Patent Grant
8105712
This application is the U.S. National Phase under 35 U.S.C. §371 of International Application No. PCT/JP2009/002854, filed on Jun. 23, 2009, which in turn claims the benefit of Japanese Application Nos. 2008-205418, filed on Aug. 8, 2008, 2008-209836, filed on Aug. 18, 2008, 2008-209838, filed on Aug. 18, 2008, and 2008-275166, filed on Oct. 27, 2008, the disclosures of which Applications are incorporated by reference herein.
The present invention relates to sealed secondary batteries and methods for fabricating sealed secondary batteries, and more particularly to a joint structure between a sealing plate and a lead extending from an electrode group.
Sealed secondary batteries, including aqueous electrolyte secondary batteries typified by high-capacity alkaline storage batteries and nonaqueous electrolyte secondary batteries typified by lithium-ion secondary batteries, are widely used as power sources for driving mobile equipment or other devices.
These sealed secondary batteries have a sealed structure in which an electrode group formed by stacking or winding a positive electrode plate and a negative electrode plate with a separator interposed therebetween is housed in a battery case together with an electrolyte, and in which an opening of the battery case is sealed with a sealing plate with a gasket sandwiched therebetween. In this structure, a lead extending from one of the electrode plates (e.g., the positive electrode plate) in the electrode group is joined to the sealing plate also serving as an external terminal at one side, whereas a lead extending from the other electrode plate (e.g., the negative electrode plate) in the electrode group is joined to the battery case also serving as an external terminal at the other side. To join the lead to the sealing plate or to the battery case, resistance welding is widely employed.
The opening of the battery case is sealed by resistance-welding the lead extending from the electrode group to the sealing plate, with the electrode group being housed in the battery case, and then bending the lead to seal the opening of the battery case with the sealing plate.
In this process, while the lead is resistance-welded to the sealing plate, substances (mainly metal particles removed from the melted lead) can be sputtered. If these sputtered substances enter the electrode group in the battery case, the separator might be damaged, resulting in an internal short. In another case where sputtered substances adhere to the gasket joined to the periphery of the sealing plate, when the opening of the battery case is sealed with the sealing plate by crimping with a gasket sandwiched therebetween, a narrowed portion of the gasket might be sheared by the adhering substances. Consequently, the battery case and the sealing plate come into contact with each other while sandwiching the adhering substances therebetween, resulting in a short circuit.
To prevent such a short circuit caused by, for example, contamination by sputtered substances, the opening of a battery case may be covered with a thin plate or the like so as to prevent sputtered substances from entering the battery case during resistance welding of the lead to the sealing plate. However, the opening cannot be completely sealed, and thus, such covering is insufficient for preventing contamination by sputtered substances.
On the other hand, joining by ultrasonic welding, instead of resistance welding, does not cause melting as caused by the resistance welding, and thus contamination by sputtered substances can be avoided in principle. However, joining by ultrasonic welding exhibits a lower joint strength than that obtained by the resistance welding. In addition, if the sealing plate has a safety mechanism for explosion protection, ultrasonic vibration might affect the function of the safety mechanism. Further, joining by ultrasonic welding is not preferable in reliability because an active material might be peeled off from the electrode plate.
Since positive electrode plates of lithium secondary batteries generally use aluminium, the leads extending from the positive electrode plates also use aluminium. In addition, to reduce the weight of batteries, the battery cases and the sealing plates have begun to use aluminium. In this case, a joint between the lead and the sealing plate means a joint between aluminium components. In general, an aluminium alloy has a higher electric conductivity and a higher thermal conductivity than those of steel. Accordingly, a large current needs to flow for a short period in resistance welding, resulting in that a welding rod badly wears, and it is difficult to maintain a stable joint for a long period. To prevent this problem, laser welding is employed for welding between the lead and the sealing plate (see, for example, PATENT DOCUMENTS 1 and 2).
This laser welding can considerably narrow a laser beam, thereby obtaining a small welding area. Accordingly, the amount of sputtered substances can be greatly reduced.
As described above, although welding between the lead and the sealing plate can be inevitably readily affected by sputtering in consideration of its process, the use of laser welding is expected to greatly reduce this influence.
However, a reliability test, including a strength test, performed by the inventors of the present invention on lithium-ion secondary batteries for each of which a lead and a sealing plate were joined by laser welding, showed a certain proportion of short-circuited batteries.
A further examination of the short-circuited batteries confirmed that an internal short circuit was caused by a short circuit occurring between the battery case and the sealing plate due to shearing of the gasket and damage on the separator. This phenomenon was analyzed, and it was found that foreign substances which have caused the short circuit contained aluminium as materials for the lead and the sealing plate.
In view of this result, the phenomenon seems to occur because sputtering is caused by variations in some external factors in fabrication processes during laser welding between the lead and the sealing plate, and the sputtered substances adhere to the gasket or enter the battery case.
It is therefore a main object of the present invention to provide a stable, reliable sealed secondary battery by reducing the influence of sputtering during laser welding between a lead and a sealing plate.
A sealed secondary battery according to the present invention is a sealed secondary battery in which an electrode group formed by stacking or winding a positive electrode plate and a negative electrode plate with a separator interposed therebetween is housed in a battery case, and an opening of the battery case is sealed with a sealing plate. In this sealed secondary battery, a lead extending from one of the positive and negative electrode plates in the electrode group is laser-welded to the sealing plate with application of a laser beam having a spot diameter smaller than a thickness of the lead.
With this configuration, even with a variation in external factors in fabrication processes in welding between the lead and the sealing plate, a joint strength between the lead and the sealing plate can be maintained with sputtering during laser welding being reduced. In this manner, a stable, reliable sealed secondary battery can be obtained.
In the sealed secondary battery, a welded portion formed by parts of the lead and the sealing plate preferably has a penetration depth greater than a bead diameter of the welded portion. With this configuration, the penetration depth of the welded portion formed by parts of the lead and the sealing plate can be increased, thereby increasing the joint strength, and further reducing sputtering during welding.
In the sealed secondary battery, a welded portion formed by parts of the lead and the sealing plate preferably has a linear shape. With this configuration, a stable joint strength can be maintained even with application of shock from various directions to the welded portion.
A method for fabricating a sealed secondary battery according to the present invention is a method for fabricating a sealed secondary battery with the foregoing configuration, and includes the steps of: preparing an electrode group formed by stacking or winding a positive electrode plate and a negative electrode plate with a separator interposed therebetween; connecting one end of a lead to one of the positive and negative electrode plates in the electrode group; housing the electrode group in a battery case; applying, to the lead, a laser beam having a spot diameter smaller than a thickness of the lead, with another end of the lead brought into contact with a sealing plate, thereby laser-welding the another end of the lead to the sealing plate; and sealing an opening of the battery case with the sealing plate.
With this method, even with a variation in external factors in fabrication processes in welding between the lead and the sealing plate, a joint strength between the lead and the sealing plate can be maintained with sputtering being reduced during laser welding. In this manner, a reliable sealed secondary battery can be obtained with stability.
In the method, the laser beam is preferably applied from a fiber laser. The lead is preferably irradiated with the laser beam, while being continuously scanned with a fiber laser. In this manner, a reliable sealed secondary battery can be obtained with stability and controllability.
The present invention can provide a stable, reliable sealed secondary battery by maintaining a joint strength between a lead and a sealing plate with sputtering being reduced during laser welding even with a variation in external factors in fabrication processes in welding the lead to the sealing plate.
a)-1(d) are cross-sectional views schematically illustrating a process of laser-welding a lead to a sealing plate with a foreign substance attached to the surface of the lead.
a)-2(d) are cross-sectional views schematically illustrating a process of laser-welding the lead to the sealing plate with a foreign substance sandwiched at the interface between the lead and the sealing plate.
a)-3(d) are cross-sectional views schematically illustrating a process of laser-welding the lead to the sealing plate with a gap created between the lead and the sealing plate.
a)-4(d) are cross-sectional views schematically illustrating a process of laser-welding the lead to the sealing plate with an end of the lead irradiated with a laser beam.
a)-6(d) are cross-sectional views schematically illustrating a process of laser-welding a lead to a sealing plate according to a first embodiment of the present invention.
a)-7(c) are views showing an example in which laser welding between the lead and the sealing plate of the first embodiment is applied to a lithium ion battery.
a)-12(d) are plan views illustrating variations of the shape of a welded portion in the second embodiment.
a) and 13(b) are plan views illustrating variations of the shape of the welded portion in a case where the welded portion of the second embodiment forms a closed line.
a)-14(d) are views illustrating a process of sealing an opening of a battery case with a sealing plate according to the second embodiment.
a)-15(d) illustrate a joint structure formed by keyhole welding.
a)-16(d) schematically illustrate a process of laser-welding a lead to a sealing plate according to a third embodiment of the present invention.
The inventors of the present invention arrived at the following idea. Despite the assumption that the influence of sputtering in welding between the lead and the sealing plate is very small because the laser welding requires a very small melted area, a short circuit which seems to be due to, for example, contamination by sputtered substances is caused by variations in some external factors in fabrication processes.
Specifically, foreign substances created in fabrication processes might adhere to the surface of the lead or the surface of the sealing plate during the welding between the lead and the sealing plate. In addition, although the lead and the sealing plate are welded together while being in contact with each other, the pressure during the welding is low, and thus a gap might be formed between the lead and the sealing plate during the welding. Further, a laser beam might strike different positions in a portion to be welded between the lead and the sealing plate.
a)-1(d) are cross-sectional views schematically illustrating a process of laser-welding a lead 11 to a sealing plate 10 with a foreign substance 20 attached to the surface of the lead 11.
As illustrated in
If the foreign substance 20 adheres to the surface of the lead 11 in the manner as described above, a rapid volume expansion due to evaporation of this foreign substance 20 exerts a compressive force, thereby increasing the amount of sputtering.
a)-2(d) are cross-sectional views schematically illustrating a process of laser-welding the lead 11 to the sealing plate 10 with a foreign substance 21 sandwiched at the interface between the lead 11 and the sealing plate 10. A phenomenon observed in this process is basically the same as that observed when the foreign substance 20 adheres to the surface of the lead 11. However, since the foreign substance 21 exists in the interface between the lead 11 and the sealing plate 10, a compressive force exerted by volume expansion of gas generated from the foreign substance 21 causes melted metal to be partially sputtered, thereby increasing the amount of sputtering. Accordingly, as illustrated in
a)-3(d) are cross-sectional views schematically illustrating a process of laser-welding the lead 11 to the sealing plate 10 with a gap created between the lead 11 and the sealing plate 10.
In this case, as illustrated in
a)-4(d) are cross-sectional views schematically illustrating a process of laser-welding the lead 11 to the sealing plate 10 with a shift of an application position of a laser beam, i.e., in a situation where an end of the lead 11 is irradiated with the laser beam 12.
In this case, as illustrated in
Problems as described above inevitably arise during laser welding between the lead 11 and the sealing plate 10 because of variations in external factors in fabrication processes. Therefore, laser welding which does not cause sputtering even with such a variation in external factors, is required.
Since the thickness of the lead 11 is much thinner (typically about 0.2 mm) than that of the sealing plate 10, conventional laser welding employs welding of a heat conduction type so as not to form a recess in a welded portion of the lead 11 as described above. However, this type of welding increases the melted area, resulting in difficulty in reducing sputtering due to variations in external factors.
In view of this fact, the inventors of the present invention thought that deep penetration welding (i.e., keyhole welding), instead of the heat conduction type welding, would reduce a melted area, and thereby, laser welding with reduced sputtering would be achieved even with a variation in external factors.
At this time, surface energy E (X) of the keyhole 102 is generally expressed by the following Equation (1):
E(X)=πG[hX+½(D2−X2)] Equation (1)
where G is the surface energy of liquid metal of the plate member 100, and D is the diameter of the melted region 103 (see, for example, Isamu Miyamoto; “High speed precision welding of thin metal foil by single-mode fiber laser”; the 58th Laser Processing Conference of Japan Laser Processing Society; March, 2003).
From Equation (1), Equation (2) is obtained as follows:
dE/dX=πG(h−X) Equation (2)
According to Equation (2), if X>h, the relationship of dE/dX<0 is established.
In this case, an increase in the diameter X (dX) of the keyhole 102 reduces the surface energy E (dE), resulting in that the diameter X of the keyhole 102 increases. On the other hand, if X<h, the relationship of dE/dX>0 is established. In this case, an increase in the diameter X (dX) of the keyhole 102 increases the surface energy E (dE), resulting in that the diameter X of the keyhole 102 decreases, and the surface tension Ps is balanced with the evaporation repulsive force Pa.
Accordingly, the use of a laser beam 101 having a spot diameter smaller than the thickness h of the plate member 100 enables stable keyhole welding.
As described above, since the lead 11 typically has a thickness of about 0.2 mm, a YAG laser used in conventional laser welding has a spot diameter of at least about 0.3 mm. Thus, stable keyhole welding cannot be performed with such a YAG laser.
Although an increase in the thickness of the lead 11 in an amount corresponding to the thickness of a welded portion of the lead 11 enables keyhole welding to be performed, the volumetric efficiency decreases according to the amount of increase in the thickness of the lead 11, and an increase in the battery capacity is inhibited. Thus, it is difficult to actually employ this technique. In addition, power of a laser beam needs to be increased according to the increase in the thickness of the lead 11, thereby promoting occurrence of sputtering.
In view of these facts, the inventors of the present invention have focused on fiber laser. Specifically, the spot diameter of the fiber laser can be greatly reduced to about 0.02 mm, which is sufficiently smaller than (typically about ⅕ to about 1/10 of) the thickness of the lead 11, thereby achieving stable keyhole welding. Accordingly, deep penetration welding can be performed, thereby obtaining a small melted area between the lead and the sealing plate. Consequently, even with a variation in external factors in fabrication processes, it is possible to perform laser welding, while reducing sputtering.
Since the spot diameter of the fiber laser is about 1/10 of that of a YAG laser, the joint strength might decrease as the melted area decreases. However, if a linear melted portion is formed by continuous scanning with a continuously oscillating fiber laser, a joint strength almost equal to or greater than that obtained with a YAG laser can be maintained.
Embodiments of the present invention will be described hereinafter with reference to the drawings. It should be noted that the present invention is not limited to the following embodiments. Various changes and modifications may be made without departing from the scope of the present invention. The following embodiments may be combined as necessary.
a)-6(d) are cross-sectional views schematically illustrating a process of laser-welding a lead 11 to a sealing plate 10 according to a first embodiment of the present invention.
As illustrated in
As illustrated in
At this time, the welded portion 15 formed by parts of the lead 11 and the sealing plate 10 has a structure of deep penetration welding. The shape of the welded portion 15 is not specifically limited, but the penetration depth of the welded portion 15 formed by parts of the lead 11 and the sealing plate 10 is preferably larger than the bead diameter in the welded portion 15. The shape of this welded portion 15 is controlled by adjusting the spot diameter, the power density, and the application time of the laser beam 12, for example. The spot diameter of the laser beam 12 needs to be smaller than the thickness of the lead 11 in order to perform keyhole welding, and is preferably less than or equal to ½, and more preferably less than or equal to ⅕, of the thickness of the lead 11 in order to perform more stable keyhole welding.
a)-7(c) are views showing an example in which laser welding between the lead 11 and the sealing plate 10 of the present invention is applied to a lithium ion battery. Specifically,
Here, the lead 11 extending from the positive electrode in the electrode group of the lithium ion battery was made of aluminium foil having a thickness of 0.15 mm and a width of 4 mm. The sealing plate 10 was made of an aluminium plate having a thickness of 0.1 mm (in a portion welded to the lead 11) and a diameter of 16.8 mm. The laser beam having a spot diameter of 0.02 mm and a power density of 7×107 W/cm2 was employed, and was continuously applied at a scanning speed of 5 m/min.
As shown in
No sputtering was observed during the laser welding, and the joint strength was about 30 N. This result shows that even with a variation in external factors in fabrication processes, laser welding with reduced sputtering is enabled, and that continuous scanning with a laser beam to form the linear welded portion 15 maintains a joint strength almost equal to or greater than the joint strength obtained with a YAG laser. The linear shape of the welded portion 15 formed by parts of the lead 11 and the sealing plate 10 can maintain a stable joint strength even with an application of shock from various directions to the welded portion 15.
As shown in
This configuration can reduce sputtering during laser welding, while maintaining the joint strength between the lead 11 and the sealing plate 10, even with a variation in external factors in fabrication processes in welding between the lead 11 and the sealing plate 10. Accordingly, a stable, reliable sealed secondary battery can be obtained.
The sealed secondary battery of this embodiment can be fabricated in the following manner.
First, an electrode group 4 formed by stacking a positive electrode plate 1 and a negative electrode plate 2 with a separator 3 interposed therebetween, is prepared, and an end of the lead 11 is connected to one of the positive and negative electrode plates in the electrode group 4. Thereafter, the electrode group 4 is housed in a battery case 5, the other end of the lead 11 is brought into contact with the sealing plate 10, and then the surface of the lead 11 is continuously scanned with a laser beam, thereby laser-welding the other end of the lead 11 (i.e., the end of the lead 11 which is in contact with the sealing plate 10) to the sealing plate 10. Then, an opening of the battery case 5 is sealed with the sealing plate 10 by crimping, with a gasket 6 sandwiched therebetween, thereby completing fabrication of a sealed secondary battery.
The spot diameter of a fiber laser is about 1/10 of that of a YAG laser. Thus, the joint strength might decrease as the welding area decreases. Accordingly, a large number of welded portions are necessary for ensuring a sufficient joint strength. However, laser welding of a plurality of portions with a laser beam producing pulse oscillation causes repetitive state changes among heating, melting, and solidification, resulting in that sputtering readily occurs. In addition, some welded portions might be unstable, and as a result, a stable joint strength might not be obtained.
In view of these problems, in order to obtain a stable joint structure without occurrence of sputtering, a technique for forming a linear melted portion by performing continuous scanning with a continuously oscillating fiber laser is proposed in this embodiment. With this technique, a joint structure having a joint strength almost equal to or greater than the joint strength obtained with a YAG laser can be obtained. In addition, the linear shape of the welded portion formed by parts of the lead and the sealing plate can maintain a stable joint strength even with an application of shock from various directions to the welded portion.
For example, when a lead 11 made of aluminium foil having a thickness of 0.15 mm and a width of 4 mm was laser-welded to a sealing plate 10 made of an aluminium plate having a thickness of 0.1 mm (in a portion welded to the lead 11) and a diameter of 16.8 mm by applying a laser beam having a spot diameter of 0.02 mm and a power density of 7×107 W/cm2 at a scanning speed of 10 m/min. for 18 msec., the resultant welded portion 15 had a welding length L of about 2 mm and a welding width W of 0.3 mm. At this time, the joint strength was about 28 N, which is almost equal to or greater than the joint strength with a YAG laser. During the laser welding, no sputtering was observed.
In this embodiment, the linear shape of the welded portion 15 is not specifically limited. However, to increase the joint strength between the lead 11 and the sealing plate 10 or to reduce the contact resistance between the lead 11 and the sealing plate 10, the welded portion 15 preferably has linear shapes as illustrated in
a) illustrates an example in which the welded portion 15 is made of at least two separate lines. In this example, the total length of the welded portion 15 is increased, thereby increasing the joint strength between the lead 11 and the sealing plate 10. In the example illustrated in
b) and 12(c) illustrate examples in which the welded portion 15 forms a continuous closed line and a continuous closed curve, respectively. Specifically,
The “linear shape” herein includes a zigzag pattern as illustrated in
If the welded portion 15 is in the shape of a closed line or a closed curve as illustrated in
a)-14(d) are views illustrating processes after laser-welding the lead 11 extending from one of the electrode plates in the electrode group 4 to the sealing plate 10, and before sealing the opening of the battery case 5 with the sealing plate 10.
First, as illustrated in
Next, as illustrated in
To prevent this problem, the welded portion 15 is formed to have a linear portion A which is perpendicular to the longitudinal direction of the lead 11, as illustrated in
Further, in sealing the opening of the battery case 5 with the sealing plate 10 while bending the lead 11, the lead 11 might be peeled off in the longitudinal direction of the lead 11. To prevent peeling, the welded portion 15 is formed to have another linear portion which is parallel to the longitudinal direction of the lead 11, as illustrated in
Specifically, in the process of sealing the opening of the battery case 5 with the sealing plate 10 while bending the lead 11, in order to solve the problem of contact between part of the lead 11 and the battery case 5 and the problem of peeling-off of the lead, the welded portion 15 is preferably rectangular, as illustrated in
The inventors of the present invention conducted keyhole joining between a lead 11 and a sealing plate 10 with a method according to the present invention, and studied the resultant joint structure, to find out the following phenomena.
As illustrated in
a)-15(d) show the results of the above-described process. Specifically,
As illustrated in
This phenomenon seems to be because of the following reasons. In application of a laser beam 12 with constant power, the amount of heat input per a unit area was large until the scanning speed reaches a predetermined value. In addition, a rapid temperature rise in an irradiated portion of the lead 11 increased the penetration depth. When the scanning was stopped, the amount of heat input per a unit area increased as the scanning speed decreased, thereby forming the recess 16.
In a laser welding process providing such a joint structure, the melt state of the lead 11 (and the sealing plate 10) is unstable, and thus melted metal might be partially sputtered. In addition, when a positional shift occurs in adjusting the scanning path of the laser beam 12 to cause the scanning start/end point to reach a region where the lead 11 does not exist, the laser beam 12 is applied directly to the surface of the sealing plate 10, resulting in that the sealing plate 10 might be perforated.
In this embodiment, in order to reduce formation of such an unstable joint structure, a technique for achieving stable through-hole welding by reducing the influence of sputtering during laser welding between the lead and the sealing plate, is proposed.
a)-16(d) schematically illustrate a process of laser-welding the lead 11 to the sealing plate 10 according to this embodiment. Specifically,
In a manner similar to the method shown in
At this time, as shown in
d) is a micrograph showing a plan view of the welded portion 15 obtained by bringing an end of the lead 11 made of aluminium foil with a thickness of 0.15 mm and a width of 4 mm into contact with the sealing plate 10 made of an aluminium plate with a thickness of 0.1 mm (in a portion welded to the lead 11) and a diameter of 16.8 mm, and irradiating the lead 11 with a laser beam having a spot diameter of 0.02 mm and a power density of 7×107 W/cm2, while scanning the lead 11 at a scanning speed of 10 m/min so as to laser-welding the lead 11 to the sealing plate 10. The laser irradiation was performed for 18 msec. in such a manner that the power density of the laser beam 12 was increased for 3 msec. after the start of the scanning, and is reduced for 3 msec. before the stop of the scanning. During this irradiation, no sputtering was observed.
The laser irradiation is preferably performed with the power of the laser beam 12 kept constant in an interval after a lapse of a period after the start of the scanning and before a period before the stop of the scanning (i.e., time t1 to time t2). Alternatively, the power of the laser beam 12 may be changed within a range in which the melting state does not rapidly change as long as a sufficient joint strength is ensured.
The laser irradiation of this embodiment may employ fiber laser scanning illustrated in
It should be recognized that the foregoing embodiments are only preferred examples of the present invention, and should not be taken as limiting the scope of the present invention, and various changes and modifications may be made. For example, in the above embodiments, the lead 11 and the sealing plate 10 are made of the same aluminium material. Alternatively, the lead 11 and the sealing plate 10 may be made of different types of metal. To seal the opening of the battery case 5, the sealing plate 10 to which the lead 11 is welded is not necessarily crimped onto the opening of the battery case 5, and may be welded to the opening of the battery case 5.
In the above embodiments, after the electrode group 4 from which the lead 11 extends has been housed in the battery case 5, the lead 11 is laser-welded to the sealing plate 10. Alternatively, the lead 11 may be laser-welded to the sealing plate 10 before the electrode group 4 in which the lead 11 is welded to the sealing plate 10 is housed in the battery case 5. In this case, after housing the electrode group 4 in the battery case 5, the opening of the battery case 5 is sealed with the sealing plate 10.
The type of a sealed secondary battery according to the present invention is not specifically limited, and the present invention is also applicable not only to lithium-ion secondary batteries, but also to nickel-metal hydride storage batteries. Further, the present invention is applicable not only to cylindrical secondary batteries, but also to rectangular secondary batteries. The electrode group is not necessary formed by winding a positive electrode plate and a negative electrode plate with a separator interposed therebetween, and may be formed by stacking a positive electrode plate, a negative electrode plate, and a separator.
The present invention can provide a stable, reliable sealed secondary battery, and is useful for power sources for driving, for example, mobile equipment.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2008-205418 | Aug 2008 | JP | national |
| 2008-209836 | Aug 2008 | JP | national |
| 2008-209838 | Aug 2008 | JP | national |
| 2008-275166 | Oct 2008 | JP | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/JP2009/002854 | 6/23/2009 | WO | 00 | 4/26/2010 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2010/016182 | 2/11/2010 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 20020017513 | Nagura et al. | Feb 2002 | A1 |
| 20030134193 | Hanafusa et al. | Jul 2003 | A1 |
| 20090136835 | Nakai et al. | May 2009 | A1 |
| 20100247992 | Miyata et al. | Sep 2010 | A1 |
| Number | Date | Country |
|---|---|---|
| 10-249561 | Sep 1998 | JP |
| 2000-210784 | Aug 2000 | JP |
| 2000-299099 | Oct 2000 | JP |
| 2003-109576 | Apr 2003 | JP |
| 2004-288656 | Oct 2004 | JP |
| 2005-005215 | Jan 2005 | JP |
| 2005-038866 | Feb 2005 | JP |
| 2007-234276 | Sep 2007 | JP |
| Number | Date | Country | |
|---|---|---|---|
| 20100247992 A1 | Sep 2010 | US |
