This invention pertains to the field of roll-to-roll electroless plating, and more particularly to a system and method for providing low dissolved oxygen content in the plating solution.
Electroless plating, also known as chemical or auto-catalytic plating, is a non-galvanic plating process that involves chemical reactions in an aqueous plating solution that occur without the use of external electrical power. Typically, the plating occurs as hydrogen is released by a reducing agent and oxidized, thus producing a negative charge on the surface of the part to be plated. The negative charge attracts metal ions out of the plating solution to adhere as a metalized layer on the surface. Using electroless plating to provide metallization in predetermined locations can be facilitated by first depositing a catalytic material in the predetermined locations. This can be done, for example by printing features using an ink containing a catalytic component.
Touch screens are visual displays with areas that may be configured to detect both the presence and location of a touch by, for example, a finger, a hand or a stylus. Touch screens may be found in televisions, computers, computer peripherals, mobile computing devices, automobiles, appliances and game consoles, as well as in other industrial, commercial and household applications. A capacitive touch screen includes a substantially transparent substrate which is provided with electrically conductive patterns that do not excessively impair the transparency—either because the conductors are made of a material, such as indium tin oxide, that is substantially transparent, or because the conductors are sufficiently narrow that the transparency is provided by the comparatively large open areas not containing conductors. For capacitive touch screens having metallic conductors, it is advantageous for the features to be highly conductive but also very narrow. Capacitive touch screen sensor films are an example of an article having very fine features with improved electrical conductivity resulting from an electroless plated metal layer.
Projected capacitive touch technology is a variant of capacitive touch technology. Projected capacitive touch screens are made up of a matrix of rows and columns of conductive material that form a grid. Voltage applied to this grid creates a uniform electrostatic field, which can be measured. When a conductive object, such as a finger, comes into contact, it distorts the local electrostatic field at that point. This is measurable as a change in capacitance. The capacitance can be measured at every intersection point on the grid. In this way, the system is able to accurately track touches. Projected capacitive touch screens can use either mutual capacitive sensors or self capacitive sensors. In mutual capacitive sensors, there is a capacitor at every intersection of each row and each column. A 16×14 array, for example, would have 224 independent capacitors. A voltage is applied to the rows or columns. Bringing a finger or conductive stylus close to the surface of the sensor changes the local electrostatic field which reduces the mutual capacitance. The capacitance change at every individual point on the grid can be measured to accurately determine the touch location by measuring the voltage in the other axis. Mutual capacitance allows multi-touch operation where multiple fingers, palms or styli can be accurately tracked at the same time.
WO 2013/063188 by Petcavich et al. discloses a method of manufacturing a capacitive touch sensor using a roll-to-roll process to print a conductor pattern on a flexible transparent dielectric substrate. A first conductor pattern is printed on a first side of the dielectric substrate using a first flexographic printing plate and is then cured. A second conductor pattern is printed on a second side of the dielectric substrate using a second flexographic printing plate and is then cured. The ink used to print the patterns includes a catalyst that acts as seed layer during subsequent electroless plating. The electrolessly plated material (e.g., copper) provides the low resistivity in the narrow lines of the grid needed for excellent performance of the capacitive touch sensor. Petcavich et al. indicate that the line width of the flexographically printed material can be 1 to 50 microns.
Flexography is a method of printing or pattern formation that is commonly used for high-volume printing runs. It is typically employed in a roll-to-roll format for printing on a variety of soft or easily deformed materials including, but not limited to, paper, paperboard stock, corrugated board, polymeric films, fabrics, metal foils, glass, glass-coated materials, flexible glass materials and laminates of multiple materials. Coarse surfaces and stretchable polymeric films are also economically printed using flexography.
Flexographic printing members are sometimes known as relief printing members, relief-containing printing plates, printing sleeves, or printing cylinders, and are provided with raised relief images onto which ink is applied for application to a printable material. While the raised relief images are inked, the recessed relief “floor” should remain free of ink.
Although flexographic printing has conventionally been used in the past for printing of images, more recent uses of flexographic printing have included functional printing of devices, such as touch screen sensor films, antennas, and other devices to be used in electronics or other industries. Such devices typically include electrically conductive patterns.
To improve the optical quality and reliability of the touch screen, it has been found to be preferable that the width of the grid lines be approximately 2 to 10 microns, and even more preferably to be 4 to 8 microns. In addition, in order to be compatible with the high-volume roll-to-roll manufacturing process, it is preferable for the roll of flexographically printed material to be electroless plated in a roll-to-roll electroless plating system. More conventionally, electroless plating is performed by immersing the item to be plated in a tank of plating solution. However, for high volume uniform plating of features on both sides of the web of substrate material, it is preferable to perform the electroless plating in a roll-to-roll electroless plating system.
Roll-to-roll electroless plating systems are commercially available from Chemcut Corporation, for example. However, commercially available roll-to-roll electroless plating systems are adapted to be used with plating solutions that include a relatively high amount of dissolved oxygen, for example greater than three parts per million. Such plating solutions can work well for plating copper in the context of printed circuit board manufacture where the minimum line width is on the order of 100 microns. However, it has been found that such oxygen-rich plating solutions do not provide uniform metallization at high yield on features having line widths of 10 microns or less.
Dissolved oxygen content of an electroless plating solution influences the rate and quality of the plating. As indicated in U.S. Pat. No. 4,616,596 Helber Jr. et al., entitled “Electroless plating apparatus,” U.S. Pat. No. 4,684,545 to Fey et al., entitled “Electroless plating with bi-level control of dissolved oxygen,” and U.S. Patent Application Publication No. 2011/0214608 to Ivanov et al., entitled “Electroless Plating System,” increased oxygen content tends to stabilize plating and decrease the plating rate. Decreased oxygen content tends to increase plating activity.
It has been found that a copper electroless plating solution made by Enthone is well-suited to provide high quality plating on features having minimum line widths of 10 microns or less in a low dissolved oxygen content tank plating system, but not in a commercially available roll-to-roll electroless plating system. What is needed is a roll-to-roll plating system and method that can provide and maintain low dissolved oxygen content in the plating solution.
The present invention represents a roll-to-roll electroless plating system, comprising:
a reservoir containing plating solution;
a web advance system for advancing a web of media from an input roll through the plating solution in the reservoir to a take-up roll, wherein a plating substance in the plating solution is plated onto predetermined locations on a surface of the web of media as it is advanced through the plating solution in the reservoir; and
a distribution system for injecting an inert gas into the plating solution, wherein the distribution system includes an injector for injecting the inert gas into the plating solution, wherein the injector includes:
This invention has the advantage that the inert gas for reducing the amount of dissolved oxygen can be injected from a low pressure gas source into the plating solution downstream of a pump.
It has the additional advantage that the injector can form micro-bubbles of the inert gas which are more efficient at reducing the dissolved oxygen content in the plating solution.
It the further advantage that the injection of the inert gas reduces the amount of dissolved oxygen in the plating solution to provide dissolved oxygen levels appropriate for use with plating solutions whose performance degrades at higher levels of dissolved oxygen.
It is to be understood that the attached drawings are for purposes of illustrating the concepts of the invention and may not be to scale.
The present description will be directed in particular to elements forming part of, or cooperating more directly with, an apparatus in accordance with the present invention. It is to be understood that elements not specifically shown, labeled, or described can take various forms well known to those skilled in the art. In the following description and drawings, identical reference numerals have been used, where possible, to designate identical elements. It is to be understood that elements and components can be referred to in singular or plural form, as appropriate, without limiting the scope of the invention.
The invention is inclusive of combinations of the embodiments described herein. References to “a particular embodiment” and the like refer to features that are present in at least one embodiment of the invention. Separate references to “an embodiment” or “particular embodiments” or the like do not necessarily refer to the same embodiment or embodiments; however, such embodiments are not mutually exclusive, unless so indicated or as are readily apparent to one of skill in the art. It should be noted that, unless otherwise explicitly noted or required by context, the word “or” is used in this disclosure in a non-exclusive sense.
The example embodiments of the present invention are illustrated schematically and not to scale for the sake of clarity. One of ordinary skill in the art will be able to readily determine the specific size and interconnections of the elements of the example embodiments of the present invention.
References to upstream and downstream herein refer to direction of flow. Web media moves along a media path in a web advance direction from upstream to downstream. Similarly, fluids flow through a fluid line in a direction from upstream to downstream.
As described herein, the example embodiments of the present invention provide a roll-to-roll electroless plating system and methods for providing and maintaining low dissolved oxygen content in the plating solution. The roll-to-roll electroless plating system is useful for metalizing printed features in sensor films incorporated into touch screens. However, many other applications are emerging for printing and electroless plating of functional devices that can be incorporated into other electronic, communications, industrial, household, packaging and product identification systems (such as RFID) in addition to touch screens. In addition, roll-to-roll electroless plating systems can be used to plate items for decorative purposes rather than electronic purposes and such applications are contemplated as well.
The flexographic printing system 100 includes two print modules 120 and 140 that are configured to print on the first side 151 of substrate 150, as well as two print modules 110 and 130 that are configured to print on the second side 152 of substrate 150. The web of substrate 150 travels overall in roll-to-roll direction 105 (left to right in the example of
Each of the print modules 110, 120, 130, 140 includes some similar components including a respective plate cylinder 111, 121, 131, 141, on which is mounted a respective flexographic printing plate 112, 122, 132, 142, respectively. Each flexographic printing plate 112, 122, 132, 142 has raised features 113 defining an image pattern to be printed on the substrate 150. Each print module 110, 120, 130, 140 also includes a respective impression cylinder 114, 124, 134, 144 that is configured to force a side of the substrate 150 into contact with the corresponding flexographic printing plate 112, 122, 132, 142. Impression cylinders 124 and 144 of print modules 120 and 140 (for printing on first side 151 of substrate 150) rotate counter-clockwise in the view shown in
Each print module 110, 120, 130, 140 also includes a respective anilox roller 115, 125, 135, 145 for providing ink to the corresponding flexographic printing plate 112, 122, 132, 142. As is well known in the printing industry, an anilox roller is a hard cylinder, usually constructed of a steel or aluminum core, having an outer surface containing millions of very fine dimples, known as cells. Ink is provided to the anilox roller by a tray or chambered reservoir (not shown). In some embodiments, some or all of the print modules 110, 120, 130, 140 also include respective UV curing stations 116, 126, 136, 146 for curing the printed ink on substrate 150.
As the substrate 250 is advanced through the plating solution 210 in the pan 220, a metallic plating substance such as copper, silver, nickel or palladium is electrolessly plated from the plating solution 210 onto predetermined locations on one or both of a first surface 251 and a second surface 252 of the substrate 250. As a result, the concentration of the metal in the plating solution 210 in the pan 220 decreases and the plating solution 210 needs to be refreshed. To refresh the plating solution 210, it is recirculated between the sump 230 and the pan 220. A lower lift pump 232 moves plating solution 210 from the sump 230 through a pipe 233 to a lower flood bar 222 for distribution into the pan 220 below the substrate 250. Likewise, an upper lift pump 234 moves plating solution 210 from the sump 230 through a pipe 235 to an upper flood bar 224 for distribution into the pan 220 above the substrate 250. Excess plating solution 210 waterfalls back into the sump 230 at freefall return 236. Occasionally the plating solution 210 is chemically analyzed, for example by titration, and fresh plating solution 210, or components of the plating solution 210, are added to the sump 230 as needed. Air inlet tubes 240 are provided to provide additional oxygen to the plating solution 210 in sump 230 as needed.
Although the prior art roll-to-roll electroless plating system 200 shown in
As the substrate 350 is advanced through the plating solution 310 in pan 320, a metallic plating substance such as copper, silver, nickel or palladium is electrolessly plated from the plating solution 310 onto predetermined locations on one or both of a first surface 351 and a second surface 352 of the substrate 350. The predetermined locations can be provided, for example, by the prior printing of a catalytic ink.
A number of modifications have been made relative to the prior art similar to a configuration available from roll-to-roll electroless plating system 200 of
Modifications for reducing turbulence in the roll-to-roll electroless plating system 300 of
In addition to reducing splashing and other forms of turbulence, drain pipe 336 also reduces the exposure of plating solution 310 to ambient air. The top of drain pipe 336 is within the plating solution 310 in pan 320, and the bottom of drain pipe 336 is within the plating solution 310 in sump 330. Other measures for reducing the exposure of plating solution 310 to ambient air include providing a sump cover 338 and optionally providing a pan cover 328 (see
Preferred embodiments of the invention also include modifications that provide for the displacement of dissolved oxygen from the plating solution 310. This is done by injecting an inert gas into the plating solution 310 via a distribution system. As used herein, the term inert gas refers to a gas that does not take part in the chemical reactions necessary for electroless plating. Nitrogen is an example of such an inert gas. Another example of an inert gas would be argon. In various embodiments, the inert gas can also be injected into one or both of the sump 330 and pan 320.
Within the context of the present invention, micro-bubbles are defined as bubbles having a diameter between about one micron (one thousandth of a millimeter) and one millimeter. Since the ratio of surface area to volume of a sphere is inversely dependent upon diameter, micro-bubbles have a larger surface area to volume ratio than larger bubbles, thereby facilitating efficient dissolution into the plating solution 310. In addition, micro-bubbles tend to stay suspended longer in the plating solution 310 rather than rising and bursting rapidly. As described below, there are a variety of ways to inject the inert gas into the plating solution 310 in the form of micro-bubbles.
It is also advantageous to control the amount of flow of inert gas into the plating solution 310 according to a measured amount of dissolved oxygen in the plating solution 310. An oxygen sensor 360 can be immersed into, or periodically dipped into, the plating solution 310 to measure the dissolved oxygen content. The data from the oxygen sensor 360 can be provided to a controller 315 to control the rate of flow of inert gas injected into plating solution 310 from inert gas source 340 or inert gas source 345, for example by controlling flow rate through a needle valve (not shown).
An advantage of injecting inert gas on the low pressure inlet side of a pump is that the inert gas source 376 can be a low pressure source for improved flow control. However, a potential disadvantage of injecting inert gas into a pump inlet is cavitation damage within the pump.
In some embodiments, a static mixer (not shown) having a tortuous flow path around baffles can be inserted in-line with pipe 333 to facilitate dissolution of the inert gas micro-bubbles within the plating solution 310 being returned to pan 320 through pipe 333.
Although
For configurations where the inert gas is provided downstream of the outlet of a pump (i.e., on the high pressure side of the pump), it is advantageous to provide a local low pressure region where the inert gas can be injected. For example, in
Having described exemplary embodiments of the roll-to-roll electroless plating system 300, a context has been provided for describing further details of methods for controlling the dissolved oxygen content to be at its desired low range (e.g., in the range of about 0.5 to about 2 parts per million). As described above, an amount of dissolved oxygen in the plating solution 310 is measured using oxygen sensor 360. The measured amount of dissolved oxygen is compared to a target range of dissolved oxygen. If the measured amount of dissolved oxygen is greater than the target range of dissolved oxygen, then the rate of injecting the inert gas is increased, for example by further opening a needle valve through which the inert gas flows to increase the flow rate. If the measured amount of dissolved oxygen is less than the target range of dissolved oxygen, then the rate of injecting the inert gas is decreased, for example by further closing a needle valve through which the inert gas flows to decrease the flow rate.
In some embodiments, the measuring of the amount of dissolved oxygen can be repeated at specified time intervals, for example once every five minutes or once every hour. During start-up of the electroless plating process, prior to injecting inert gas, the plating solution 310 tends to be somewhat oxygen rich. Therefore, it can be advantageous to measure the dissolved oxygen content at a relatively high repetition frequency (e.g., once every five minutes) during a start-up phase, and then to measure the dissolved oxygen content at a lower repetition frequency (e.g., once per thirty minutes) after the system has stabilized and the dissolved oxygen content has reached the target range.
In some embodiments, measurement of dissolved oxygen content can also be initiated by the controller 315 if it detects that an environmental condition has changed. For example, a measurement can be initiated if the controller 315 senses that the temperature of the plating solution 310 has changed by more than a predetermined threshold, as gas solubility is a function of temperature.
In some embodiments, measurement of dissolved oxygen content can also be initiated when a system operating condition changes. For example, a measurement can be initiated if the pan cover 328 is removed for service, thereby exposing the surface of the plating solution 310 to the air. Likewise, a measurement can be initiated when fresh plating solution 310, or components of the plating solution 310, are added to the sump 330.
In some embodiments, measurement of dissolved oxygen content can also be initiated when an indication is detected that the system may not be performing in the intended manner. For example, a measurement can be initiated if it is observed that elements of the plating solution 310 are plating onto extraneous surfaces other than the intended features on the substrate 250.
In some embodiments, a user interface can be provided to enable the measurement of dissolved oxygen to be manually initiated by an operator. For example, if it is observed that the system performance has been degraded.
For embodiments where the inert gas is injected into the plating solution 310 for delivery into both the sump 330 and the pan 320, the rates of injection can be independently controlled by controller 315. For example, the injection of the inert gas into the plating solution 310 for delivery into the sump 330 can be done at a first rate, and the injection of inert gas into the plating solution 310 for delivery into the pan 320 can be done at a second rate that is different from the first rate.
Alternatively, in some embodiments conductive pattern 450 can be printed using one or more print modules configured like print modules 110 and 130, and conductive pattern 460 can be printed using one or more print modules configured like print modules 120 and 140 of
With reference to
The invention has been described in detail with particular reference to certain preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.
Reference is made to commonly-assigned, co-pending U.S. patent application Ser. No. ______ (Docket K001833), entitled “Roll-to-roll electroless plating system with low dissolved oxygen content” by G. Wainwright et al.; and to commonly-assigned, co-pending U.S. patent application Ser. No. ______ (Docket K001834), entitled “Method for roll-to-roll electroless plating with low dissolved oxygen content” by G. Wainwright et al., each of which is incorporated herein by reference.