Si, S, Ca, Cr, Fe and Ni is 50 ppm or less, can be obtained. Further a high purity Mn, which has a purity of 5N (99.999%) or more except for gas components, and in which the total amount of impurity elements B, Mg, Al, Si, S, Ca, Cr, Fe and Ni is 10 ppm or less, can be obtained.
(2) Further each of O and N as gas components can be reduced to less than 10 ppm.
(3) Without the need for special equipment, a common furnace can be used for manufacturing a high purity Mn at a lower cost and higher yield as compared with the conventional distillation method.
Below, embodiments of the invention will be described in detail.
Commercially available (a 2N level) flake-like electrolytic Mn can be used as a raw material in the method for manufacturing a high purity Mn according to the present invention. However, there is no particular limitation for the raw material since the method is not affected by the purity of the raw material.
When manufacturing a high purity Mn, first, an Mn raw material is placed in a magnesia crucible, and subjected to melting with the use of a vacuum induction melting furnace (VIM furnace) at a melting temperature of 1240 to 1400° C. under an inert atmosphere of 500 Torr or less (primary VIM step).
If the temperature is less than 1240° C., Mn does not melt, and the VIM treatment cannot be performed. If the temperature is more than 1400° C., suspended materials of oxides and/or sulfides are re-melted into Mn due to the high temperature. Therefore, the concentrations of magnesium (Mg), calcium (Ca), oxygen (O) and sulfur (S) after the primary VIM step will be in an order of hundreds of ppm to thousands of ppm, and the intended purity in the present invention ultimately cannot be achieved. Results are shown in Table 2.
Then, Ca in a range of 0.5 to 2.0% of the weight of Mn was gradually added to this molten Mn to perform deoxidation and desulfurization. After the completion of the deoxidation and desulfurization, the resultant is cast in an iron mold to manufacture an ingot. After cooling the ingot, slags adhered to the ingot are removed.
Next, this Mn ingot is placed in a magnesia crucible to perform melting with the use of a vacuum induction melting furnace (VIM furnace) at a melting temperature, which is adjusted to 1200 to 1450° C. and maintained for 10 to 60 minutes, under an inert atmosphere of 200 Torr or less (secondary VIM step). Then, the resultant is cast in an iron mold to manufacture an ingot. After cooling the ingot, slags adhered to the ingot are removed.
Here, in the primary VIM step, since Ca as a deoxidizing/desulfurizing agent is added to molten Mn during melting, a small amount of Ca is contained in an Mn ingot after the primary melting, and the melting point of Mn decreases. Therefore, even in a case where a temperature of the secondary VIM is in a temperature range lower than that of the primary VIM, melting can be performed.
Further, in the secondary VIM step, the deoxidizing/desulfurizing agent (Ca) added during the primary VIM step can be removed. When a temperature of the secondary VIM is more than 1450° C., volatilization loss of Mn significantly increases, resulting in a decreased yield and increased cost; therefore, it is not preferable.
Next, this metal Mn ingot is placed in an alumina crucible, the pressure is reduced to 0.01 to 1 Torr with a vacuum pump, and then heating is performed. Next, a sublimation/distillation reaction is developed at a sublimation/distillation temperature of 1100 to 1250° C. to manufacture a high purity Mn. Mn volatilized by the sublimation/distillation reaction is guided to a cooling cylinder where deposited Mn is recovered.
Note that preferably, the sublimation/distillation step is stopped when the amount of Mn recovered in the sublimation/distillation reaction reaches 70% of the weight of the Mn material charged in the alumina crucible. This stop operation can prevent impurity elements which remain in the crucible from sublimating to contaminate Mn deposited in the cooling cylinder to reduce the purity. The outlines of this step are shown in
In the case of Mn obtained by this manufacturing method, a high purity Mn having a purity of 4N5 (99.995%) or more except for gas components in which the sum (the total amount) of impurity elements, B, Mg, Al, Si, 5, Ca, Cr, Fe and Ni is 50 ppm or less can be obtained.
Further, by changing the conditions in the above sublimation/distillation purification, a high purity Mn having a purity of 5N (99.999%) or more in which the sum (the total amount) of impurity elements, B, Mg, Al, Si, S, Ca, Cr, Fe and Ni is 10 ppm or less can be obtained. Specifically, purification can be performed at a sublimation/distillation temperature of 1200 to 1250° C.
Then, when performing sublimation purification, each of O and N as gas components can be reduced to less than 10 ppm.
A high purity Mn can be obtained by placing a metal Mn ingot in a cylindrical alumina crucible for performing the sublimation and distillation; vertically aligning a similarly-shaped alumina cylinder on top of the above cylindrical crucible; and developing a sublimation and distillation reaction to deposit Mn inside the upper alumina cylinder.
The structure is simple as cylindrical alumina crucibles (cylinders) are piled, and equipment with such a structure contributes to the reduction in a manufacturing cost.
It is necessary to heat the cylindrical alumina crucible in which the above metal Mn ingot has been placed. A carbon heater can be attached to the outside of the crucible for heating. This equipment structure is also simple, and contributes to the reduction in a manufacturing cost.
When performing sublimation/distillation purification, it is preferred to perform heating of the Mn inside the cylindrical alumina crucible at 1100 to 1250° C. and at a sublimation rate of 20 to 184 g/h. In this case, the duration of sublimation/distillation purification is about 8 to 75 hours.
By adjusting the temperature and sublimation rate of the sublimation/distillation purification, the amount of impurities can be controlled. The sublimation/distillation rate is preferably 20 to 184 g/h, more preferably 103 to 184 g/h.
Further, the sublimation/distillation reaction step was stopped when the amount of Mn recovered by deposition reached 70% (recovery rate) of the weight of the Mn raw material charged in the alumina crucible.
In the sublimation/distillation step, as distillation progresses, the impurity concentrations in the raw material Mn increase, and impurity elements are sublimated more significantly at the final stage of the step. Therefore, contamination of impurities into the distilled Mn can be prevented by stopping the step when Mn recovered by deposition reaches 70 wt % of the weight of the raw material Mn.
Descriptions below with reference to Examples and Comparative Examples are provided for purposes of better understanding of the present invention. The present invention shall not be limited by Examples or Comparative Examples.
As a starting material, a commercially available flake-like electrolytic Mn (purity 2N: 99%) was used. Impurities in the raw material Mn were B: 15 ppm, Mg: 90 ppm, Al: 4.5 ppm, Si: 39 ppm, S: 280 ppm, Ca: 5.9 ppm, Cr: 2.9 ppm, Fe: 11 ppm, Ni: 10 ppm, O: 720 to 2500 ppm, and N: 10 to 20 ppm.
The above Mn raw material was placed in a magnesia crucible, and melting was performed using a vacuum induction melting furnace (VIM furnace) at a melting temperature of 1300° C. under an inert atmosphere of 200 Torr or less. Then, Ca in 1 wt % of the weight of Mn was gradually added to this molten Mn to perform deoxidation and desulfurization. After the completion of the deoxidation and desulfurization, the resultant was cast in an iron mold to manufacture an ingot. After cooling the ingot, slags adhered to the ingot were removed.
Impurities in the ingot after this primary melting were B: 12 ppm, Mg: 130 ppm, Al: 1.2 ppm, Si: 20 ppm, S: 3.4 ppm, Ca: 520 ppm, Cr: 0.25 ppm, Fe: 2.2 ppm, Ni: 1.4 ppm, O: 10 ppm, and N: 10 ppm. Results are shown in Table 1.
As shown in Table 1, Ca is increased in the cast Mn due to the Ca reduction step. Mg is also increased because Mg is a constituent element of the magnesia crucible and susceptive to reduction by Ca, and a portion thereof contaminates the cast Mn. Meanwhile, the results reveals that S is significantly decreased, and other elements are also reduced.
Next, the Mn ingot obtained from the primary VIM was placed in a magnesia crucible, and a secondary VIM was performed using a vacuum induction melting furnace (VIM furnace) at a melting temperature, which was adjusted to 1400° C. and maintained for 30 minutes, under an inert atmosphere of 100 Torr or less. Then, the resultant was cast in an iron mold to manufacture an ingot. After cooling the ingot, slags adhered to the ingot were removed.
Impurities in the ingot after this secondary melting were B: 10 ppm, Mg: 13 ppm, Al: 1.9 ppm, Si: 20 ppm, S: 0.58 ppm, Ca: 25 ppm, Cr: 0.28 ppm, Fe: 2.4 ppm, Ni: 1.2 ppm, O: 10 ppm, and N: 10 ppm. Results are also shown in Table 1.
As shown in Table 1, the results reveal that Ca and Mg, which increased in the primary melting, are significantly reduced after the secondary melting. S is also reduced. This can be explained if volatile impurities are removed in the secondary melting.
The metal Mn ingot obtained through the above primary VIM step and the secondary VIM step was placed in a cylindrical alumina crucible, and a similarly-shaped alumina cylinder was vertically aligned on top of this cylindrical crucible to develop a sublimation and distillation reaction.
After pressure was reduced to 0.1 Torr with a vacuum pump, heating was performed to develop a sublimation and distillation reaction of Mn. Then, Mn was allowed to be deposited inside of the upper alumina cylinder, and a high purity Mn was recovered therefrom. Note that the cylindrical alumina crucible into which the Mn ingot was placed was heated with a carbon heater attached to the outside of the crucible.
When performing sublimation/distillation purification, Mn in the cylindrical alumina crucible was heated to 1050 to 1250° C., and the sublimation rate was 3 to 184 g/h. In this case, the duration of sublimation purification was about 8 to 75 hours.
The impurity removing effect of sublimation/distillation purification is significantly affected by the heating temperature and the sublimation/distilling rate. Therefore, it is performed in varying temperatures within a range of 1050 to 1250° C. and sublimation/distilling rates within a range of 3 to 184 g/h, as described above. Specific examples (Examples and Comparative Examples) are shown below.
Further, the sublimation/distillation step was stopped when the amount of Mn recovered in the sublimation/distillation reaction reached 70% (recovery rate) of the weight of the Mn raw material charged in the alumina crucible to prevent the distilled Mn from being contaminated by impurities. In order to determine when the sublimation/distillation step is to be stopped, the relationship between the heating temperature and the sublimation/distillation rate is preliminarily investigated, and the amount of Mn to be deposited in a sublimation/distillation rate at each heating temperature is calculated to determine the time to stop the step.
In a case where sublimation/distillation is performed at a heating temperature: 1050° C. and a sublimation rate: 3 (g/h), impurities in the metal Mn after this sublimation purification were B: 0.2 ppm, Mg: 20 ppm, Al: 0.15 ppm, Si: 0.05 ppm, S: 0.03 ppm, Ca: 30 ppm, Cr: 0.05 ppm, Fe<0.1 ppm, Ni: 0.01 ppm, O<10 ppm, and N<10 ppm. Results are shown in Table 1.
In this case, since the temperature was low and the sublimation rate was small, the effects of sublimation purification were not sufficient, and the intended purity of 4N5 (99.995%) or more in the present invention was slightly unachievable. This is provided as the Reference Example or Comparative Example.
Sublimation/distillation purification was performed at a heating temperature of 1100° C. and a sublimation rate of 23 (g/h).
Impurities in the metal Mn after this sublimation purification were B: 0.61 ppm, Mg: 17 ppm, Al: 0.25 ppm, Si: 0.28 ppm, S: 0.07 ppm, Ca: 7.3 ppm, Cr: 0.05 ppm, Fe<0.1 ppm, Ni: 0.03 ppm, O<10 ppm, and N<10 ppm. Results are shown in Table 1 as well.
In this case, the effects of sublimation purification were sufficient, and the intended purity of 4N5 (99.995%) or more in the present application was able to be achieved. This is a preferred Example.
Sublimation/distillation purification was performed at a heating temperature of 1200° C. and a sublimation rate of 103 (g/h).
Impurities in the metal Mn after this sublimation purification were B: 0.46 ppm, Mg: 0.17 ppm, Al: 1.4 ppm, Si: 1.2 ppm, S: 0.02 ppm, Ca: 2.1 ppm, Cr: 0.69 ppm, Fe: 0.21 ppm, Ni: 0.08 ppm, O<10 ppm, and N<10 ppm. Results are also shown in Table 1 as well.
In this case, the effects of sublimation purification were sufficient, and the intended purity of 5N (99.999%) or more in the present application was able to be achieved. This is a further preferred Example.
Sublimation/distillation purification was performed at a heating temperature of 1250° C. and a sublimation rate of 184 (g/h).
Impurities in the metal Mn after this sublimation purification were B: 1.1 ppm, Mg<0.01 ppm, Al: 0.85 ppm, Si: 3.6 ppm, S: 0.04 ppm, Ca: 1.9 ppm, Cr: 1.4 ppm, Fe: 0.77 ppm, Ni: 0.18 ppm, O<10 ppm, and N<10 ppm. Results are shown in Table 1 as well.
In this case, the effects of sublimation purification were sufficient, and the intended purity of 5N (99.999%) or more in the present application was able to be achieved. This is a preferred Example.
According to the present invention, Mn having ultra-high purity can be obtained by a relatively simple manufacturing process at a reduced manufacturing cost. Therefore, it is useful as: a metal Mn used for wiring materials, electronic component materials such as magnetic materials (magnetic recording heads), and semiconductor component materials; and a sputtering target material for forming a thin film thereof, in particular an Mn-containing thin film. Since the present invention can be manufactured with a common furnace without the need for special equipment, and a high purity Mn can be obtained at a lower cost and higher yield as compared with the conventional distillation method, it can be said that it has high value regarding industrial use.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2013-222126 | Oct 2013 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2014/072969 | 9/2/2014 | WO | 00 |
