Patent Grant
10052647
The invention relates to a self-cleaning nozzle for use in a spray apparatus to apply a dispersed fluid to a moving web in a web forming process. Motive fluid delivered to an annular flow channel at the nozzle face imparts a helical swirl to process liquid delivered via a central spray outlet, thereby dispersing and uniformly distributing it onto a web moving through the spray apparatus.
The invention concerns a self-cleaning nozzle particularly suitable for use in a plurality in a spray apparatus for the application of a fluid, such as a liquid suspension of starch, binder, adhesive, colorant or other material such as a surface coating agent, onto at least one surface of a paper web in a papermaking process.
In the manufacture of paper, board and similar cellulosic products, a fluid stock consisting of from about 1% solids suspended in about 99% water is ejected at high speed and precision from a headbox slice onto a moving forming fabric, or between two fabrics, in the forming section of a papermaking machine. The stock is drained through the fabric or fabrics by gravity and/or vacuum so that, by the end of the forming section, a cohesive nascent web of fibers is provided. This web is then transferred to a downstream press section where further water removal occurs by mechanical means as the web, together with one or more press fabrics is passed through at least one, and usually a series, of nips formed between pairs of rotating press rolls so as to remove a further portion of the water entrained in the web. At the end of the press section, the web is transferred to the dryer section where its remaining moisture is removed by evaporative means as it is passed, together with one or more dryer fabrics, over a series of steam heated rotating drums known as dryer cans or cylinders.
The paper product thus obtained will usually require at least one or more subsequent chemical or physical treatments so as to render it suitable for its intended use and impart to it various properties, such as smoothness, gloss, impermeability, rigidity, color, and so on, as desired. These properties are often obtained by applying a surface sizing agent or other material (such as a colorant, optical brightener, or water resistant film or other coating) during or following drying. This is frequently done by passing the sheet through a pond sizer so that it is immersed in the desired solution, or by applying size as a film using a film sizing apparatus as the sheet passes through a nip. In addition, it is often necessary to apply water onto the sheet so as to improve the uniformity of the moisture content across the full width of the manufactured web.
A wide variety of both pond and film sizing application devices are available on the market today, and numerous patents cover various aspects of their technology. Although suitable for use in certain applications, the known devices are limited in machine speed potential and cannot exceed these limits without causing process instabilities, or web breaks to occur due to strength losses and/or absorbency variations in the web that is delivered to the sizing apparatus. It is also difficult to precisely control the average amount of material applied to the sheet independently of machine speed with the known devices, and the specific amount applied at different locations across the full width of the manufactured web. As well, the known devices are difficult to keep clean.
It has been found that one means of overcoming at least a portion of the aforementioned problems of the known film or pond coating methods is to spray the desired process liquid directly on to the sheet as it passes beneath or through one or more arrays of spray nozzles. Both the average amount and the cross-directional uniformity of spray application are less dependent on sheet properties than by conventional application means, and it is also possible to use relatively high concentrations of suspended or dissolved materials in the process liquid. In addition, a spray apparatus allows for more precise control of the amount, and type, of materials to be delivered as the liquid and solids concentration provided to at least a portion of the nozzles can be proportioned to allow for a somewhat profiled delivery to the sheet. However, a problem common to the known spray apparatuses is that it is difficult to keep the nozzle areas clean and free of contaminants, particularly where a sizing material is being applied. Typically, the solids in the process liquid will become deposited proximate the nozzle tip, and their build up will eventually disrupt the spray pattern and clog the nozzle outlet.
Nozzles for spraying a dispersed mist onto a moving web, and arrangements of such nozzles, are well known, and have been described, for example, by Sundholm et al. EP 435904 and EP 682571; Kangas et al. U.S. Pat. No. 6,866,207 and U.S. Pat. No. 6,969,012; and Diebel et al. EP 2 223 748. Others are known and used.
Tynkkynen et al. EP 2 647 760 describes a nozzle in which the tip or end is provided with means for controlling its temperature so as to prevent or at least minimize the adherence of undesirable matter from the fluid spray that is applied to the moving web. However, this is a high pressure type nozzle with a small tip opening, and the solution proposed in the disclosure is not appropriate to nozzles having a relatively larger spray opening at the tip, where the process liquid is dispersed by a flow of pressurized air.
None of the known prior art effectively addresses the issue of preventing deposits of the sprayed material and/or contaminants being formed around the nozzle discharge outlet that affects the spray dispersion quality as well as the spray pattern.
In order to address the issue of preventing deposits for nozzles, particularly of the type having a nozzle body with a liquid flow path defined therethrough having an inlet and a spray outlet, with a carrier body that surrounds the nozzle body having an annular gas flow channel with a gas discharge outlet located around the spray outlet, according to the invention a porous surface, preferably in the form of a porous disk, is provided that surrounds the annular gas flow channel at the gas discharge outlet. A low velocity fluid is delivered to the porous surface and is discharged therethrough to minimize deposition of undesirable matter adjacent the spray outlet. A radiused surface is formed in the carrier body around the air discharge outlet where it acts to decompresses a motive fluid to assist in uniformly dispersing process liquid delivered to the spray outlet, as well as provides a radially outwardly expanding flow to the porous surface, keeping this transition area free of deposits. This can be incorporated into new nozzles or provided by an adapter for existing nozzles.
In a first preferred embodiment, a nozzle assembly with a self-cleaning discharge end face is provided having a nozzle body with a liquid flow path defined therethrough having an inlet and a spray outlet. A carrier body is provided in which the nozzle body is mounted, and an annular gas flow channel is defined around the spray outlet that is provided with a source of pressurized fluid. A porous surface is located on the face of a discharge end of the nozzle assembly, and is in fluid communication with a preferably annular pathway. The porous surface is adapted to provide a low velocity fluid discharge of the pressurized fluid delivered to the annular pathway. A radiused surface is formed in the carrier body around the air discharge outlet where it acts to decompresses a motive fluid so that it expands the flow outwardly to the porous surface. This arrangement reduces or prevents the deposition of spray material and contaminants around the discharge end of the spray nozzle, minimizing the need to shut down a production line for cleaning and/or replacement of the spray nozzles by providing a nozzle with a self-cleaning face provided with a low velocity fluid discharge that prevents deposition of contaminants about the spray outlet.
In the first preferred embodiment, a motive fluid such as a pressurized gas is provided to an air path in the nozzle assembly from an outside source and then passes through a stator where angled guide vanes impart a helical swirling motion to the fluid flow. As a first portion of the motive fluid proceeds downstream towards the discharge end though an annular gas flow channel, it is compressed due to a tapering of the channel from a larger cross-sectional area upstream to a smaller cross-sectional area proximate the spray outlet downstream. Process liquid is separately supplied to the liquid flow path via an inlet. As the motive fluid emerges from the gas flow channel, it passes over the radiused surface and exits at the gas discharge outlet where it decompresses, thereby atomizing and, via the rotary motion imparted to it, dispersing the process liquid delivered to the spray outlet to ensure uniform deposition of liquid droplets onto a surface of a moving web to which it is to be applied during use. A second portion of the motive fluid entering the annular gas flow channel is diverted into and delivered via at least one radial channel to the annular pathway which is in fluid communication with a porous disk. A portion of this motive fluid passes through the porous disk and provides a low velocity fluid discharge as it exits the disk through its porous surface thereby removing contaminants and other matter before they become deposited on or around the porous surface and the spray outlet. The flow of motive fluid over the radiused surface also provides a radially outwardly expanding flow to the porous surface, keeping this transition area free of deposits. In this embodiment, a portion of the motive fluid supplied to the annular gas flow channel downstream of the stator is also directed to the annular pathway via the radial channel(s).
In a second preferred embodiment, the motive fluid is provided to the air path in the nozzle assembly from an outside source. A first portion passes through the stator where angled guide vanes impart to it a helical swirling motion; this motive fluid then proceeds downstream towards the discharge end along the annular gas flow channel where it is compressed due to a tapering of the channel from a larger cross-sectional area upstream to a smaller cross-sectional area proximate the spray outlet downstream. Process liquid is separately supplied to the liquid flow path via the inlet. As the motive fluid emerges from the gas flow channel at the gas discharge outlet, it passes over a radiused surface where it decompresses, thereby atomizing and, via the rotary motion imparted to it, dispersing the process liquid delivered to the spray outlet to ensure uniform deposition of droplets of process liquid onto a surface of the moving web to which it is to be applied when in use. A second portion of the motive fluid entering the air path is separately directed to at least one air inlet. From the inlet, this motive fluid proceeds along at least one outside channel to the preferably annular pathway which is in fluid communication with the porous disk. A portion of this motive fluid passes through the porous disk and provides a low velocity fluid discharge as it exits the disk through the porous surface so as to remove contaminants and other matter before they become deposited on or around the porous surface and the spray outlet. The flow of motive fluid over the radiused surface also provides a radially outwardly expanding flow to the porous surface, keeping this transition area free of deposits. Thus, in this second embodiment of the invention, a portion of the motive fluid delivered to the nozzle is directed via the air inlet and separate outside channel(s) to the annular pathway prior to or separately from passing through stator, while in the first embodiment, the motive air is directed through the stator to annular gas flow channel where a portion is then directed to the annular pathway via the radial channel(s).
In a third preferred embodiment of the invention, a first motive fluid is delivered under pressure from an external source to an air path in the nozzle from which it passes through the stator to the annular gas flow channel. As the motive fluid emerges from the channel, it passes over the radiused surface where it decompresses as it exits the nozzle at gas discharge outlet, thereby atomizing and, via the rotary motion imparted to it by stator, uniformly disperses process liquid delivered to the spray outlet via the inlet so as to ensure uniform deposition of liquid droplets onto a surface of the moving web to which it is to be applied. A second fluid is separately supplied to the air inlet via an external fluid inlet. This second fluid may be the same as, or different from, the first motive fluid supplied to the air path from the external source. This second fluid moves from the air inlet along the outside channel to a preferably annular pathway, and then through the porous disk to provide a low velocity fluid discharge over the porous surface so as to remove contaminants and other matter before they become deposited on or around the porous surface and the spray outlet. The flow of motive fluid over the radiused surface also provides a radially outwardly expanding flow to the porous surface, keeping this transition area free of deposits.
In this third embodiment of the invention, the second fluid supplied to the porous disk via the external fluid inlet is provided separately from the first motive fluid supplied to the stator via the air path, and thus may be the same as, or different from, that fluid. For example, the fluid delivered to the external fluid inlet may be a cleaning agent, steam or otherwise. In this embodiment, the supply of second fluid to the porous disk may be provided either continuously or intermittently as it may be separately controlled from the supply of the first motive fluid. By comparison, the fluid delivered to the porous disk in the first and second embodiments must always be the same as the motive fluid provided to the air pathway.
In a fourth preferred arrangement of the invention, a nozzle adaptor is provided which is structured and arranged so as to be located in surrounding engagement with a nozzle housing including a nozzle assembly which may either be an air & liquid type such as described previously, or a high pressure nozzle, either of which may be used in the application of an atomized fluid in a web forming process. The adaptor includes an adaptor body in which is located a nozzle assembly receptacle opening that is adapted to be a close surround fit over the nozzle housing including the nozzle assembly and the outlet. The adaptor is separately supplied with a fluid, such as a cleaning solvent, or a gas such as steam, damp or humid air, or ambient air, via an adaptor inlet. The fluid delivered via the adaptor inlet is directed to a fluid inlet to an outside channel in fluid communication with a preferably annular pathway and is delivered from there to a porous surface, preferably a porous disk, located in surrounding relation to the opening where it provides a low velocity fluid discharge through porous surface. The opening is sized to accommodate a spray outlet including a liquid flow path of the nozzle assembly. As mentioned, the nozzle assembly is provided with a separate source of motive fluid shown diagrammatically as provided through the fluid path while a process liquid is delivered from an external source via the inlet via a liquid flow path. The adaptor preferably also includes the radiused surface about the discharge outlet for the motive fluid to promote a radially outwardly expanding flow to the porous surface, keeping a transition area between the discharge outlet and the porous surface free of deposits. The adaptor allows for retrofitting of a wide variety of nozzles with the features of the self-cleaning face of the present invention, including nozzles which were not originally constructed to incorporate them, including, but not limited to, nozzles that do not use motive air for process liquid dispersion. In this embodiment, it is possible to provide a fluid (such as a liquid cleaning agent) or a gas (such as air, steam, or damp/humid/ambient air) to the porous disk separately from any motive fluid that may be provided to disperse process liquid. Such fluid can be provided as needed to the porous disk as it is separately supplied.
In the first, second and third embodiments of the invention, the nozzle assembly preferably includes a stator located in the annular gas flow channel. The stator preferably includes a series of guide vanes oriented at an angle to the process liquid flow path so that a helical rotary swirling motion is imparted to it as the liquid passes under pressure through angled vanes in stator.
Preferably, the air path is in communication with a source of pressurized motive fluid that creates an active fluid flow on the porous surface. Alternatively, the porous surface is supplied with a pressurized fluid via an external fluid inlet.
Preferably, the pressurized motive fluid is directed to the porous disk downstream of the stator. Alternatively, the motive fluid is directed to the porous disk via a fluid inlet channel located upstream of the stator.
Preferably, the annular pathway is provided with a motive fluid selected from a gas and a liquid. Preferably, the motive fluid is damp air which creates an active fluid flow on the porous surface.
In another aspect, the invention provides a spray assembly for a liquid, which includes a liquid chamber adapted to contain liquid to be sprayed, a fluid chamber adapted to contain pressurized fluid, and a plurality of nozzles connected to the chamber. Each of the nozzles includes: a nozzle body with a liquid flow path defined therethrough having an inlet and a spray outlet a carrier body in which the nozzle body is mounted; a preferably annular pathway defined around the spray outlet that is provided with a source of pressurized fluid; and a porous surface located on the face of discharge end and in fluid communication with the annular pathway; the porous surface is adapted to provide a low velocity fluid discharge from the pressurized fluid delivered to the annular pathway at the porous surface. The annular pathway is connected to the air path or an outside channel to provide a low velocity fluid discharge through the porous surfaces surrounding the nozzles that prevents deposition of contaminants about the spray outlets of the nozzles.
In another aspect, the invention provides a method of spraying a liquid on an object, which includes the steps of:
Further features and embodiments of the invention are described below and in the claims, which are expressly incorporated into this Summary section, and have not been reproduced here for the sake of brevity.
The foregoing summary, as well as the following detailed description of the preferred embodiment of the present invention will be better understood when read in conjunction with the appended drawings. For the purposes of illustrating the invention, there is shown in the drawings two embodiments which are currently preferred. It should be understood, however, that the invention is not limited to the precise arrangements shown. The invention will now be described with reference to the appended Figures in which:
Certain terminology is used in the following description for convenience only and is not limiting. The words “front,” “rear,” “upper” and “lower” designate directions in the drawings to which reference is made. The words “inwardly” and “outwardly” refer to directions toward and away from the parts referenced in the drawings. “Axially” refers to a direction along the axis of the nozzle. “Stator” refers to a fixed set of guide vanes located in air path 30 oriented to impart helical motion to the fluid. A reference to a list of items that are cited as “at least one of a, b, or c” (where a, b, and c represent the items being listed) means any single one of the items a, b, or c, or combinations thereof. The terminology includes the words specifically noted above, derivatives thereof and words of similar import.
Referring to
A stator 50 is located in surrounding relation to nozzle body 12 interior to carrier body 20 and in communication with the air path 30. Motive fluid such as ambient or hot damp air is delivered under pressure from the air path 30 to the stator 50 and then to the annular gas flow channel 24. As shown in detail in
The cross-sectional dimension of annular gas flow channel 24, thus its volume, progressively decreases from the stator 50 to a minimum prior to the radiused surface 28 and then increases rapidly at the gas discharge outlet 26. This initial volume decrease compresses the spinning fluid delivered through the angled guide vanes of the stator 50; the fluid then rapidly decompresses as it passes over radiused surface 28 at the gas discharge outlet 26. This rapid decompression of the fluid, in combination with the helical swirling motion imparted by the guide vanes 52 of the stator 50, causes the fluid to effectively explode outwardly as it exits the outlet 26. Process liquid delivered to the spray outlet 18 via the liquid flow path 14 is completely atomized and uniformly dispersed by the explosive effect created by the rapid expansion of the swirling fluid as it exits gas discharge outlet 26 surrounding spray outlet 18.
In this first embodiment of the invention, a first portion of the fluid delivered to air channel 24 from upstream stator 50 is directed to gas discharge outlet 26 to disperse the process liquid, while a second portion of the motive fluid entering channel 24 is diverted into radial channel 38 from which it passes to a preferably annular pathway 36 in fluid communication with porous disk 40. A portion of this motive fluid passes through porous disk 40 and provides a low velocity fluid discharge as it exits the disk 40 through porous surface 42, thereby removing contaminants and other matter before they become deposited on or around porous surface 42 and spray outlet 18. The radiused surface 28 also promotes a radially outwardly expanding flow to the porous surface 42, keeping this transition area free of deposits. Thus, in this embodiment, a portion of the motive fluid supplied to annular gas flow channel 24 downstream of stator 50 is also directed to annular pathway 36 via radial channel 38.
A stator 50 is located in surrounding relation to nozzle body 12 interior to carrier body 20 and in communication with the air path 30 to which a first portion of a motive fluid, such as ambient or hot damp air, is delivered under pressure. This motive fluid passes through the stator 50 and then to the annular gas flow channel 24. As shown in detail in
A second portion of the same motive fluid entering air path 30 is separately directed to air inlet 37 and does not pass through stator 50. From inlet 37, this motive fluid proceeds along outside channel 39 to a preferably annular pathway 36 which is in fluid communication with porous disk 40. A portion of this motive fluid passes through porous disk 40 and provides a low velocity fluid discharge as it exits through porous surface 42 which assists in preventing deposition of contaminants adjacent the nozzle. Again, the radiused surface 28 also promotes a radially outwardly expanding flow to the porous surface 42, keeping this transition area free of deposits. Thus, in this second embodiment of the invention, a first portion of the motive fluid delivered to nozzle 10′ is directed through the stator 50 to annular gas flow channel 24, and a second portion of the motive fluid delivered to nozzle 10′ is directed via air inlet 37 and separate outside channel 39 to the annular pathway 36 and does not pass through stator 50.
Beginning at the right of
In this embodiment, a second fluid is separately supplied under pressure to air inlet 37 via external fluid inlet 31. This second fluid may be the same as, or different from, the motive fluid supplied to air path 30 from external source 3. This second motive fluid moves from air inlet 37 along outside channel 39 to a preferably annular pathway 36, and then through porous disk 40 to provide a low velocity fluid discharge as it exits through porous surface 42 which assists in preventing deposition of contaminants adjacent the nozzle. The radiused surface 28 here also promotes a radially outwardly expanding flow to the porous surface 42, keeping this transition area free of deposits.
It will be appreciated that, in this third embodiment of the invention, the second fluid supplied to the porous disk 40 via external fluid inlet 31 is provided separately from the first motive fluid supplied to the stator 50 via the air path 30, and thus may be the same as, or different from, that fluid. For example, the fluid delivered to external fluid inlet 31 may be a cleaning agent, steam, ambient air, or otherwise and may be provided to the annular pathway (and the porous disk 40) either continuously or intermittently as this supply may be separately controlled. By comparison, the fluid delivered to the porous disk 40 in the first and second embodiments shown in
Referring now to
The opening 119 is sized to accommodate the spray outlet 118 which includes a liquid flow path 114 of the nozzle assembly 100. As mentioned, the nozzle adaptor 110 is provided with a separate source of motive fluid shown diagrammatically as provided through the fluid path 130. During operation, a process liquid is delivered from an outside source such as 66A to a coupling 2 attached to the nozzle assembly 100 via inlet 116 to a liquid flow path 114.
The adaptor unit 110 allows for retrofitting of a wide variety of nozzles with the features of the self-cleaning face of the present invention, including nozzles which were not originally constructed to incorporate the self-cleaning face technology according to the invention, including, but not limited to, nozzles that do not use motive air for process liquid dispersion. In this embodiment, as in the third embodiment shown in
As noted above, the channel 24 is shaped so as to decrease in cross-sectional area, and thus volume, as it progresses from the stator 50 towards the radiused surface 28. As the compressed gas moves outwards over the surface 28 it expands rapidly in a somewhat explosive manner which, along with the rotary motion imparted by the angular vanes of the stator 50, produces an outcome similar to the known Bernoulli or Coanda type effects. This causes complete atomization and dispersion of the process liquid as it exits the nozzle at the spray outlet 18. Process liquid delivered to the spray outlet 18 is thus directed away from the outlet 18 and the porous surface 42 of the porous disk 40. The nozzle face is self-cleaning in that low velocity fluid discharge through the disk 40 directs and removes any ambient particulate matter or fluid droplets away from the vicinity of the discharge end 32 so that they do not otherwise coalesce, while the Bernoulli or Coanda swirl effect disperses the fluid and directs it to the moving paper sheet towards which it is directed.
The porous disk 40, 140 is preferably made from one of either a ceramic material or a sintered metal such as stainless steel. If ceramic, one suitable material has been found to be Pall Carbo filter element type 30 available from Pall Corp. If made from metal, a filter such as is available from GKN Sinter Metals GmbH under designation SIKA-R 1.4404 appears to be satisfactory. The liquid flow path 14 is preferably formed from one of either stainless steel coated with Teflon® [PTFE—polytetrafluoroethylene], or polyetheretherketone (PEEK) or other low surface energy polymer. The stator 50 may be comprised of PEEK, brass or other metal or polymer material as may be suitable depending on the intended end use. The carrier body 20 including the tool engaging surfaces 22 may be formed from stainless steel, PEEK or other materials as may be suitable depending on the intended end use.
Use of one of either a metal or ceramic material in porous disk 40, 140 including end face 42 may be dictated by the type of environment and end use application in which the nozzle assembly is to be used. For example, if it is anticipated that the liquid to be sprayed onto the moving web and supplied to the nozzle will be “hot” (e.g.: at or near 100° C., for example) it may be preferred to use a ceramic material such as described above and which is available from Pall Corp. The ceramic material may be somewhat insulated from the temperature of the liquid and will thus tend to remain relatively cooler during operation, thereby inhibiting deposition of suspended materials such as starch in the liquid supplied to the nozzle. On the other hand, if the liquid is anticipated to be “cooler” (e.g. <100° C., for example) either the aforesaid ceramic, or a sintered metal material such as is available from GKN Sinter Metals GmbH may prove satisfactory.
Having thus described the present invention in detail, it is to be appreciated and will be apparent to those skilled in the art that many physical changes, only a few of which are exemplified in the detailed description of the invention, could be made without altering the inventive concepts and principles embodied therein. It is also to be appreciated that numerous embodiments incorporating only part of the preferred embodiment are possible which do not alter, with respect to those parts, the inventive concepts and principles embodied therein. The present embodiment and optional configurations are therefore to be considered in all respects as exemplary and/or illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all alternate embodiments and changes to this embodiment which come within the meaning and range of equivalency of said claims are therefore to be embraced therein.
Nozzle Adaptor Parts
| Number | Date | Country | Kind |
|---|---|---|---|
| 10 2014 100 605 | Jan 2014 | DE | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/US2015/011686 | 1/16/2015 | WO | 00 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2015/112436 | 7/30/2015 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 2572538 | Teters | Oct 1951 | A |
| 3581998 | Roche | Jun 1971 | A |
| 3637141 | Gores | Jan 1972 | A |
| 4210534 | Molvar | Jul 1980 | A |
| 4341348 | Dearling | Jul 1982 | A |
| 4502629 | McGhee | Mar 1985 | A |
| 4890791 | Hoffman | Jan 1990 | A |
| 4976607 | Grimard | Dec 1990 | A |
| 5656084 | Focke et al. | Aug 1997 | A |
| 5845846 | Watanabe et al. | Dec 1998 | A |
| 5932293 | Belashchenko et al. | Aug 1999 | A |
| 6269821 | Berke | Aug 2001 | B1 |
| 6474569 | Brundish | Nov 2002 | B1 |
| 6716484 | Brynolf | Apr 2004 | B2 |
| 6866207 | Kangas et al. | Mar 2005 | B2 |
| 6969012 | Kangas et al. | Nov 2005 | B2 |
| 7124574 | Horn | Oct 2006 | B2 |
| 7967221 | Snyder | Jun 2011 | B2 |
| 8789769 | Fenton | Jul 2014 | B2 |
| Number | Date | Country |
|---|---|---|
| 2223748 | Sep 2010 | EP |
| 2647760 | Oct 2013 | EP |
| 2002-102765 | Apr 2002 | JP |
| 2002102765 | Apr 2002 | JP |
| 9003225 | Apr 1990 | WO |
| 9411116 | May 1994 | WO |
| 2004056487 | Jul 2004 | WO |
| Number | Date | Country | |
|---|---|---|---|
| 20160296960 A1 | Oct 2016 | US |
