Patent Grant
7816065
The present invention relates to the preparation of imageable lithographic plates, and especially to such plates as used for printing.
Plates of this type have a radiation-sensitive, oleophillic polymer resin coating on a hydrophilic substrate. After image-wise exposure at ultraviolet, visible, or infrared wavelengths, the plates are developed to remove the non-exposed regions of the coating, thereby producing a substantially planographic pattern of oleophillic and hydrophilic regions. The developed plates are then ready for mounting on a cylinder of a printing press, where the plates are subjected to fountain fluid and ink for transfer of ink to a target surface according to the pattern of oleophillic and hydrophilic regions on the plate.
The present innovation is that a novel coating for plates of this general type can be imagewise exposed to radiation and then directly processed with only water to remove the non-exposed regions of the coating.
As a consequence, unlike in conventional systems, with the present invention the plates can be delivered directly from the imager to the press, where fountain fluid “develops” the plates on-press. The non-imaged (non-exposed) regions quickly dislodge to reveal the underlying substrate, which has an affinity for fountain fluid, while the ink-receptive imaged regions are retained. The immersion of the plate in fountain fluid and the contact of the wet plate with a cylinder in the press removes the non-imaged regions without a distinct developing step, and without the need for monitoring or intervention. The resulting printing plates can be run in the conventional manner to produce the printed product. As an optional configuration, the imaged plates may be sent to a water processing station, where no special treatment is required other than contact with neutral water.
The most evident advantage is that no separate developing equipment or step is required between the imager and the press. A second significant advantage, whether or not the plate is passed through a water processor, is that there is little or no chemical treatment required of the waste stream associated with developing the plate. A third significant advantage is that because dissolution of the polymer resin is not relied upon for processing the plate, higher molecular weight resins can be used in the coating, thereby producing more durable oleophillic regions and longer plate life on press.
The invention is thus directed to a novel coating formulation, and to a coated plate having a novel imageable coating. A negative working, actinically and/or IR imageable coating is deposited from a solvent (non-aqueous) solution on a hydrophilic planar surface. The coating comprises a polymer, a monomer and/or oligomer, polymerization or cross link initiator, stabilizer, and dye or pigment, such that after imaging, the non-imaged resin areas are removable from the planar surface by penetration of water through the non-imaged coating without dissolution of the resin components of the coating, to form a lithographic printing plate with clearly defined image and non-image areas.
Coatings based on the present invention can comprise one or more components capable of cross linking by free radical polymerization. The polymerization arises as a result of exposure to the imaging radiation. The radiation absorbers and/or initiators facilitate the cross linking efficiency. The coatings also comprise a solvent soluble, partially water soluble, non-polymerizable organic component as the stabilizer that enables the coating to be removable by water in the non-cross linked areas.
In an alternative embodiment, the imageable coating is applied over a subcoating, and a topcoat is applied over the imageable coating. The top coat is typically a water soluble film former that serves to prevent atmospheric oxygen from diffusing into the coating and quenching the free radicals. The subcoat facilitates the release of the coating from the substrate in the non-imaged areas.
The presence of processing or fountain water on the plate coupled with the partial solubility of the non-polymerizable organic compound in the coating, produces paths in the non-imaged regions for the water to penetrate the surface. It is believed that fissures or the like form in the coating, enabling the film or layer of water on the surface of the coating to penetrate the coating, for example by one or more of seepage, percolation, or diffusion. The water appears to penetrate to the surface of the substrate, where it may spread laterally under the coating. The water penetration facilitates the release of the coating from the substrate.
In another embodiment, the invention is directed to a process for preparing a lithographic plate for offset printing. The steps include selecting a plate having a hydrophilic substrate and an overlying oleophillic, radiation sensitive coating, which coating cross links where exposed to radiation in a particular wavelength range, and imagewise exposing the plate to radiation in that particular wavelength range, thereby producing a pattern of cross linked, highly cohesive oleophillic regions and less cohesive oleophillic regions. The entire coating is then exposed to water, whereby water penetrates only the less cohesive regions to the substrate, undermining the adhesion of and completely dislodging these regions from the substrate to form a printing plate having an image pattern of cross linked, oleophillic regions of said coating and hydrophilic regions of the substrate.
In yet another embodiment, the invention is directed to a printing process in which the imaged plates are developed on press, in the presence of fountain fluid. These steps include selecting a plate having a hydrophilic substrate and an overlying oleophillic, less cohesive, radiation sensitive coating, which coating cross links where exposed to radiation in a particular wavelength range. The next step is imagewise exposing the plate to radiation in that particular wavelength range, thereby producing a pattern of cross linked oleophillic regions and less cohesive oleophillic regions. Without further treatment, the plate is mounted on a lithographic printing press cylinder. On press, the plate is subjected to a press fluid comprising at least one of water or fountain solution, whereby the water or fountain solution penetrates through only the less cohesive regions to the hydrophilic substrate. Contact of the coating with an opposed blanket cylinder pulls the less cohesive regions from the plate to form a printing plate having an image pattern of cross linked, oleophillic regions of the coating and hydrophilic regions of the substrate. At substantially the same time or shortly thereafter, ink is applied to the printing plate for transferring ink to the blanket cylinder and further transfer of ink to a target surface to be printed.
A key feature of the invention is the penetration of water through the non-imaged regions of the imaged plate, to dislodge these regions without weakening or deterioration of the cross-linked imaged regions. However, within that broad functionality, one of ordinary skill based on the following detailed description and examples, can vary several constituents of the coating to optimize imaging speed, wavelength sensitivity, strength of the cross linked, oleophillic, radiation-imaged regions, and ease of removal of the non-imaged regions to reveal the hydrophilic substrate. One basis for optimization, is whether the imaged plates will be processed in a water bath upstream of the press, or directly on-press. The non-imaged coating regions are generally more easily removed on press than in a bath with wiping, so the optimization for on-press processing can be biased toward higher molecular weight polymer resins, or higher ratio of polymer to monomer. If high imaging speed is the basis for optimization, a high monomer to polymer ratio is utilized, thereby promoting rapid cross linking upon exposure to imaging radiation. The susceptibility to water penetration of the coating due to the presence of the stabilizer, is also affected by the monomer to polymer ratio.
Furthermore, it is believed that the presence of the partially water soluble stabilizer compound in the hydrophobic resin, plays a key role in facilitating relatively rapid water penetration through the non-image regions while having little or no such facilitating effect in the cross linked, image regions. Although the coating and/or the substrate can include a more highly water soluble material, for accelerating the release of the non-imaged coating regions, it is believed that the window of effectiveness for commercial use requires a significant presence of the partially water soluble material, which can be balanced off against a lesser presence of full water soluble material. Moreover, the partially soluble material for implementing the present invention, can play a dual role in the coating, e.g., an optimized presence of a partially water soluble polymerization initiator or a radiation sensitive dye, may not require a separate partially water soluble stabilizer.
The term “stabilizer” as used herein, connotes a material that is soluble in the non-aqueous solvent for the resin, but also has partial solubility in water. Solubility in the solvent means that the material is substantially homogeneously distributed in the resin and monomer of the coating liquid as it is applied onto the substrate. In the dried coating the stabilizer can also provide the function of enhancing the shelf life, in addition to effectuating the penetration of water to the substrate during post-image processing. This is another aspect of the feature described above, wherein it is not always necessary to have a distinct stabilizer material apart from the other constituents; some constituents can play a dual role if they exhibit an effective degree of partial water solubility.
Further optimization can trade off the presence of one or more water-soluble release accelerators or agents, as to one or both of the coating and a subcoating on the substrate. Also, whether a plate was top coated with an aqueous solution can affect the efficiency of water penetration for a given coating composition.
Another optimization can be obtained by utilizing co-initiators, such as a combination of triazine and a smaller amount of an organo-borate compound.
In yet another embodiment, a thermally imageable negative working plate having a coating according to the improvements previously described herein, can be exposed to heat for a short period of time after imaging, such that the imaged portions become more stable and tougher, while the portions of the coating that are to be removed are not significantly affected. This thermal enhancement step increases the difference in removability between the imaged and non-imaged regions. The heating step preferably, but not necessarily, immediately follows the imaging step, and can be at a different location from the imaging step.
Printing Press Process
Unlike conventional systems, in the present invention the imaged plates can be delivered directly to the press 16, where exposure to fountain fluid 18 “develops” the plates on-press, by quickly dislodging the non-image regions to reveal the underlying substrate, which has an affinity for fountain fluid, and retaining the imaged regions, which have an affinity for ink. The immersion of the plate in fountain fluid and the contact of the wet plate with the blanket in the press removes the non-imaged regions without a distinct developing step, and without the need for monitoring or intervention of any type. The resulting printing plates can be run in the conventional manner to produce the printed product, which is output at 22.
As an optional configuration, the imaged plates may be sent to a water processing station 24, where no special treatment is required other than contact with pH neutral water (e.g., tap water) for a period typically in the range of about 10-60 seconds. The non-imaged regions quickly become susceptible to removal by simple wiping, ultrasound cleaning, or pressurized water spraying. A suitable spray can be achieved with a nozzle pressure in the range of 100-300 psi, directing a fan pattern about 6-12 inches wide at a distance of about 6-12 inches from the plate. This wiping can be achieved as part of or immediately after the water processing at 24. The plates can then be dried and stacked, before a fully processed plate is sent to the press 16. Optionally, the plates may be subjected to a gumming step (typically with a gum Arabic solution) prior to mounting on press. This is a well known practice in the printing industry, and is especially preferred if the plate will not be placed on press immediately after development.
It is well known in this art, that fountain fluid can have a range of pH and include other additives such as surfactants and the like for optimizing the operation of the press or the quality of the product. With the present invention, the fountain fluid can be pure water, or water with additives to improve the printing process, but no solvent or pH adjustment is needed for removing the non-imaged regions of the plate, whether the plate is delivered to the press directly from the imager 14, or first subjected to water developer 24 upstream of the press.
The most evident advantage of the foregoing process, is that no separate developing equipment or step is required between the imager 14 and the press 16. A second significant advantage, whether or not the plate is passed through a water processor 24, is that little or no chemical treatment is required of the waste stream associated with developing the plate. Not only is the fresh developer fluid non-toxic and non-reactive, but in a surprising discovery, little or none of the coating removed from the non-exposed regions of the plate is dissolved or dispersed into the process water. Rather, all or most of this coating detaches from the substrate in sufficiently large pieces that can be readily removed by filtration and relatively easily disposed of.
Imageabale Plate
In a conventional developing process, the developer is typically one of two primary types. One type is a developer that contains some level of a solvent, most typically benzyl alcohol. This type of developer is very common for negative working UV plates. The second type of developer is a high pH composition containing typically alkali silicate and/or alkali hydroxide. This type of developer is widely used for positive working thermal plates. The developer dissolves or disperses the unexposed regions 30a, 30b, and 30c, leaving only the exposed regions 32a, 32b. According to the present invention, the regions 30a, 30b, and 30c can be removed as a result of immersion or spraying with water, and the wiping away of the non-imaged regions.
One significant advantage arising from the present invention is that the non-imaged area of the plate will have less tendency to retain ink receptive coating residue than a conventionally developed plate. With conventional development, the coating must be completely dissolved and removed in the developing step. It is sometimes problematic to ensure that all coating is removed from the interstices of the substrate grain. Any residual will remain during the printing process and cause some level of ink pick-up in the background. With the present invention, the coating in the background areas is not adhesively bound to the substrate, and is removable by the press. Any residual coating will tend to be removed during the printing start-up, resulting in a cleaner background.
Another significant advantage of the present invention is that the integrity of the imaged coating is not adversely affected by the processing liquid, i.e., water or fountain fluid. For conventional plates, the imaging process causes a change in the solubility of the coating in the developer. The change is never 100% efficient; that is, even the imaged coating will have some level of solubility in the developer. This residual solubility may significantly alter the adhesive and/or cohesive integrity of the coating. The present invention does not suffer from this problem. This will be illustrated in the examples described herein.
Direct Coating of Representative Embodiment
In one particular embodiment of the invention having the basic configuration shown in
Advantageously, the coating comprises from about 35 to about 75 wt % based on solids content, of a polymerizable monomer, a polymerizable oligomer, or combination thereof, that is similarly insoluble in water. Some suitable radically polymerizable (cross linkable) materials are a multifunctional acrylate such as Sartomer 399 and Sartomer 295 commercially available from Sartomer Co.
The coating comprises an initiator system capable of initiating a polymerization reaction upon exposure to imaging radiation. Some suitable initiator systems comprise a free radical generator such as a triazine or an onium salt.
Advantageously, the coating comprises from about 5 to about 15 wt % based on solids content of a “stabilizer” that is soluble in organic solvents and only partially soluble in water. Some suitable stabilizers include a substituted aromatic compound, such as DTTDA (an allyl amide derived from tartaric acid) and tetra methyl tartaramide.
Additional optional components include dyes that absorb the imaging radiation (e.g. infrared absorbing dyes) and pigments or dyes that serve as colorants in the coating.
The coating advantageously comprises a “release agent” such as 4-hydroxybenzene sulfonic acid, sodium salt 4-HBSA, 4-hydroxybenzoic acid or sodium benzoate. In a different embodiment the release agent is disposed as a sub-coating between the hydrophilic substrate and the imageable coating.
Physical Transformation of Coating
The difference in adhesion of the imaged coating to the substrate can be demonstrated by a simple test using an adhesive tape. The tape is pressed by hand onto the developed coated areas for the plate of
It is believed the fissures alone do not undermine the integrity of the non-imaged regions. Only after water at the surface penetrates through the coating to the substrate, does the adhesion deteriorate to the extent that the coating can be easily dislodged. The solubility of the stabilizer should be substantially 100% in the non-aqueous solvent used to formulate the imageable coating, but only partially soluble in water, preferably less than about 15%. As an example, if the stabilizer content in the coating is in the range of 5-15 wt % and the solubility of the stabilizer is 10%, the overall solubility of such (pre-imaged) coating is about 0.5-1.5 wt %. The water solubility must not be so great as to overcome the hardening of the imaged regions and compromise the ability of these areas to remain on the plate after water processing. The water solubility must be sufficient to facilitate the penetration through the non-imaged regions.
Coating Chemistry
The following tables contain descriptions of the coating constituents and variations in the percentage content, associated with multiple examples. In each instance, the plates were prepared in a conventional manner in a laboratory, with conventional coating weight of 100 mg/sq. ft., drawn down with a wire wound stainless steel rod, and dried for two minuets at 90° C. All plates had a topcoat of PVOH at 140 mg/sq. ft. All plates having triazine were imageable with UV, and all plates with a dye sensitive to 830 nm light source, such as the KF-1151, were imageable with IR. The results reported with each table are based on conventional IR imaging at about 90-100 mj/sq. cm. A dash in a column indicates that the wt % value is the same as the entry in the previous column of the same row.
A coating formulation for a basic plate that contains a polymer, a monomer, a radically polymerizable monomer, an initiator system capable of generating radicals, and a DTTDA stabilizer can readily be produced, for processing with only water or fountain fluid. The strong wiping action of the press roll against the plate facilitates such removal.
If the plates are to be processed in a dedicated station upstream of the press by immersion in water and a wiping action milder than what a plate experiences on-press, the stabilizer could be augmented by a release agent, as shown in Table 1. Plate #4 of Table 1, in which the coating had 0.40 wt % DTTDA stabilizer and 0.12 wt % 4-HBSA release agent, exhibited the best results.
Table 2 shows that for a given polymer (Clar. Poly 123) and monomer (Sartomer 399) combination, the relative weight percent is a significant variable. Ratios of monomer to polymer in the range of at least about 1:1 to about 5:1 are likely to work well, given that the ratio of 0.5:1 (Plate #4) produced only fair results, the ratio of 4:1 (Plate #3) produced excellent results, and the ratio of about 9:1 (Plate #2) produced only fair results.
Table 3 shows the result that satisfactory plates can be made from polymer resins that do not necessarily have a reaction to radiation exposure. The coatings of Plates #1 and #3 have reactive resins that produced good results, and the coatings of Plates #4 and #5 have non-reactive resins that produced good to fair results. The potential for use of non-reactive resins opens the door for use of resins having a much higher molecular weight than presently used resins.
Table 4 demonstrates that not all monomers at a given weight percent of the coating, produce equivalent results, with some producing poor results. Similarly, Table 5 demonstrates that potential stabilizers other than DTTDA that are soluble in the non-aqueous solution and are partially soluble in water, do not necessarily produce satisfactory results.
Table 6 demonstrates that potential release agents other than 4-HBSA that are fully soluble in both non-aqueous solutions and water can be successfully utilized.
Table 7 demonstrates that a coating that is sensitive to both UV and IR radiation can be successfully imaged and processed in water according to the invention.
Table 8 demonstrates that good results do not depend on use of only one kind of initiator.
Table 9 shows that the use of coinitiator compounds and/or post-imaging heating, can improve the performance of the plates.
In Table 9 the organo-borate compound is P3B, made by Showa Denko K.K., headquartered in Tokyo, Japan. The P3B can be used as the sole initiator. It is believed that used individually, the listed initiators would rank from strongest to weakest as Diphenyl Iodonium hexaflouro phosphate, Triazine AC, and P3B. The reason for using a coinitiator system rather then increasing a single initiator is that there is a synergistic effect between the organo-borate and either the triazine or onium catalyst. Given a fixed amount of energy the initiators individually (at their optimum level) will only produce a certain amount of free radicals. However, when the organo-borate is combined with one of the other catalysts, free radicals are generated at a faster rate by the triazine or onium catalyst while free radicals are still generated (at a normal rate) from the organo-borate. Therefore the efficiency of the system is increased in both rate and population. By using this combination, a much higher degree of cross-linking is realized, which improves both adhesion and cohesion of the image. With an increase in adhesion and cohesion, an increased amount of release agent can be used, thereby providing for better development.
Depending on the type of equipment used for the post-imaging thermal enhancement, a different range of times and temperatures should be used. With a convection oven, both the temperature and dwell time are greater than with a small preheat oven unit (where the plate comes in direct contact with the heating element). As a rough guide, 200 deg. F. at 1 minute in a convection oven has approximately the same effect as 175 deg. F. for 7 seconds in a preheat oven. With a typical commercially available preheat unit, the window would be 175 to 250 deg. F. for a time period of 5 to 15 seconds.
Tests were also run on the six formulations shown in Table 9, for comparison of UV versus IR exposures. Previous formulations which did not contain the organo-borate co-initiator system were UV sensitive only when they contained the Triazine AC. The onium salt by itself was not UV sensitive. Incorporating the organo-borate into the formulation rendered the formulations that contained the onium salt UV sensitive. All six of the formulations that contained the co-initiator system produced a good image when exposed to either IR or UV. In order to simplify the testing formulation #5 was chosen for testing in UV exposures.
Using an Ugra scale for comparison, plates were exposed for 250, 125 and 62.5 mjs. The plates were then developed through a water bath with two molleton socks at 4 feet per minute at 75 degrees F. The resulting step wedges were 250 mj—solid 9 steps with 2 gray steps to a total of 11, 125 mj—solid 7 steps with 2 gray steps to a total of 9 and 62.5 mj—solid 5 steps with 2 gray steps to a total of 7. All of the images from the different exposures exhibited very good solvent resistance. The best resolution that was received was at 62.5 mjs, which yielded an open 15 micron line target and good screen values from 2% to 99%.
(a) Solvent (1-Methoxy-2-Propanol, Propylene Glycol Methyl Ether available from Arco Chemical Company)
(b) Monomer (Dipentaerythritol Monohydroxypentaacrylate available from Sartomer Company, West Chester, Penn.)
(c) Polymer
(d) Initiator
(e) Stabilizer
(f) Release Agent
(g) Dye
(h) Pigment
This application claims priority under 35 U.S.C. §119(e) from U.S. Provisional Application No. 60/704,140 filed Jul. 29, 2005, for “Imageable Printing Plate for On-Press Development”.
| Number | Name | Date | Kind |
|---|---|---|---|
| 3136637 | Larwon et al. | Jun 1964 | A |
| 3867150 | Ketley | Feb 1975 | A |
| 3904412 | Serrien et al. | Sep 1975 | A |
| 4058443 | Murata et al. | Nov 1977 | A |
| 4123272 | Quinn | Oct 1978 | A |
| 4186006 | Kobayashi et al. | Jan 1980 | A |
| 4229520 | Bratt et al. | Oct 1980 | A |
| 4315065 | Pigeon et al. | Feb 1982 | A |
| 4329422 | Langlais | May 1982 | A |
| 4370406 | Jones | Jan 1983 | A |
| 4391940 | Kuhls et al. | Jul 1983 | A |
| 4468453 | Nakamura et al. | Aug 1984 | A |
| 4533620 | Walls et al. | Aug 1985 | A |
| 4562142 | Kakumaru et al. | Dec 1985 | A |
| 4563410 | De Jaeger et al. | Jan 1986 | A |
| 4645730 | Fromson et al. | Feb 1987 | A |
| 4708925 | Newman | Nov 1987 | A |
| 4956261 | Pawlowski et al. | Sep 1990 | A |
| 5141841 | Wade | Aug 1992 | A |
| 5216201 | Ohishi et al. | Jun 1993 | A |
| 5227265 | DeBoer et al. | Jul 1993 | A |
| 5254429 | Gracia et al. | Oct 1993 | A |
| 5260180 | Sahyun et al. | Nov 1993 | A |
| 5319422 | Ohishi et al. | Jun 1994 | A |
| 5337113 | Kagawa et al. | Aug 1994 | A |
| 5344731 | Deboer et al. | Sep 1994 | A |
| 5395734 | Vogel et al. | Mar 1995 | A |
| 5480752 | Nishikiori et al. | Jan 1996 | A |
| 5484684 | Telser et al. | Jan 1996 | A |
| 5503074 | Hirano et al. | Apr 1996 | A |
| 5506090 | Gardner, Jr. et al. | Apr 1996 | A |
| 5552260 | Vogel et al. | Sep 1996 | A |
| 5571658 | Sonokawa et al. | Nov 1996 | A |
| 5698361 | Aoshima | Dec 1997 | A |
| 5786122 | Konrad et al. | Jul 1998 | A |
| 5871883 | Hirano et al. | Feb 1999 | A |
| 5888696 | Hirano et al. | Mar 1999 | A |
| 5925490 | Loerzer et al. | Jul 1999 | A |
| 5939237 | Gardner, Jr. et al. | Aug 1999 | A |
| 6228559 | Oda | May 2001 | B1 |
| 6335144 | Murota et al. | Jan 2002 | B1 |
| 6423471 | Sorori et al. | Jul 2002 | B1 |
| 6468711 | Sorori et al. | Oct 2002 | B1 |
| 6475700 | Higashi et al. | Nov 2002 | B1 |
| 6569603 | Furukawa | May 2003 | B2 |
| 6590011 | Rappoport et al. | Jul 2003 | B1 |
| 6645403 | Park et al. | Nov 2003 | B1 |
| 6686127 | Sonokawa | Feb 2004 | B2 |
| 6689537 | Urano et al. | Feb 2004 | B2 |
| 6723495 | Ray et al. | Apr 2004 | B2 |
| 6727044 | Fujimaki et al. | Apr 2004 | B1 |
| 6727045 | Fuji | Apr 2004 | B2 |
| 6749995 | Matsumura | Jun 2004 | B2 |
| 6841336 | Kondo | Jan 2005 | B2 |
| 6878505 | Shibuya | Apr 2005 | B2 |
| 6884561 | Fromson et al. | Apr 2005 | B2 |
| 6899994 | Huang et al. | May 2005 | B2 |
| 6899998 | Figov | May 2005 | B2 |
| 7011928 | Takamuki | Mar 2006 | B2 |
| 7041429 | Ohta et al. | May 2006 | B2 |
| 7041431 | Urano | May 2006 | B2 |
| 7189494 | Knight et al. | Mar 2007 | B2 |
| 20030054282 | Fromson et al. | Mar 2003 | A1 |
| 20030186165 | Gries et al. | Oct 2003 | A1 |
| 20030207202 | Fujita et al. | Nov 2003 | A1 |
| 20050069811 | Mitsumoto et al. | Mar 2005 | A1 |
| 20050123853 | Munnelly et al. | Jun 2005 | A1 |
| 20050130064 | West et al. | Jun 2005 | A1 |
| 20050266350 | Suzuki et al. | Dec 2005 | A1 |
| 20060024614 | Williamson | Feb 2006 | A1 |
| 20060046191 | Sakata | Mar 2006 | A1 |
| 20060046199 | Mitsumoto et al. | Mar 2006 | A1 |
| 20060188814 | Sakata | Aug 2006 | A1 |
| 20060254738 | Anderson et al. | Nov 2006 | A1 |
| 20070009829 | Teng | Jan 2007 | A1 |
| 20070072127 | Teng | Mar 2007 | A1 |
| 20070101886 | Teng | May 2007 | A1 |
| 20070172765 | Teng | Jul 2007 | A1 |
| 20070214987 | Sonokawa et al. | Sep 2007 | A1 |
| Number | Date | Country |
|---|---|---|
| WO 02051639 | Jul 2002 | WO |
| Number | Date | Country | |
|---|---|---|---|
| 20070026342 A1 | Feb 2007 | US |
| Number | Date | Country | |
|---|---|---|---|
| 60704140 | Jul 2005 | US |
