Patent Application
20130252515
This invention relates to a method of polishing the diamond-surface and, more specifically, to a method of polishing the various kinds of diamond product-surface.
As is well known, the diamond which is a crystal of carbon has been used for a variety of applications owing to its very high hardness, excellent resistance against abrasion as well as excellent slipping property, heat conductivity and high refractive index. For instance, it has been used for the tools for cutting, such as cutting tool, end mill and file, metal molds for plastic machining, such as punch and dies, sliding members such as valve lifter and bearing, heat-radiating members such as heat sink, electronic circuit boards and optical parts such as lens and window.
In order for their properties to be exhibited to a sufficient degree, these diamond products must have the diamond-surface polished to assume smooth surface.
The diamond-surface had so far been mechanically polished by using grains or a grind stone of diamond requiring extended periods of time. Besides, since both of them are abraded, there occurred such problems as short life of the tool and not being suited for polishing rugged three-dimensional surfaces. In an effort to improving the above defects, therefore, various kinds of polishing methods have now been proposed.
A patent document 1, for example, proposes a polishing method which conducts the polishing by using a polishing member constituted by a metal that easily reacts with carbon in the diamond crystals, applying ultrasonic waves onto the polishing member, and pushing the polishing member onto the surfaces of the diamond while the polishing member is undergoing ultrasonic oscillation. Here, examples of the metal that easily reacts with carbon include a γ-Fe-containing stainless steel, titanium (Ti), zirconium (Zr) and tantalum (Ta).
A patent document 2 proposes a polishing method by using, as a grind stone, an intermetallic compound of at least one metal element selected from the group consisting of Al, Cr, Mn, Fe, Co and Ni and at least one metal element selected from the group consisting of Zr, Hf, V, Nb, MO, Ta and W, and pushing the grind stone onto the diamond-surface that is moving relative thereto while, as required, heating the grind stone at 100 to 800° C.
A patent document 3 proposes a method of polishing the diamond-surface by focusing the laser beam on the diamond-surface.
A patent document 4 proposes a method of polishing a diamond film by sliding a metal and the diamond relative to each other at a point where the two are contacting to each other while continuously varying the temperature over a range of 700° C. to 1000° C. at the portion where the metal and the diamond are contacting to each other.
The methods proposed by the above prior arts, however, still leave problems that must be solved, and improvements have been desired.
For example, the method proposed by the patent document 1 executes the polishing by causing the metal constituting the polishing member to undergo chemical reaction with carbon on the diamond-surface by utilizing the heat of friction produced by ultrasonic oscillation. Upon utilizing the heat of friction produced by ultrasonic oscillation, however, the temperature must be controlled relying on the frequency and the pushing force involving great difficulty, and it is not easy to conduct the polishing maintaining stability and constant efficiency.
Upon utilizing the heat of friction, further, the energy efficiency is low and to elevate the temperature, the polishing member must be pushed onto the diamond-surface with a considerable pushing force. Besides, the hardness of the metal constituting the polishing member is very lower than that of the diamond. Accordingly, the polishing member abrades conspicuously and has only a short life.
Besides, since the polishing member must be pushed onto the diamond-surface with a considerable pushing force, the polishing machine and, specifically, the surrounding of the polishing member must have an increased toughness resulting in an increase in the size of the apparatus.
According to the method proposed in the patent document 2, the polishing is carried out by using a grind stone that contains as grains a very hard intermetallic compound. However, use of the special intermetallic compound drives up the cost strikingly. Further, since the polishing is conducted by pushing the hard intermetallic compound (hardness Hv of 500 to 1000) onto the diamond-surface, abraded powder generates much due to the abrasion of grains. Besides, the surfaces of the powder are highly and chemically active and, therefore, the abraded powder that is generated much may cause ignition and explosion. Moreover, the mechanical polishing by pushing the grind stone onto the diamond-surface needs the apparatus that tends to become bulky.
According to the method proposed in the patent document 3, the polishing is conducted by gasifying carbon in the diamond-surface by being heated by using a laser beam. However, the laser beam must be emitted so as to be focused on a convex portion on the diamond-surface, and it is very difficult to control the emission of the laser beam. Therefore, there remains a problem in that a very extended period of time is required for polishing a material having an area that is wide to some extent (e.g., several tens of square centimeters or more).
According to the method proposed in the patent document 4, the polishing is conducted by sliding the metal and the diamond relative to each other at a portion where they are contacting to each other while continuously varying the temperature over a range of 700° C. to 1000° C. at the portion where they are contacting to each other. According to this method, heating is conducted by a heater and the temperature cannot be instantaneously varied imposing limitation on adjusting the amount of polishing. According to the patent document 4, further, the polishing member is formed in a spherical shape to prevent deviated abrasion, and is rotated at a low speed. When the axis of rotation is fixed, however, the same contacting state can be maintained for only one turn. When it is attempted to utilize a wider surface, therefore, the axis of rotation must be freely varied causing the apparatus to become complex.
It is, therefore, an object of the present invention to provide a method of polishing the diamond-surface which generates abraded powder less, enables the polishing member to maintain an extended life and to be easily controlled, makes it possible to obtain the surface of a high degree of smoothness, and can be easily applied to polishing rugged three-dimensional surface, too.
Another object of the present invention is to provide a method of polishing the diamond-surface that is capable of conducting the polishing without using an expensive material obtained by a special production method, such as intermetallic compound but using a polishing member formed by using an inexpensive simple metal.
According to the present invention, there is provided a method of polishing a diamond-surface by:
using a polishing member that has a linear, belt-like or rod-like shape and has a metal-surface that easily reacts with carbon or has a carburizing metal-surface;
polishing the diamond-surface with said polishing member while continuously or intermittently varying a polishing surface of said polishing member; and
heating said polishing member and/or said the diamond-surface prior to polishing with said polishing member.
In the present invention, the metal that easily reacts with carbon is a metal having a temperature region in which a change in the Gibb's free energy (ΔG) in the carbide-forming reaction assumes a negative sign and, particularly preferably, is a metal of which the amount of change in the free energy (ΔG) in the carbide-forming reaction is not more than −20 kcal/mol in a temperature region that does not exceed the temperature (750 to 850° C.) at which the diamond carbonizes. Amounts of change in the Gibb's free energy of various metals in the carbide-forming reaction have been known as described, for example, in the Metals Data Book, 4th Edition (Edited by The Japan Institute of Metals, Maruzen Co.).
Further, the carburizing metal is a metal into which carbon can be diffused and permeated from the surface thereof.
In the polishing method of the present invention, it is desired that:
In the present invention, the polishing is conducted by rubbing the diamond-surface with the polishing member-surface. Here, the polishing member-surface is formed of a metal that easily reacts with carbon or of a carburizing metal, and the polishing member or the diamond-surface is heated prior to polishing with the polishing member. In the polishing, therefore, carbon on the diamond-surface reacts with the easily reacting metal that is forming the polishing member-surface, or diffuses and permeates in the layer of the carburizing metal-surface. As a result, the diamond-surface is robbed of carbon and is effectively polished.
In the invention, further, the polishing member that is used has a linear, belt-like or rod-like shape, and the polishing is conducted while continuously or intermittently varying the polishing member-surface formed of the above-mentioned metal material. That is, since the diamond-surface is slide-rubbed while varying the contacting portion, the reaction (reaction of the easily reacting metal with carbon on the diamond-surface, or diffusion and permeation of carbon) does not reach the saturated state, the surface pressure is not changed by abrasion, and the process continues maintaining stability at all times. Accordingly, the polishing can be continued maintaining stability for extended periods of time.
In the present invention, it is desired to use Zr, Ta, Ti or Al as the metal that forms the polishing member-surface and easily reacts with carbon. These metals are all soft metals and have Vickers' hardnesses (Hv) which are all not higher than 200 and are not only very lower than that of the diamond-surface but also considerably lower than the hardness of 500 to 1000 of the grind stone of an intermetallic compound used in the above patent document 2. Since the diamond-surface is slide-rubbed by the metal of such a low hardness so as to be polished, generation of the abraded powder can be effectively suppressed as compared to when a highly hard metal or metal compound is used making it possible to lengthen the life of the polishing member, which is a great advantage of the present invention.
Further, it is desired to use Fe, Ni or Co as the carburizing metal that forms the polishing member-surface. These metals have a property that permits carbon to diffuse and permeate therein from the surface thereof.
In the invention, further it is desired that the diamond-surface is heated by the laser beam-irradiation prior to polishing and to polish the laser beam-irradiated portion by using the polishing member. Namely, laser beam-irradiation is simply for heating at such a temperature at which the metal of the polishing member-surface reacts with carbon or at such a temperature at which the polishing member-surface is carburized with carbon on the diamond-surface. It should be noted that the laser beam-irradiation is not for vaporizing or volatilizing the carbon on the diamond-surface. Therefore, there is no need of adjusting the polishing conditions in a complex manner, and it is allowed to fabricate the apparatus in a compact size, to effectively apply the polishing method even to polishing rugged and three-dimensional surface and curved surface enabling the diamond-surface to be effectively smoothed.
Further, in heating the diamond-surface by the laser beam-irradiation, the diamond-surface is locally heated, i.e., a spot on the surface is heated instantaneously. Therefore, in polishing a diamond film formed on a predetermined substrate, the diamond film is not damaged by a difference in the thermal expansion between the diamond film and the substrate. Besides, since the heating is locally conducted, the energy can be utilized very highly efficiently.
Moreover, the intensity of the laser beam can be varied instantaneously making it possible to adjust the amount of polishing by varying the temperature of heating. Concretely, the surface property is monitored and the data are fed back to improve the evenness of the surface or to form fine ruggedness on the surface.
In the present invention, it is desired to heat both the polishing member and the diamond-surface prior to polishing the diamond-surface with the polishing member. In polishing the diamond-surface, the heating further accelerates the reaction of carbon on the diamond-surface with the metal forming the polishing member-surface or further accelerates carburization of the metal surface contributing to conducting the polishing efficiently and in a short period of time.
According to the present invention, further, the polishing member is formed using an existing simple metal instead of using a special compound such as intermetallic compound offering advantage from the standpoint of cost, too.
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Referring to
The diamond-surface 1a of the workpiece 1 is polished by using a polishing device 3 equipped with a polishing member 3a that rubs the diamond-surface 1a sliding on it. In the embodiment of the invention shown in
The polishing device 3 is equipped with the polishing member 3a that rubs the diamond-surface 1a sliding on it, the polishing member 3a being formed of a metal that easily reacts with carbon or of a carburizing metal.
As described above, the metal that easily reacts with carbon is a metal having a temperature region in which a change in the Gibb's free energy (ΔG) in the carbide-forming reaction assumes a negative sign, and its examples include Zr, Ta, Ti, W, Nb and Al. Among them, Zr, Ta, Ti, and Al are preferred. As described above, these metals have surface hardnesses Hv (Vickers' hardnesses) which are very low; e.g., Ta being about 100 to 150, Zr being about 120 to 200, Ti being about 100 to 200, and Al being about 15 to 50. Therefore, upon conducting the polishing by using such soft metals, it is allowed to effectively suppress the abrasion or deformation even when the polishing is conducted with a slide-rubbing force based on the above small pushing force making it possible not only to effectively prevent the abraded powder from being generated in large amounts but also to lengthen the life of the polishing member 3a and to conduct the polishing maintaining stability and good precision for extended periods of time.
Among the above soft metals, Zr, Ta and Ti are most desired. These metals have amounts of change in the Gibb's free energy (ΔG) in the reaction for forming carbide (ZrC, TaC, TiC) of not more than −20 kcal/mol and, specifically, as small as about −30 to −45 kcal/mol in a temperature region that does not exceed the temperature (750 to 850° C.) at which the diamond carbonizes. Due to the slide-rubbing after heated by the irradiation with the laser beam 5, therefore, the metal very easily reacts with carbon on the diamond-surface 1a and effectively polishes the diamond-surface 1a. For example, as demonstrated by the experimental results (see
As the carburizing metal, there can be exemplified Fe, Ni and Co. Among them, it is desired to use Ni for forming the surface of the polishing member 3a. Namely, when the polishing member 3a having the carburizing metal-surface is used, carbon atoms on the diamond-surface 1a diffuse in the surface of the polishing member 3a at the time of polishing with the polishing member 3a, and the diamond-surface can be effectively polished.
Polishing with the polishing member 3a is conducted by rubbing the portion irradiated with the laser beam by using the polishing member 3a that slides thereon; i.e., no large pushing force is necessary for the slide-rubbing. Though an appropriate pushing force may differ depending on the shape and material of the polishing member, it has been confirmed that the polishing can be conducted with a pushing force of about 5 N (0.5 kgf). On the other hand, the true contact area increases with an increase in the pushing force, and the polishing tends to accelerate. Therefore, the pushing force may be suitably set depending on the shape of the workpiece, shape and material of the polishing member corresponding thereto, and rigidity of the apparatus. In any way, the present invention does not require such a pushing force that causes an end of the polishing member to be greatly deformed. Therefore, the polishing member and the holding fitting can be realized in small sizes offering advantage from the standpoint of polishing the workpieces that have complex shapes and holes of small diameters therein.
In the invention, the diamond-surface 1a is locally heated by being irradiated with the laser beam 5 so that the metal forming the surface of the polishing member 3a easily reacts with carbon, and the degree of heating is determined by the density of the laser irradiation energy and the energy absorbency of the diamond. Concretely, the laser output, width of irradiation (spot diameter) and rate of working are suitably set based on the energy absorbency of the diamond to the laser source used for the polishing.
The temperature was measured by using a radiation thermometer (FTK9-R220A-2.5B11) manufactured by Japan Sensor Co.
According to the above relationship, the temperature increases with an increase in the density of the irradiated energy. If the density of the irradiated energy increases too much, the diamond is carbonized at around 750 to 850° C., and the temperature does not rise any more.
According to the present invention, therefore, the radiation conditions such as the density of the laser beam irradiation energy must be so set that the diamond-surface 1a is heated to a temperature range that does not exceed the temperature (750 to 850° C.) at which the diamond carbonizes. When a metal that easily reacts is used for the polishing member 3a, the temperature range is not lower than 200° C. and, specifically, is from 220° C. to 800° C. and when a carburizing metal is used, the temperature range is not lower than 600° C. and, specifically, is from 700° C. to 800° C. The irradiation condition may then be so set that the diamond-surface is heated at a temperature within the above range but does not exceed the melting point of the metal used for the polishing member 3a.
A variety of kinds of laser sources have been known for emitting the laser beam 5. In the present invention, the level of heating is so low that the laser source is not limited, and any known laser can be used. To conduct the polishing maintaining stability and, for example, in the field of welding and machining, solid lasers have been widely used, such as YAG and fiber laser. According to the present invention, however, it is also allowable to use gas lasers such as carbon dioxide gas laser and excimer laser in addition to the solid lasers.
Though there is no special limitation on the width of irradiation (spot diameter) of the laser beam 5, it is desired that it is close to the width over which the polishing member 3a comes in contact with the diamond from the standpoint of energy efficiency of the laser beam and the efficiency of polishing. For example, if the width of irradiation is very smaller than the width of contact between the two, the polishing does not proceed on the portions where the temperature is low (portions that are not irradiated) and, as a result, an extended period of time is required for the polishing. If the width of irradiation is set to be too wide, on the other hand, then the portions that need not be heated (that are not polished) are heated resulting in a loss of energy and making it necessary to undesirably increase the output of the laser beam or to decrease the rate of machining. The width in which the polishing member 3a comes in contact with the diamond can be roughly calculated in compliance with the widely known Hertz's law.
In the present invention, a portion is irradiated with the laser beam 5 and, thereafter, the irradiated portion is polished with the polishing member 3a. Here, the timing of polishing is that the surface of the irradiated portion is still maintained at about a temperature at which the metal of the polishing member 3a undergoes the reaction (or carburization) with carbon on the diamond-surface 1a. Here, however, since the diamond has a very high thermal conductivity (tends to be quickly cooled), it is desired to bring the irradiated portion as close to the polishing member 3a as possible so far as it is permitted by the installation space to shorten the time.
In the present invention, it is also allowable to heat the diamond-surface 1a by a known heating means such as various kinds of heaters, hot air, heating by flowing an electric current through a resistor, induction heating or high-energy beam instead of irradiation with the laser beam under a condition that the diamond is not carbonized. As described above, however, it is most desired to heat the diamond-surface 1a by the laser beam-irradiation.
In the invention as shown in
It is also allowable to polish the portion irradiated with the laser beam 5 by rotating the polishing device 3 (polishing member 3a) and the source of irradiating the laser beam 5 instead of rotating the workpiece 1. It is, however, a generally accepted practice to rotate the workpiece 1 since it does not cause the apparatus to become bulky. If the polishing cannot be accomplished to a sufficient degree by the polishing of one time only, then the above-mentioned operation may be repeated a plurality of times to further continue the polishing.
Depending on the shape of the surface of the workpiece 1, further, the workpiece 1 or the polishing device 3 (polishing member 3a) and the source of irradiating the laser beam 5 may be caused to linearly slide to conduct the polishing. Referring, for example, to
In order to efficiently conduct the polishing by causing the carbon atoms on the diamond-surface to react with the metal on the polishing surface of the polishing member or by causing the carbon atoms on the diamond-surface to diffuse and permeate into the polishing member-surface in the present invention, it is important that the polishing member 3a has a linear shape (wire shape), belt-like shape or rod-like shape and, further, that the contacting portion of the polishing member is varied continuously or intermittently while conducting the polishing. That is, the polishing member-surface (contacting portion) that is in contact with the diamond-surface varies at all times, enabling the carbon atoms to react with the metal or enabling the carbon atoms to diffuse and permeate efficiently at all times and permitting the polishing to be stably conducted at all times without any change in the surface pressure that is caused by the abrasion. As a result, the polishing can be conducted maintaining stability over extended periods of time.
Referring, for example, to
Referring to
Referring to
Upon driving the pulley 13 or the roller 17, the endless wire 15 or the endless belt 19 polishes the diamond-surface 1a while continuously or intermittently varying its rubbing surface. Further, the rod 21 is continuously or intermittently delivered so as to conduct the polishing.
Upon conducting the polishing by continuously or intermittently driving the polishing member 3a or, preferably, by continuously driving the polishing member 3a, the surface thereof that contacts to the diamond is not worn out through the polishing and is not abraded. Therefore, the surface pressure does not change, and the polishing can be continued maintaining stability over extended periods of time.
Further, when the polishing member 3a has a spherical shape as described in, for example, the patent document 4, the same effect can be expected by rotating the sphere. If the axis of rotation is fixed, however, the polishing member can be used for only one turn. To make the axis of rotation free, however, the apparatus becomes complex.
In the present invention, it is most desired to employ, specifically, the linear shape (endless wire 15) as shown in
In the present invention, further, the polishing member 3a is heated in advance to attain a synergistic effect. This makes it possible to further elevate the temperature on the diamond-surface and to accelerate the reaction of carbon in the diamond-surface 1a with the metal on the surface of the polishing member 3a or to accelerate the carburization of the metal surface (diffusion of carbon). As a result, the output of the laser beam can be maintained low.
When the polishing is conducted by heating the polishing member 3a, the diamond-surface can be polished maintaining a certain degree of efficiency relying only on the slide-rubbing with the polishing member 3a without being irradiated with the laser beam.
The above heating is effected such that the diamond-surface 1a or the surface of the polishing member 3a or the two are heated at a temperature of not lower than 200° C. and, specifically, not lower than 220° C. but that the temperature at which the diamond carbonizes is not exceeded.
As means for heating the polishing member 3a, further, there can be employed such known heating means as various kinds of heaters, hot air, heating by flowing an electric current through a resistor, induction heating or high-energy beam depending upon the form of the polishing member 3a.
As described earlier, the above heating means can also be used as means for heating the diamond-surface instead of irradiating the laser beam.
The above polishing method of the present invention makes it possible to conduct the polishing without using a polishing member made of a particularly expensive compound but using a polishing member made of a simple metal, as well as to easily control the polishing. It is, therefore, allowed to effectively polish not only flat surfaces but also rugged three-dimensional surface and curved surface lending the polishing method well for polishing the workpieces having diamond surfaces of various shapes.
Further, though it pertains to a widely known method, it is also allowable to apply a laser absorber onto the diamond-surface prior to or during the polishing working to improve the energy absorbing efficiency of the diamond.
In order to enhance the reactivity of the polishing member with the diamond, further, the polishing may be conducted while blowing an oxygen gas or the like gas. To maintain the quality of polishing, further, the polishing may be conducted while effecting the evacuation or continuously or intermittently blowing the high-pressure air or a very small amount of washing solution to remove metal carbide or foreign matter produced by the polishing.
The invention will now be described by way of the following Experiments.
In the Experiments, the surface roughness was measured by a method described below.
Surface roughness.
By using a surface roughness meter (Surfcom 575A) manufactured by Tokyo Seimitsusha Co., a maximum height Rz was measured in compliance with the JIS-B-0601.
Use was made of a polish tester of a structure schematically shown in
As a polishing member, a Ta wire having a circular shape in cross section and a diameter of 1 mm was attached to the above polish tester (see
The contacting portion of the wire was changed every after 5 times of slide-rubbing of the same portion of the test piece. Further, a maximum height Rz of the polished portion was measured. The results were as shown in
Table 1 shows the experimental conditions and the results of the following Experiments. Further,
<Experiment 2>
The polishing test was conducted in quite the same manner as in Experiment 1 but without irradiated with the laser beam. As a result, the diamond-surface was not quite polished.
The polishing test was conducted in quite the same manner as in Experiment 1 but decreasing the intensity of the laser beam down to 50 W.
As a result, the polishing did not much proceed with 50 W as compared to Experiment 1 (100 W). When the intensity of the laser was decreased down to 25 W, the polishing was not almost conducted.
The polishing test was conducted in quite the same manner as in Experiment 1 but without effecting the slide-rubbing with the polishing member.
As a result, it was confirmed that the diamond-surface was not quite polished.
The polishing test was conducted in quite the same manner as in Experiment 1 but increasing the pushing force to 20 N.
As a result, it was confirmed that the polishing was conducted faster than in Experiment 1 (10 N).
The polishing tests were conducted in quite the same manner as in Experiment 1 but changing the polishing member to Ti, Zr and Al. As a result, it was confirmed that the polishing proceeded faster when Ti and Zr were used than when Ta was used, but the polishing did not much proceed when Al was used.
Table 2 shows the experimental conditions and the results of the following Experiments.
The polishing test was conducted in quite the same manner as in Experiment 1 but changing the movement of the test piece as described below, without irradiating the laser beam and heating the polishing member at 700° C. by using a heater.
It was confirmed that the maximum height Rz decreased with an increase in the number of times of slide-rubbing and the polishing was conducted.
The polishing test was conducted in quite the same manner as in Experiment 9 but heating the polishing member at 800° C.
As a result, it was confirmed that the polishing proceeded faster than in Experiment 9 (700° C.).
The polishing test was conducted in quite the same manner as in Experiment 9 but heating the polishing member at 500° C.
As a result, it was confirmed that the polishing proceeded slower than in Experiment 9 (700° C.).
The polishing test was conducted in quite the same manner as in Experiment 9 but changing the polishing member to Fe.
As a result, it was confirmed that the polishing proceeded faster than in Experiment 9 (Ta).
<Experiment 13>
The polishing test was conducted in quite the same manner as in Experiment 12 but heating the polishing member at 500° C.
As a result, it was confirmed that the diamond-surface was not quite polished.
The polishing test was conducted in quite the same manner as in Experiment 1 but changing the polishing member to Ni.
As a result, it was confirmed that the polishing proceeded faster than in Experiment 11 (Fe).
The polishing test was conducted in quite the same manner as in Experiment 1 but changing the conditions as described below, moving the polishing member from the inner diameter toward the outer diameter at a rate of 0.025 mm/rev while rotating the test piece, ending the polishing when the end point is reached, changing the contacting portion of the wire and, thereafter, starting again the polishing from the inner diameter.
A maximum height Rz of the polished portion was measured on the same portion of the test piece every after 5 times of slide-rubbing.
As a result, it was confirmed that the maximum height Rz decreased with an increase in the number of times of slid-rubbing and the polishing was conducted. It was also confirmed that the polishing became slow as the polishing proceeded from the start point of polishing toward the end point.
The polishing test was conducted in quite the same manner as in Experiment 13 but continuously feeding the Ta wire at 0.5 mm/s and changing the contacting portion.
As a result, it was confirmed that the amount of polishing was nearly constant irrespective of the position from the start point of polishing.
The results of the polishing tests after the slide-rubbings of 15 times were judged as follows when the amounts of polishing (−ΔRz) were:
less than 0.1 μm: ×
0.1 to less than 0.5 μm: Δ
not less than 0.5 μm: ◯
| Number | Date | Country | Kind |
|---|---|---|---|
| 2010-292145 | Dec 2010 | JP | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/JP2011/066952 | 7/26/2011 | WO | 00 | 6/3/2013 |
