This invention relates generally to thermal inkjet print heads. More particularly, the invention pertains to a thermal inkjet print head with resistance to organic solvents.
A known structure for interconnecting a thermal inkjet print head and its electrical components to a printing system controller is a tape automated bonded (TAB) interconnect circuit. TAB interconnect circuits used with thermal inkjet print heads are disclosed in U.S. Pat. Nos. 4,989,317; 4,944,850 and 5,748,209. A TAB circuit may be fabricated using a flexible polyimide substrate for supporting a metal conductor such as a gold plated copper. Known fabrication methods such as the “two layered process” or the “three layered process” may be used to create the components including device windows, contact pads and inner leads, for the TAB conductor circuit. In addition, a die-cut insulating film is applied to the conductor side of the TAB circuit to isolate the contact pads and traces from a cartridge housing on which the TAB circuit is affixed.
The print head is affixed to the TAB circuit in spaced relation to the contact pads, and the traces provide an electrical connection between the contact pads and the print head electrical components. When the TAB circuit, including the print head, is affixed to an inkjet cartridge, the print head portion of the TAB circuit is affixed to one side of the cartridge in fluid communication with an ink supply. That portion of the TAB having the contact pads is affixed to an adjacent side of the cartridge housing that is typically disposed perpendicular to the side of the cartridge housing to which the print head is attached. The contact pads are positioned on the cartridge housing for alignment with electrical leads on the printing system thereby electrically interconnecting the print head with a printing system controller to carry out print commands.
A typical thermal inkjet print head is essentially a silicon chip/substrate with thin-film structures such as an array of resistive heaters and corresponding transistors that switch the power pulses to the heaters. The print head may also include other components such as an identification circuit that provides coding information of print head characteristics and an electrostatic discharge component or electronic logics for multiplexing the firing of the heaters. After forming the film structures and circuits on the chip, an ink barrier layer is formed over the thin-film structures and etched or is otherwise treated to create a plurality of ink flow channels and ink chambers. Known ink flow channel and ink chamber architectures are disclosed in U.S. Pat. Nos. 4,794,410 and 4,882,595. In addition, an ink slot is formed by cutting a slot through a middle portion of the print head using known cutting techniques such as sand-blasting. This slot completes an ink flow network and places the print head in fluid communication with an ink supply.
A nozzle plate having a plurality of orifices is bonded to the ink barrier layer whereby each orifice is aligned with a corresponding ink chamber; and, for each ink chamber there is an associated heater and transistor. When power pulses are transmitted in accordance with print commands to the print head, the resistive heaters heat the ink in the ink chamber to create one or more pressure bubbles in the chamber that forces ink to eject in droplet form through respective orifices onto a print medium.
The resistive heaters and corresponding orifices in the nozzle plates have been arranged in at least two columns or rows depending on the orientation of the print head. The heaters and nozzles in a single row are offset relative to one another, and each of the columns is vertically or horizontally offset relative to one another. This type of arrangement of heaters and nozzles is used to minimize cross-talk between the heaters in a column, which may cause misfiring of ink drops. Multiplex drive circuits have been provided to control firing timing so that adjacent heaters in a column are not simultaneously fired to minimize cross-talking between fired heaters. Multiplexing may also reduce the number of signal lines in a circuit and the area required to complete the circuits, which area becomes a premium due to the crowding from other electrical components on a flex circuit.
Embodiments of an inkjet printing system comprise a print head in fluid communication with an ink reservoir. The print head includes a plurality of nozzles and a plurality of associated ink ejection chambers, each of the chambers being associated with a respective one of a plurality of transistor drivers controlling a corresponding heater. In response to print command signals the heater is activated and ejects ink drops from the chamber and through the nozzles onto a print medium. A controller in electrical communication with the print head generates the print command signals which identify the transistor drivers and heaters to be activated and a sequence for activating the transistor drivers and heaters relative to one another for completing a printing operation.
In an embodiment, an inkjet printing system includes a print head in fluid communication with an ink reservoir and having a plurality of orifices and a corresponding plurality of associated ejection chambers. The print head includes a substrate and a barrier layer disposed on the substrate. The barrier layer defines in part a plurality of fluid channels and the plurality of ejection chambers. The barrier layer includes a material selected from epoxy-based photo resist materials and methyl methacrylate-based photo resist materials. An orifice plate is disposed over the substrate. The orifice plate includes the plurality of orifices in fluid communication with the ejection chambers. The system includes a reservoir containing an organic solvent-based ink composition, wherein the ink composition includes an organic solvent selected from C1-C4 alcohols, C3-C6 ketones, C3-C6 esters, C4-C8 ethers, and mixtures thereof, in an amount 60% or more by weight of the ink composition.
In another embodiment, an inkjet printing system includes a print head in fluid communication with an ink reservoir and having a plurality of orifices and a corresponding plurality of associated ejection chambers. The print head includes a substrate and a barrier layer disposed on the substrate. The barrier layer defines in part a plurality of fluid channels and the plurality of ejection chambers. The barrier layer includes a material selected from epoxy-based photo resist materials and methyl methacrylate-based photo resist materials. An orifice plate is disposed over the substrate. The orifice plate includes the plurality of orifices in fluid communication with the ejection chambers. The orifice plate comprises a material selected from polyimides and nickel.
The print head may be affixed to an end of a tape automated bonded (TAB) flex circuit having an electrical interconnection thereon distal to the print head. In an embodiment, the TAB flex circuit is mounted on a snout of an inkjet print cartridge and the electrical interconnection is disposed at acute angle relative to the print head.
A more particular description of the invention briefly described above will be rendered by reference to specific embodiments thereof that are illustrated in the appended drawings. Understanding that these drawings depict only typical embodiments of the invention and are not therefore to be considered to be limiting of its scope, the invention will be described and explained with additional specificity and detail through the use of the accompanying drawings.
Reference will now be made in detail to the embodiments consistent with the invention, examples of which are illustrated in the accompanying drawings. Wherever possible, the same reference numerals are used throughout the drawings and refer to the same or like parts. While the invention is described below in reference to a thermal inkjet printer, the invention is not so limited and may be incorporated into other inkjet printing systems that utilize other technologies, such as piezo-transducers to eject ink. The term “nozzle” as used herein shall mean the orifices formed in a print head cover plate through which ink is ejected and/or shall also include such orifices and other components of the print head such as an ejection chamber from which the ink is ejected. In addition, the described system and method for an inkjet printing system is not limited to applications with a print head assembly mounted to a cartridge housing, which may or may not be a disposable cartridge. The present invention may be used with print heads permanently mounted in printing systems and an ink supply is provided as necessary for printing. So the term cartridge may include a permanently mounted print head only and/or the combination of the print head with the ink source.
The present disclosure relates to a thermal inkjet print head composed of materials that offer resistance to solvent-based inks. In particular, the print head components include materials and surface treatments that provide a print head assembly that does not significantly dissolve, delaminate, shrink, swell, or otherwise distort when exposed to strong solvents for months or years.
Prior thermal inkjet printing systems were designed to print aqueous inks. Even if such systems were capable of printing organic solvent based inks, because the components were not designed to handle organic solvents, the components would suffer from degradation, such as dissolving, delaminating, shrinking, swelling, or otherwise distorting. Additionally, because a particular printhead architecture is designed to fit a particular type of ink, when the structure of the printhead changes due to these effects, the printhead performance is no longer optimal.
The present system is preferably capable of containing an organic solvent-based ink for a period of at least one month, two months, three months, six months, and preferably at least 12 months, while maintaining full functionality of the printing system. The system is also preferably capable of printing an organic solvent-based ink for a period of at least one month, two months, or three months of use, while maintaining full functionality. In other words, a system including the print head can safely store and print an organic solvent-based ink for a commercially feasible period of time.
Preferably, the use of an organic solvent-based ink does not cause any dissolving, delaminating, shrinking, swelling, or other distortion of the print head materials that materially affects the printing performance of the system over the specified time periods. It is known that temperature affects the interaction between a solvent and the printhead materials; in particular, the higher the temperature, the more likely the solvent will cause some deformation of the printhead materials. Under normal operation, the bulk printhead temperature is typically below 65° C. and ambient temperature is typically below 40° C.
A material effect on the printing performance of the system can be characterized in many ways by those skilled in the art. For example, the printing performance may be characterized by drop weight, drop trajectory, frequency response, microsatellite formation, or break off. The present system is able to operate with organic-solvent based inks while maintaining these factors at acceptable levels. When using the disclosed system, the drop weight is preferably maintained within at most 10% higher or lower of the target drop weight across the full operating frequency range of the print head. The drop trajectory is preferably maintained within a defined angular tolerance that consistently creates clear and crisp images up to the maximum specified throw distance and line speed. For example, to maintain a 10% tolerance of drop position at 240 dpi the maximum angular deviation at 0.5 mm throw distance is 21.2 mrad, at 1.0 mm throw distance is 10.6 mrad, at 2.0 mm throw distance is 5.3 mrad. The frequency response is preferably in the range from less than 100 Hz to greater than 10 kHz.
Microsatellite formation is an undesirable condition whereby the ink droplets elongate during formation and break off to form multiple drops of varying sizes, shapes, trajectories and velocities. Microsatellites can create problems such as poor print quality due to misplaced drops on the substrate, and ink buildup in undesirable areas such as the print head, production line, and the like.
A polymer may be characterized as resistant to organic solvents by having a mass loss or gain of less than 5%, preferably less than 2%, more preferably less than 0.5%. The print head structures or components are sufficiently dimensionally stable such that any changes in any dimension of the structures or components are less than 5%, preferably less than 2%, more preferably less than 1% of the original value. The polymer may have a sufficient cross link density in order to minimize solvent swelling or dimensional stability.
Organic solvents that are contemplated for use with the printing system include ketones, especially methyl-ethyl ketone, acetone, and cyclohexanone; alcohols, especially ethanol; esters; ethers; polar aprotic solvents, and combinations thereof. Suitable inks that may be used with the disclosed printhead are described in U.S. Pat. No. 8,142,559, the contents of which are incorporated by reference. The ink composition may include volatile organic solvents selected from C1-C4 alcohols, C3-C6 ketones, C3-C6 esters, C4-C8 ethers, and mixtures thereof. The volatile organic solvents are preferably selected from C1-C4 alcohols, C3-C6 ketones, and mixtures thereof. Examples of C1-C4 alcohols include methanol, ethanol, 1-propanol, and 2-propanol. Examples of C3-C6 ketones include acetone, methyl ethyl ketone, methyl n-propyl ketone, and cyclohexanone. Examples of C4-C8 ethers include diethyl ether, dipropyl ether, dibutyl ether and tetrahydrofuran. Examples of C3-C6 esters include methyl acetate, ethyl acetate and n-butyl acetate.
The total amount of the one or more volatile organic solvents can be in any suitable amount, for example, in an amount 50% or more, about 60% or more, about 70% or more, about 80% or more, or about 90% or more by weight of the ink composition. In an embodiment, the total amount of one or more volatile organic solvents can be present in an amount from 50% to about 99%, preferably from about 60% to about 95%, and more preferably from about 70% to about 90% of the ink composition. In one embodiment, if water is present in the ink composition, it is present in an amount less than 25% by weight, less than 10% by weight, less than 5% by weight, or less than 2% by weight of the ink jet ink composition.
The thermal inkjet print head may incorporate a tape automated bonding (TAB) flex circuit. With respect to
With respect to
With reference to
A sectional view of the print head 11 is shown in
U.S. Pat. No. 5,774,148 discloses an inner-layer dielectric having a BPSG on top of a CVD oxide; however, BPSG is known to be prone to thermal shock fatigue. In addition, the processing tools and fabrication processes require special attention. In the print head 11 of the subject invention, an additional oxide layer is deposited, using plasma-enhanced or low pressure chemical vapor pressure processes, on top of the BPSG. This additional oxide layer is more resistant to thermal stresses as compared to BPSG. A similar structure is disclosed in a United States patent application Publication No. U.S. 20060238576 A1.
The resistive heaters 18 are fabricated on top of the NMOS drivers or transistors 19. The resistive heaters 18 include a thermal barrier layer 30, a resistive film 31, a conductor layer 32, a passivation layer 33, a cavitation protective layer 34 and a layer 36 of Au on top forming the bonding pads 48. The barrier layer 30 comprises a TiN film deposited over the ILD layer 26. The resistive film 31 preferably comprises a layer of TaAl deposited over the TiN barrier layer 30; and, the conductor 32 preferably comprises a film of AlCu that is deposited over the TaAl resistive film 31. The TiN barrier layer 30, the resistive film 31 and conductor 32 are deposited using sputter deposition processes and then etched by lithography according to a predetermined design of print head 11. Then the three TiN barrier layer 30, TaAl resistive film 31 and conductor 32 are photo-lithographically patterned together in the same masking step so the TiN barrier layer is disposed between the ILD layer 26 and TaAl resistive film 31 and extends entirely underneath the TaAl resistive film 31. In addition, the TiN barrier layer is in direct contact with the sources 27 and drains 28 of the transistors 19.
The disposition of the TaAl resistive film 31 relative to the sources 27 and drains 28 of the transistors 19 is different than the configuration disclosed in U.S. Pat. No. 5,122,812, which discloses a resistive film in direct contact with the transistor components. In the present invention, the TiN barrier film 30 extends under all areas of the TaAl resistive film so the resistive film 31 is not in contact with or is not deposited on the transistor 19 components. Moreover, the TiN barrier layer 30 serves as a thermal-shock barrier layer underneath the resistive film 31 which serves as the heater for the firing chamber 18. The TiN barrier 30 has a higher electrical sheet resistance than that of the resistive film 31 to ensure that most of the electrical pulse power is directed through the resistive film 31. In addition, the TiN barrier film 30 has a higher thermal conductivity as compared to the ILD layer 26; therefore, the TiN barrier 30 serves as a heat diffusing layer for the heat generated by it and the resistive film 31 during firing.
Heater areas, over which the firing chambers 21 are disposed, are exposed by locally dissolving the AlCu conductor 32 on top of the TaAl resistive film 31 using wet etching processes which allow conductor 32 to be tapered at the junction of the TaAl resistive film 30 as shown in
As described above, an ink flow network includes an ink slot 20 and fluidic channels 22 to direct ink from a bulk source to the firing chambers 21. An ink barrier layer 35 is formed over the NMOS drivers or transistors 19 and resistive heaters 18. For use with strong organic solvents typically used in high-performance industrial inks such as ketones, especially methyl-ethyl ketone, acetone, and cyclohexanone; alcohols, especially ethanol; esters; ethers; polar aprotic solvents, and combinations thereof, an epoxy/novolac-based or methyl methacrylate-based negative photo resist may be used. An example of an epoxy/novolac-based photo resist is SU-8 3000 BX, manufactured by MicroChem Corporation. Another example of an epoxy/novolac-based photo resist is PerMX 3000, manufactured by DuPont. An example of a methyl methacrylate-based photo resist is Ordyl PR100 acrylic dry film, manufactured by Toyko Ohka Kogyo. Other negative photoresist materials include bis-benzocyclobutene (BCB) (Shinetsu material), and poly cis-isoprene. Examples of positive photoresist materials are meta-cresol novolac co-polymers with diazonapthoquinine (DNQ) additives, and poly(4-hydroxystyrene) co-polymers with photoacid generators.
The ink barrier layer 35 is laminated over the entire die surface, including the transistors 19, resistive heaters 18, fluidic channels 22, and ink slot 20. A mask with an ink flow network including the fluidic channels 22 and firing chambers 21 is provided and the photoresist is exposed to an ultraviolet light source through the mask. The level of irradiation may vary according to the type of material used for the barrier layer 35. For example, the level of irradiation used for the SU-8 3000 photo resist may range from about 150 mJ to about 250 mJ. The level of irradiation used for the PerMX 3000 photo resist may range from about 300 mJ to about 500 mJ. The level of irradiation used for the PR100 photo resist may range from about 65 mJ to about 200 mJ. After irradiation, the barrier layer 35 and fluidic architecture is developed in a high pressure wash step using a solvent the removes the unexposed polymer, leaving the desired structure.
In one embodiment, the barrier layer and the orifice plate may be made of the same material. In one embodiment, the barrier layer and orifice plate may be integrally formed together. In this case, because the barrier layer and interface are formed integrally, there is no interface for solvents to attack.
The thickness of the ink barrier layer 35 and dimensions of the firing chambers 21 and fluidic channels 22 may vary according to printing demands. With respect to
In the embodiment shown in
Due to the different properties of organic solvent-based inks compared to aqueous inks, it has been found that a different fluid architecture should be used for solvent-based inks than is used for aqueous inks. In particular, solvent based inks produce smaller bubbles than aqueous inks. To increase the bubble size and velocity, a larger resistor 18 may be used than is used for aqueous inks. In particular, the ratio of the resistor length to the orifice diameter is larger than that used for aqueous inks. The ratio of resistor length D to orifice diameter C is preferably between 1.7 and 2.1.
The previously described photolithography steps applied to substrate 14 are used to form an opening in the temporary photoresist layer with predetermined dimensions of the ink slot 20, and thus exposing the substrate 14. The exposed areas intended for the ink slot 20 are rid of any films before the sand-blasting step for forming the ink slot 20. The substrate 14 is then sand-blasted one side at a time to form the ink slot 20 using an X-Y scanning sand-blasting machine. This step is different than the technique disclosed in U.S. Pat. No. 6,648,732, which discloses a procedure that includes a plurality of thin film layers formed on a chip substrate and the ink slot is formed through the plurality of thin film layers in the ink slot area to prevent chipping during the grit-blasting procedure. According to embodiments of the present invention, films forming the resistive heaters 18 and transistors 19 are removed from the area intended for the ink slot 20, so the chip substrate 14 is directly exposed to the sand-blasting.
The ink slot 20 may be formed using a two-sided sand-blasting process. After, the resistive heaters 18 and transistors 19 are formed and etched as described above, the ink slot 20 is formed through the chip substrate 14. A single photosensitive thick film or photoresist is laminated on both sides of the wafer or chip substrate 17. This process is different than a technique disclosed in U.S. Pat. No. 6,757,973 which discloses a technique that incorporates a dual photo-resist layer.
The nozzle plate 23 and arrangement of nozzles 24 is discussed in reference to
For use with strong organic solvents as described above and the above-described barrier layer, an oxygen plasma etched polyimide material may be used. Examples of polyimide that may be used are sold under the names of Kapton®, Kaptrex and Upilex®. Surface treatments other than the oxygen plasma etch that may be used for polyimide films include chromium atom bombardment or a caustic etch. Alternatively, gold plated nickel-based orifice plates may be used. Other suitable materials for the orifice plate include silicon-based materials or polymers with high mechanical strength and chemical resistance.
Each of the nozzles 24 is aligned with a respective resistive heater 18 and firing chamber 21. The bonding of the nozzle plate 23 to the ink barrier layer 35 to form the firing chambers 21 is different than the print heads disclosed in U.S. Pat. Nos. 5,907,333; 6,045,214; and, 6,371,600 that integrate the fluidic channels and firing chambers as part of the nozzle plate. In addition, the conductors of the resistive heaters are not integrated with the nozzle plate as disclosed in U.S. Pat. No. 5,291,226.
The nozzle plate 23 may be fabricated from a roll of raw polyimide film that is processed in a serial fashion by passing the film by a mask-guided laser cutting stations to cut/drill the nozzle orifices 24 through the film. The roll of film is then treated by passing through an adhesion promoter bath. Other surface treatments may also be applied to the nozzle plate material. After the film is cleaned and dried, individual nozzle plates are punched from the roll. In general, the nozzle plate materials may be treated when the material is in the roll form or after the individual nozzle plates are formed. However, the time period between treatment and the assembly of the nozzle plate to the print head is preferably minimized to avoid any degradation of material properties.
With respect to an embodiment of the present invention, the array of resistive heaters 18 on the print head 11 and nozzles 24 on the nozzle plate 23 includes two rows/columns that span a distance of about ½″ on the print head 11. Depending on the orientation of the print head 11, the nozzles 24 may be arranged in either columns or rows. For purposes of describing an embodiment of the invention and in reference to
The assembly of the nozzle plate 23 onto the ink barrier layer 35 is similar in some respects to a thermal bonding process disclosed in U.S. Pat. No. 4,953,287. In a first step, the nozzle plate 23 and the barrier layer 35 are optically aligned and tacked together using a thermo-compression process by applying pressure under elevated temperatures at various points of the nozzle plate 23. This may be performed on an individual basis for each nozzle plate 23. Then nozzles plates 23 are again subjected to a thermo-compression process in which constant pressure at elevated temperatures is applied to all areas of the nozzle plate 23 for a predetermined time. This process may be performed on multiple nozzle plates 23 in a single step. The nozzle plate 23 having been secured to the barrier layer 35, the entire print head 11 is subjected to heat at temperatures ranging from about 200° C. to 250° C. for about 2 hours to cure the barrier layer 35.
Adhesion promoters may also be used to improve the bonding between the nozzle plate 23 and the barrier layer 35, and the substrate 14 and the barrier layer 35. The use of adhesion promoters (also known as coupling agents) is a method for improving interfacial adhesion. However it can be challenging to find an adhesion promoter that is effective in a particular application. The surface chemistries of key barrier layer/orifice plate interfaces are considered in selecting a suitable adhesion promoter. The adhesion promoter may be selected from methacrylic silane, chromium methacrylate complex, zircoaluminate, amino silane, mercapto silane, cyano silane, isocyanato silane, tetraalkyl titanate, tetraalkoxy titanate, chlorobenzyl silane, chlorinated polyolefin, dihydroimidazole silane, succinic anhydride silane, vinyl silane, ureido silane, and epoxy silane. The adhesion promoters may be applied to the surface as a very thin layer. Alternatively, an adhesion layer may be provided with a thickness of 2 micron or greater. The adhesion layer may provide enhanced bonding between the nozzle plate 23 and the barrier layer 35, and the substrate 14 and the barrier layer 35.
Fabrication of the TAB 10 is now described. The TAB 10 may be fabricated using known processes to form a two or three-layered flex circuit. The three-layered flex circuit includes a polyimide film layer 37, shown in
For a two-layered TAB 10, shown in
In reference to
An encapsulant may be used to protect the metal leads that connect the TAB flex circuit 10 to the print head. An encapsulant may also be used to protect other areas of the TAB circuit flex circuit 10. The encapsulant should withstand exposure to organic solvents without swelling or loss of adhesion to silicon carbide, gold, copper, and polyimide. In general, the encapsulant material is preferably a snap-cure epoxy-based adhesive system designed for robust chemical resistance and adhesion to engineering plastics and silicon thin films. Emerson & Cuming LA3032-78 is a preferred encapsulant, since it exhibits insignificant swelling when exposed to organic solvent inks and has good adhesion to polyimide. Emerson & Cuming A316-48 or GMT Electronic Chemicals B-1026E may also be used.
The TAB flex circuit 10 may be attached to the snout portion 14 with a hot-melt bonding film, such as one manufactured by 3M Corporation (3M bonding film #406). In one embodiment, the bonding film is used to adhere the polyimide and metal on the TAB flex circuit 10 to the PPS material of the snout portion 14. The bonding film may be a single layer of ethylene acrylic acid copolymer (EAA), and may also serve to provide electrical and chemical protection. A combination of direct heat staking and adhesive may also be used to attach the TAB flex circuit to the snout portion 14.
The print head 11 may be attached to the cartridge housing 13A using an adhesive. The adhesive should be able to withstand exposure to organic solvents, and like the previously-described encapsulant material, may be snap-cure epoxy-based adhesive systems designed for robust chemical resistance and adhesion to engineering plastics and silicon thin films. Emerson & Cuming E-3032 is a suitable adhesive. Other suitable adhesives include Loctite 190794, Loctite 190665, and Master Bond 10HT.
While the preferred embodiments of the present invention have been shown and described herein, it will be obvious that such embodiments are provided by way of example only and not of limitation. Numerous variations, changes and substitutions will occur to those skilled in the art without departing from the teaching of the present invention. Accordingly, it is intended that the invention be interpreted within the full spirit and scope of the appended claims.
This application claims priority to U.S. application Ser. No. 13/874,067, filed Apr. 30, 2013, which in turn claims priority to U.S. Pat. No. 8,454,149, filed Jun. 28, 2010, which in turn claims priority to U.S. Provisional Application No. 61/221,439 filed Jun. 29, 2009, the contents of all of which are incorporated herein by reference in their entirety.
Number | Name | Date | Kind |
---|---|---|---|
6145963 | Pidwerbecki et al. | Nov 2000 | A |
6447102 | Chen et al. | Sep 2002 | B1 |
6527376 | Itaya et al. | Mar 2003 | B1 |
7086726 | Takashima et al. | Aug 2006 | B2 |
8053046 | Taguchi et al. | Nov 2011 | B2 |
20040155943 | Kim et al. | Aug 2004 | A1 |
Number | Date | Country |
---|---|---|
0761448 | Nov 2002 | EP |
2004-161341 | Apr 1992 | JP |
2005-116315 | May 1993 | JP |
2006-226977 | Aug 1994 | JP |
2001-71509 | Mar 2001 | JP |
2002-25948 | Jan 2002 | JP |
2002-205407 | Jul 2002 | JP |
2006-168233 | Jun 2006 | JP |
2006-218671 | Aug 2006 | JP |
2007-290234 | Nov 2007 | JP |
WO2004060676 | Mar 2005 | WO |
WO2011008485 | Jan 2011 | WO |
Entry |
---|
English translation of Office Action for corresponding Japanese Application 2012-517815 dated Jan. 15, 2014. |
Number | Date | Country | |
---|---|---|---|
20140118441 A1 | May 2014 | US |
Number | Date | Country | |
---|---|---|---|
61221439 | Jun 2009 | US |
Number | Date | Country | |
---|---|---|---|
Parent | 12824424 | Jun 2010 | US |
Child | 13874067 | US |
Number | Date | Country | |
---|---|---|---|
Parent | 13874067 | Apr 2013 | US |
Child | 14149132 | US |