Patent Application
20110133881
The present invention relates to a laminated inductor, and more particularly to a laminated power choke coil used in DC/DC converters.
Superimposition characteristics are important product characteristics for power choke coils used in DC/DC converters and other power supply circuit components.
Laminated power choke coils (laminated choke coils) adopt the method to form a nonmagnetic layer in a location where magnetic fluxes are concentrated, by means of simultaneous sintering with a magnetic layer, to suppress magnetic saturation and thereby improve superimposition characteristics.
Patent Literatures 1 and 2 describe examples of the above method, where a nonmagnetic layer is made of, for example, Zn—Cu ferrite whose component elements are close to Ni—Zn—Cu ferrite that constitutes a magnetic layer.
In Patent Literature 3, use as a nonmagnetic layer of a ceramic material selected from ZnFe2O4, TiO2, WO2, Ta2O5, cordierite ceramics, BaSnN ceramics and CaMgSiAlB ceramics is described.
However, Patent Literature 3 does not mention using Ni—Zn—Cu ferrite as a magnetic layer, and ZnFe2O4 (zinc ferrite) is the only specific example of a nonmagnetic layer given and there is no mention of TiO2 in particular. On the other hand, Patent Literature 4 describes “a dielectric ceramic composition produced by blending TiO2 with 0.1 to 10 percent by weight of ZrO2, 1.5 to 6.0 percent by weight of CuO, 0.2 to 20 percent by weight of Mn3O4, and 2.0 to 15 percent by weight of NiO, to a total percentage by weight of 100,” while Patent Literature 5 describes “a dielectric ceramic composition characterized in that it is constituted by CuO (1.0 to 5.0 percent by weight), Mn3O4 (0.2 to 10 percent by weight), NiO (0.5 to 14 percent by weight), Ag2O (0.1 to 10 percent by weight), and TiO2 making up the remainder.” However, each only indicates that such a composition can be used as a material for capacitors used in combined inductor/capacitor components, and its use for nonmagnetic layers in laminated inductors is not indicated.
As described in Patent Literatures 1 and 2, however, use of a nonmagnetic layer made of Zn—Cu ferrite results in the Zn component of Zn—Cu ferrite diffusing to Ni—Zn—Cu ferrite in the simultaneous sintering process, and the Ni component of Ni—Zn—Cu ferrite diffusing to Zn—Cu ferrite, thereby causing a formation of Ni—Zn—Cu ferrite whose Ni concentration has a slope. These diffusion layers are constituted by Ni—Zn—Cu ferrite whose Curie point differs along the Ni concentration slope, meaning that as the temperature rises, areas of low Ni concentrations change from magnetic to nonmagnetic. This has been a problem because the apparent nonmagnetic layer thickness changes with the temperature, resulting in poor temperature characteristics of the product.
Also, a laminated choke coil has a conductive layer formation region where conductive layers constituting a coil are laminated alternately with magnetic material layers with at least one nonmagnetic layer inserted therebetween, and a yoke region constituted by magnetic material layers that are positioned at the top and bottom in the direction of lamination and serve as a yoke to connect the magnetic fluxes formed on the inner side of the coil and magnetic fluxes formed on the outer side of the coil. Accordingly when a laminated choke coil is sintered, sintering progresses as the sintering of the metal constituting the coil-constituting conductive layers interacts with the sintering of the magnetic material constituting the magnetic material layers, in the conductive layer formation region constituting the coil. In the yoke region, on the other hand, sintering progresses mainly in the magnetic material, and accordingly latent stress tends to generate between the two regions. Therefore, the nonmagnetic layers which are located in the conductive layer formation region constituting the coil and which have low affinity with magnetic material layers and coil conductive layers become thresholds of latent stress relief, and for this reason delamination occurs easily between the nonmagnetic layers and the adjacent magnetic material layers or coil-constituting conductive layers.
In addition to Zn—Cu ferrite, glass materials are generally known as nonmagnetic materials. Since their coefficients of linear expansion are different from those of ferrites, simultaneous sintering of ferrite and glass materials will cause delamination at the bonded interface.
Also a TiO2 material sintered at low temperature is applied as a nonmagnetic material that can be simultaneously sintered with magnetic layers. However, this specification does not allow a sufficient inter-diffusion interface to form and sometimes separation occurs at the interfacial layer.
The present invention was invented in light of the aforementioned situation and it is the object of the present invention to provide a laminated inductor that offers favorable DC superimposition characteristics, is free from variation in temperature characteristics, suppresses occurrence of delamination, and can be produced in a stable manner, and a method of manufacturing the same, as well as a laminated choke coil.
The present invention adopts the following means to solve the aforementioned problems:
(1) A laminated inductor used as a choke coil in power supply circuits, comprising: a rectangular parallelepiped-shaped laminated chip having a plurality of magnetic material layers constituted by Ni—Zn—Cu ferrite, a plurality of conductive layers that are laminated via the aforementioned magnetic material layers to constitute a coil, and at least one nonmagnetic layer constituted by Ti—Ni—Cu—Mn—Zr—Ag dielectric and formed in a manner contacting a plurality of the aforementioned magnetic material layers; and at least one pair of external electrodes provided at ends of the aforementioned laminated chip and electrically connected to ends of the aforementioned coil.
(2) A laminated inductor according to (1) above, wherein the aforementioned laminated chip has a bonded interface where the Ni—Zn—Cu ferrite of the aforementioned magnetic material layer and Ti—Ni—Cu—Mn—Zr—Ag dielectric of the aforementioned nonmagnetic layer are inter-diffused.
(3) A laminated inductor according to (1) or (2) above, wherein the aforementioned nonmagnetic layer is constituted by a dielectric whose main component is TiO2 and which also contains NiO, CuO, Mn3O4, ZrO2 and Ag2O or Ag.
(4) A laminated inductor according to (3) above, wherein the aforementioned dielectric contains TiO2, 2.0 to 15 percent by weight of NiO, 1.5 to 6.0 percent by weight of CuO, 0.2 to 20 percent by weight of Mn3O4, 0.1 to 10 percent by weight of ZrO2, and 0.01 to 10 percent by weight of Ag2O, based on equivalent oxide, to a total percentage by weight of 100.
(5) A method of manufacturing a laminated inductor, comprising: a step to prepare ferrite powder paste containing Fe2O3, NiO, ZnO and CuO; a step to prepare dielectric powder paste whose main component is TiO2 and which also contains NiO, CuO, Mn3O4, ZrO2 and Ag2O or Ag; a step to form magnetic sheets by coating the aforementioned ferrite powder paste and print conductive paste patterns on these magnetic sheets, and then pressure-bond these layers to form a laminate in a manner allowing the conductive paste patterns of vertically adjacent magnetic sheets to be connected via through holes to form a helical coil, and also in a manner causing at least one nonmagnetic sheet formed by coating the aforementioned dielectric powder paste or nonmagnetic pattern formed by printing the aforementioned nonmagnetic powder paste to be inserted therebetween; and a step to sinter the aforementioned laminate to obtain a laminated chip.
(6) A method of manufacturing a laminated inductor, comprising: a step to prepare ferrite powder paste containing Fe2O3, NiO, ZnO and CuO; a step to prepare dielectric powder paste whose main component is TiO2 and which also contains NiO, CuO, Mn3O4, ZrO2 and Ag2O or Ag; a step to form magnetic sheets by coating the aforementioned ferrite powder paste and print conductive paste patterns on these magnetic sheets, and also print magnetic paste patterns using the aforementioned ferrite powder paste, alternately in such a way that at least one nonmagnetic pattern formed by printing the aforementioned dielectric powder paste is inserted therebetween, to obtain a laminate; and a step to sinter the aforementioned laminate to obtain a laminated chip.
(7) A method of manufacturing a laminated inductor according to (5) or (6) above, wherein the aforementioned step to sinter the aforementioned laminate to obtain a laminated chip is such that Ni—Zn—Cu ferrite constituting the aforementioned magnetic sheet or magnetic material layer formed by the magnetic paste pattern is inter-diffused with Ti—Ni—Cu—Mn—Zr—Ag dielectric constituting the aforementioned nonmagnetic sheet or nonmagnetic layer formed by the nonmagnetic pattern, to form a bonded interface.
(8) A method of manufacturing a laminated inductor according to (5) or (6) above, wherein the aforementioned dielectric powder is constituted by blending TiO2 with 2.0 to 15 percent by weight of NiO, 1.5 to 6.0 percent by weight of CuO, 0.2 to 20 percent by weight of Mn3O4, 0.1 to 10 percent by weight of ZrO2, and 0.01 to 10 percent by weight of Ag2O, to a total percentage by weight of 100.
(9) A laminated choke coil having a conductive layer formation region where conductive layers constituting a coil are laminated alternately with magnetic material layers with at least one nonmagnetic layer inserted therebetween, and a yoke region constituted by magnetic material layers that are positioned at the top and bottom in the direction of lamination and serve as a yoke to connect the magnetic fluxes formed on the inner side of the coil and magnetic fluxes formed on the outer side of the coil, wherein the aforementioned magnetic material layer is constituted by Ni—Zn—Cu ferrite and the aforementioned nonmagnetic layer, by Ti—Ni—Cu—Mn—Zr—Ag dielectric.
The present invention provides a laminated inductor that offers favorable DC superimposition characteristics, is free from variation in temperature characteristics, suppresses occurrence of delamination, and can be produced in a stable manner, as well as a laminated choke coil.
The aforementioned object and other objects, structural characteristics, and operations and effects of the present invention are made clear by the following explanation and attached drawings.
A first embodiment of a laminated inductor conforming to the present invention is explained. As shown in
As shown in
Under the present invention, the laminated chip 1 has a plurality of magnetic material layers 3, 3 constituted by Ni—Zn—Cu ferrite, and a nonmagnetic layer 4 constituted by Ti—Ni—Cu—Mn—Zr—Ag dielectric. The aforementioned Ni—Zn—Cu ferrite is a ferrite that contains Fe2O3, NiO, ZnO and CuO. The nonmagnetic layer 4 constituted by the aforementioned Ti—Ni—Cu—Mn—Zr—Ag dielectric is a dielectric whose main component is TiO2 and which also contains NiO, CuO, Mn3O4, ZrO2 and Ag2O (Ag may be used instead of Ag2O), desirably formed by blending TiO2 with 2.0 to 15 percent by weight of NiO, 1.5 to 6.0 percent by weight of CuO, 0.2 to 20 percent by weight of Mn3O4, 0.1 to 10 percent by weight of ZrO2, and 0.01 to 10 percent by weight of Ag2O, to a total percentage by weight of 100.
By adding CuO and Mn3O4 as auxiliaries to the nonmagnetic layer 4, a liquid phase of Cu—Mn—Ti—O is produced during sintering by the reaction of these auxiliaries with a part of TiO2, and this liquid phase makes TiO2 finer at low temperature and thereby promotes rapid grain size growth. On the other hand, ZrO2 has a higher melting point than TiO2, CuO and Mn3O4, so adding Zr to the aforementioned liquid phase of Cu—Mn—Ti—O increases the melting point and viscosity of the liquid phase. As a result, the speed at which TiO2 grains grow due to sintering of the liquid phase is adjusted and a low-temperature sintered TiO2 material can be obtained which is subject to less oxygen deficiency.
Under the present invention, Ag2O (or Ag) is added further to the aforementioned low-temperature sintered TiO2 material to constitute the nonmagnetic layer 4 in order to promote the inter-diffusion of material components at the interface and thereby improve the interfacial strength. In other words, the Ni—Zn—Cu ferrite constituting the magnetic material layer 3 and Ti—Ni—Cu—Mn—Zr—Ag dielectric constituting the nonmagnetic layer 4 are inter-diffused as a result of simultaneously sintering to form a bonded interface. As shown in
Also by adding Ag2O (or Ag) further to the aforementioned low-temperature sintered TiO2 material to constitute the nonmagnetic layer 4, Ag separates from the material and precipitates in the nonmagnetic layer 4 as a metal component, as shown in
The main component TiO2 should preferably account for at least 50 percent by weight, but more preferably 70 to 98 percent by weight.
The content of Ag2O should preferably be in a range of 0.01 to 10 percent by weight because if the content is less than 0.01 percent by weight, delamination and a drop in inductance cannot be suppressed effectively, while a content exceeding 10 percent by weight causes the effects of preventing delamination/drop in inductance to saturate and a network structure where Ag grains are inter-connected is formed to cause the characteristics of the insulator to drop suddenly.
Provided above each magnetic material layer 3 is a C-shaped conductive layer 2 made of Ag or other metal material to constitute a coil. Also in each magnetic material layer 3, through holes 5, 5 are formed in such a way as to overlap with the ends of conductive layers 2, 2 constituting the coil, in order to connect the upper and lower conductive layers 2, 2 through the corresponding magnetic material layers 3, 3. Here, the through holes 5, 5 are holes pre-formed in the magnetic material layer which are filled with the same material as the conductive layer constituting the hole.
The magnetic material layers at the top and bottom provide yoke regions 7, 7, serving as yokes to connect the magnetic fluxes formed on the inner side of the coil and magnetic fluxes formed on the outer side of the coil, while also ensuring sufficient margins at the top and bottom, and therefore these magnetic material layers have no conductive layers constituting the coil or through holes.
Provided above the nonmagnetic layer 4 is a C-shaped conductive layer 2 made of Ag or other metal material to constitute a coil. Also in the nonmagnetic layer 4, a through hole 5 is formed in such a way as to overlap with the ends of conductive layers 2, 2 constituting the coil, in order to connect the upper and lower conductive layers 2, 2 through the nonmagnetic layer 4.
The conductive layers 2, 2, . . . constituting the coil are connected via through holes 5, 5, . . . to constitute a helical coil. The top conductive layer 2 and bottom conductive layer 2 of the coil have drawer parts 6, 6, respectively, where one of these drawer parts 6, 6 is connected to one of the external electrodes 8, 8, while the another of the drawer parts 6, 6 is connected to the another of the external electrodes 8, 8.
Next, a first embodiment of a method of manufacturing laminated inductor conforming to the present invention is explained.
First, when manufacturing a laminated inductor, a magnetic sheet (ferrite sheet) is produced to constitute a Ni—Zn—Cu ferrite magnetic material layer 3 of high magnetic permeability. To be specific, fine ferrite powder is produced by pre-baking and crushing a material mixture mainly constituted by Fe2O3, NiO, CuO and ZnO, and then ethanol or other solvent and PVA or other binder are added and mixed to obtain ferrite powder paste, after which this ferrite powder paste is coated flat on a film of PET, etc., using the doctor blade or other method, to obtain a magnetic sheet (ferrite sheet).
Also, a nonmagnetic sheet (dielectric sheet) or nonmagnetic pattern is produced to constitute a Ti—Ni—Cu—Mn—Zr—Ag dielectric nonmagnetic layer (4). To be specific, dielectric powder whose main component is TiO2 and which also contains NiO, CuO, Mn3O4, ZrO2 and Ag2O (or Ag) is mixed with a solvent and binder to obtain dielectric powder paste, in the same manner as above, and this dielectric powder paste is coated flat on a film of PET, etc., using the doctor blade, slurry build or other method to obtain a nonmagnetic sheet (dielectric sheet) or nonmagnetic pattern by printing the paste in a pattern.
Next, holes to form through holes 5 are stamped using dies, pierced by laser cutting, or otherwise formed in the magnetic sheet and nonmagnetic sheet according to a specified layout. Then, conductive paste for forming a conductive layer 2 constituting a coil is printed, according to a specified pattern, on the magnetic sheet and nonmagnetic sheet on which holes to form through holes have been formed, by means of screen printing, etc. For this conductive paste, metal paste whose main component is Ag can be used, for example.
Next, the magnetic and nonmagnetic sheets on which conductive paste has been printed are pressure-bonded in such a way that the conductive paste patterns 2 of the upper and lower sheets are connected via through holes 5 to constitute a helical coil, to obtain a laminate. Here, the magnetic sheet 3 and nonmagnetic sheet 4 are laminated in the order shown in
Next, this laminate is cut to unit dimensions to obtain a chip-shaped laminate. This chip-shaped laminate is then heated to approx. 400 to 500° C. for 1 to 3 hours in air to remove the binder component, and then the obtained chip-shaped laminate free from binder component is sintered at 850 to 920° C. for 1 to 3 hours in air.
To form external electrodes, conductive paste is applied at both ends of the sintered laminated chip by the dip method, etc. For this conductive paste, metal paste whose main component is Ag can be used, for example, as above. The laminated chip on which conductive paste has been applied is sintered at approx. 500 to 800° C. for 0.2 to 2 hours in air to form external electrodes. Finally, each external electrode is plated with Ni, Sn, etc., to obtain a laminated inductor 10.
Next, a second embodiment of a method of manufacturing laminated inductor conforming to the present invention is explained. (No illustration is provided.)
First, when manufacturing a laminated inductor, a magnetic sheet (ferrite sheet) is produced to constitute a Ni—Zn—Cu ferrite magnetic material layer of high magnetic permeability. To be specific, fine ferrite powder is produced by pre-baking and crushing a material mixture mainly constituted by Fe2O3, NiO, CuO and ZnO, and then ethanol or other solvent and PVA or other binder are added and mixed to obtain ferrite powder paste, after which this ferrite powder paste is coated flat on a film of PET, etc., using the doctor blade or other method, to obtain a magnetic sheet (ferrite sheet).
Next, conductive paste for forming a conductive layer to constitute a coil is printed in a certain pattern on the aforementioned magnetic sheet by means of screen printing, etc. For this conductive paste, metal paste whose main component is Ag can be used, for example.
Then, a magnetic pattern (ferrite pattern) is produced to constitute a Ni—Zn—Cu ferrite magnetic material layer of high magnetic permeability. To be specific, fine ferrite powder is produced by pre-baking and crushing a material mixture mainly constituted by Fe2O3, NiO, CuO and ZnO, and then ethanol or other solvent and PVA or other binder are added and mixed to obtain magnetic paste (ferrite powder paste), after which this ferrite powder paste is printed on the conductive pattern formed above in a manner keeping one end of the pattern to remain exposed, to obtain a magnetic pattern (ferrite pattern).
In the same manner as explained above, conductive paste for forming a conductive layer to constitute a coil is printed in a certain pattern on the aforementioned magnetic pattern by means of screen printing, etc., so as to connect to one end of the aforementioned conductive paste pattern previously formed.
In the same manner as explained above, the magnetic pattern and conductive paste pattern are printed alternately by means of screen printing, etc.
Next, a nonmagnetic pattern (dielectric pattern) is produced to constitute a Ti—Ni—Cu—Mn—Zr—Ag dielectric nonmagnetic layer. To be specific, dielectric powder whose main component is TiO2 and which also contains NiO, CuO, Mn3O4, ZrO2 and Ag2O (or Ag) is mixed with a solvent and binder to obtain dielectric powder paste, in the same manner as above, and this dielectric powder paste is printed on the laminate obtained above, to obtain a nonmagnetic pattern.
In the same manner as explained above, the magnetic pattern and conductive paste pattern are printed alternately by means of screen printing, etc.
Next, the obtained laminate is cut to unit dimensions to obtain a chip-shaped laminate. This laminate is then heated to approx. 400 to 500° C. for 1 to 3 hours in air to remove the binder component, and then the obtained chip-shaped laminate free from binder component is sintered at 850 to 920° C. for 1 to 3 hours in air.
To form external electrodes, conductive paste is applied at both ends of the sintered laminated chip by the dip method, etc. For this conductive paste, metal paste whose main component is Ag can be used, for example, as above. The laminated chip on which conductive paste has been applied is sintered at approx. 500 to 800° C. for 0.2 to 2 hours in air to form external electrodes. Finally, each external electrode is plated with Ni, Sn, etc., to obtain a laminated inductor.
When manufacturing a laminated choke coil, coil conductors and Ni—Zn—Cu ferrite magnetic material layers are laminated alternately with at least one nonmagnetic layer constituted by Ti—Ni—Cu—Mn—Zr—Ag dielectric inserted therebetween, to form a conductive layer formation region for constituting a coil, after which yoke regions 7, 7 constituted by a magnetic material layer are provided at the top and bottom in the direction of lamination in such way as to connect the magnetic fluxes formed on the inner side of the coil and magnetic fluxes formed on the outer side of the coil, and then the whole assembly is sintered under conditions similar to those explained above. In the sintering process, sintering progresses as the sintering of the metal constituting the coil-constituting conductive layers interacts with the sintering of the magnetic material constituting the magnetic material layers, in the conductive layer formation region constituting the coil. In the yoke regions 7, 7, on the other hand, sintering progresses mainly in the magnetic material, and accordingly latent stress tends to generate between the two regions. Under the present invention, however, the nonmagnetic layer is constituted by a low-temperature sintered TiO2 material to which Ag has been added (dielectric powder whose main component is TiO2 and which also contains NiO, CuO, Mn3O4, ZrO2 and Ag2O), and this reduces the stress generating in the magnetic material layer and nonmagnetic layer to prevent delamination.
The present invention is explained in greater detail below using an example.
Ethanol (solvent) and PVA binder were added to and mixed with Ni—Zn—Cu ferrite powder of the composition shown in Table 1 to prepare ferrite powder paste, and this paste was applied on a PET film to obtain a magnetic sheet (magnetic material layer) 3. Solvent and binder were also added to and mixed with powder of a dielectric (low-temperature sintered TiO2 material to which Ag has been added) whose main component is TiO2 and which also contains NiO, CuO, Mn3O4, ZrO2 and Ag2O, as shown in Table 1, to prepare dielectric powder paste in the same manner, and this paste was applied on a PET film to obtain a nonmagnetic sheet (nonmagnetic layer) 4.
On each green sheet obtained, conductive paste pattern (a C-shaped conductive layer constituting a coil) 2 was printed and then the sheets were laminated to produce a laminate, after which the obtained laminate was cut to unit dimensions to obtain a chip-shaped laminate. The obtained chip-shaped laminate was heated to 500° C. for 1 hour to remove the binder component, followed by 1 hour of sintering at 900° C. Ag external electrodes 8, 8 were attached on both ends of the laminated chip 1 obtained above, whose structure is shown in the exploded perspective view in
Ethanol (solvent) and PVA binder were added to and mixed with Ni—Zn—Cu ferrite powder of the composition shown in Table 1 and the obtained paste was applied on a PET film to obtain a magnetic sheet (magnetic material layer). Solvent and binder were also added to and mixed with powder of a dielectric (low-temperature sintered TiO2 material to which Ag has not been added) whose main component is TiO2 and which also contains NiO, CuO, Mn3O4 and ZrO2, as shown in Table 1, to prepare dielectric powder paste in the same manner, and this paste was applied on a PET film to obtain a nonmagnetic sheet (nonmagnetic layer).
On each green sheet obtained, conductive paste pattern (a C-shaped conductive layer constituting a coil) was printed and then the sheets were laminated to produce a laminate, after which the obtained laminate was cut to unit dimensions to obtain a chip-shaped laminate. The obtained chip-shaped laminate was heated to 500° C. for 1 hour to remove the binder component, followed by 1 hour of sintering at 900° C. Ag external electrodes 8, 8 were attached on both ends of the laminated chip obtained above, and then Ni/Sn plating was performed to obtain a laminated inductor of the comparative example.
(Interface Formation)
(Material Composition)
(Inductance)
Table 2 shows the inductances of obtained laminated inductors. Table 2 indicates that the inductance increases as more Ag is added to the low-temperature sintered TiO2 material constituting the nonmagnetic layer.
(Temperature Characteristics)
Inductance changes due to temperature characteristics were measured on the obtained laminated inductors. The results are shown in
(Delamination)
All 100 laminated inductors obtained were ground to their center and the interface of Ni—Zn—Cu ferrite and low-temperature sintered TiO2 material was observed with a SEM to check for delamination. For the purpose of comparison, laminated inductors using TiO2 for the nonmagnetic layer were also checked for delamination in the same manner. The results are shown in Table 3. Laminated inductors using a low-temperature sintered TiO2 material for the nonmagnetic layer showed a markedly lower delamination ratio compared to laminated inductors using only TiO2 for the nonmagnetic layer. In particular, delamination was not found in Ag-added laminated inductors obtained by the example of the present invention.
(Elution Amounts)
Table 4 shows a composition for promoting inter-diffusion. This composition shown in Table 4 was used for the nonmagnetic layer to produce a chip-shaped laminate according to the aforementioned example, after which the laminate was sintered at 900° C. for 1 hour to obtain a 3-mm square sample (veneer) showing similar formation of an inter-diffusion layer. This veneer was soaked in plating solution used in mass production, to measure the elution amounts of material components. A sample that used for the nonmagnetic layer a low-temperature sintered TiO2 material to which Ag had been added presented no elution of its material components because the chemical resistance of the material did not drop.
As shown above, laminated conductors conforming to the present invention were confirmed to offer favorable DC superimposition characteristics, be free from variation in temperature characteristics, and suppress occurrence of delamination.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2008-195575 | Jul 2008 | JP | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/JP2009/063901 | 7/30/2009 | WO | 00 | 1/25/2011 |
