WO2016181791A1 - Image developing device, image developing method, pattern forming device, and pattern forming method - Google Patents

Image developing device, image developing method, pattern forming device, and pattern forming method Download PDF

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Publication number
WO2016181791A1
WO2016181791A1 PCT/JP2016/062742 JP2016062742W WO2016181791A1 WO 2016181791 A1 WO2016181791 A1 WO 2016181791A1 JP 2016062742 W JP2016062742 W JP 2016062742W WO 2016181791 A1 WO2016181791 A1 WO 2016181791A1
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WIPO (PCT)
Prior art keywords
substrate
developer
pattern
developing
nozzle
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PCT/JP2016/062742
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French (fr)
Japanese (ja)
Inventor
浩行 小林
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富士フイルム株式会社
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Publication of WO2016181791A1 publication Critical patent/WO2016181791A1/en

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means
    • G06F3/0446—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means using a grid-like structure of electrodes in at least two directions, e.g. using row and column electrodes
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34

Definitions

  • the present invention relates to a developing device and a developing method for forming a pattern on both surfaces of a substrate, a pattern forming device having a developing device, and a pattern forming method using the developing method, and in particular, high-accuracy development that suppresses development unevenness and the like.
  • Development device and development method that can increase pattern accuracy, high-precision development and high-accuracy cleaning that suppresses uneven cleaning, etc., and at least high-precision development can be performed, and pattern accuracy is high
  • the present invention relates to a pattern forming apparatus and a pattern forming method.
  • touch panel sensors have been widely used as input devices for portable terminals and computers.
  • the touch panel sensor is disposed on the surface of the display, detects a touched position of a finger or the like, and performs an input operation.
  • the transparent conductive film is often composed of ITO (indium tin oxide).
  • ITO indium tin oxide
  • there are various uneasy factors such as the yield by vapor deposition manufacturing. From such a background, the adoption of a transparent conductive film that is made into a thin mesh by using a common metal such as copper or silver has been started.
  • the transparent conductive film in a mesh state can be produced with a high yield and has a low resistance characteristic, the quantity is increasing more and more because it can cope with a large area.
  • Patent Document 1 discloses a high pattern accuracy while using a spray development method when patterning a resin relief plate for forming an organic EL element having a large size by a relief printing method, using a photolithography method. And a method of making a plate without development unevenness is described.
  • a development stage in which an unnecessary portion of the photosensitive resin after exposure is removed and developed with a developer sprayed from a spray-type jet nozzle, and development on the photosensitive resin after development is performed.
  • the plate material transport section In the cleaning stage in which the liquid residue is removed by the cleaning liquid sprayed from the spray-type jet nozzle, the plate material transport section has an angle inclined with respect to a horizontal plane perpendicular to the transport direction.
  • Patent Document 1 it is assumed that a new cleaning liquid always exists on the substrate without the developer staying on the substrate because the plate material transport section has an inclined angle. However, even if the developer is tilted, the developer may remain on the surface of the substrate only by its own weight, so that the replacement of the developer is stagnant, and the development time that is substantially exposed to the developer varies depending on the location of the substrate. However, there is a problem that the pattern accuracy does not necessarily increase due to the occurrence of uneven development or the retention of foreign matter. Moreover, in patent document 1, it is development and washing
  • An object of the present invention is to solve the problems based on the above-described conventional technology, perform high-accuracy development that suppresses development unevenness and the like, and can develop a developing apparatus and development method that can increase pattern accuracy, high-accuracy development and It is an object of the present invention to provide a pattern forming apparatus and a pattern forming method capable of performing at least high-accuracy development among high-accuracy cleaning that suppresses unevenness of cleaning and the like, and can increase pattern accuracy.
  • a first aspect of the present invention is a developing device for developing a substrate in which photosensitive layers formed on both sides of a support are exposed in a predetermined pattern
  • a developing device characterized by having a jetting unit that jets a developer in a fine granular form intermittently on the photosensitive layer on the front surface and the photosensitive layer on the back surface of a substrate held vertically. It is to provide.
  • the fine granular developer preferably has a particle size of 5 mm or less.
  • the ejection unit preferably ejects liquid at the same timing in the same position in the vertical direction with respect to the front surface and the back surface of the substrate.
  • the ejection unit includes a nozzle that ejects a liquid, and the ejection range of the developer ejected from the nozzle is preferably equal to or less than a horizontal plane that passes through the nozzle and the front and back surfaces of the substrate.
  • a pattern of receiving wiring that constitutes the sensor area in the capacitive touch panel sensor is formed, and on the other side of the photosensitive layer, the transmission layer that constitutes the sensor area is formed. It is preferable that a pattern of trusted wiring is formed. It is preferable that the predetermined pattern formed on the photosensitive layers on both sides of the substrate support includes at least a lattice pattern.
  • a second aspect of the present invention is a developing method for developing a substrate in which photosensitive layers formed on both sides of a support are exposed in a predetermined pattern, with the substrate held vertically, It is an object of the present invention to provide a developing method characterized by having a developing step in which a developer is finely granulated and ejected intermittently on the photosensitive layer on the front surface and the photosensitive layer on the back surface of the substrate.
  • the substrate is relatively moved in the vertical direction so that the developer is finely granular and ejected intermittently.
  • the fine granular developer preferably has a particle size of 5 mm or less.
  • the developer is ejected from the nozzle, and the ejection range of the developer ejected from the nozzle is preferably not more than a horizontal plane passing through the nozzle and the front surface and the back surface of the substrate.
  • a third aspect of the present invention is a pattern forming apparatus that includes at least a developing device and a cleaning device and forms a pattern on both surfaces of a substrate, and at least the developing device of the developing device and the cleaning device is held vertically.
  • the liquid is a developer, and has a jetting unit that intermittently jets the developer into fine particles on the photosensitive layer on the front surface and the photosensitive layer on the back surface of the substrate.
  • the liquid is a cleaning liquid, and a pattern forming apparatus is provided. It is preferable to have a moving unit that relatively moves the substrate and the injection unit in the vertical direction.
  • the fine granular liquid preferably has a particle size of 5 mm or less.
  • the ejection unit preferably ejects liquid at the same timing in the same position in the vertical direction with respect to the front surface and the back surface of the substrate.
  • the ejection unit includes a nozzle that ejects liquid, and the ejection range of the liquid ejected from the nozzle is preferably equal to or less than a horizontal plane that passes through the nozzle and the front and back surfaces of the substrate. It is preferable that the substrate has a photosensitive layer formed on both sides of the support.
  • a pattern forming method for forming a pattern on both sides of a substrate, wherein the photosensitive layer formed on both sides of the support is exposed vertically to a predetermined pattern.
  • a developing process in which a developer is intermittently sprayed into a fine granular form on the photosensitive layer on the front surface and the photosensitive layer on the back surface, and a state in which the substrate is further held vertically after the developing process
  • the present invention provides a pattern forming method comprising a cleaning step of intermittently spraying a cleaning liquid in a fine granular form on the photosensitive layer on the front surface of the substrate and the photosensitive layer on the back surface.
  • the substrate is relatively moved in the vertical direction so that the developer and the cleaning liquid are finely granulated and intermittently ejected.
  • the fine granular developer and the fine granular cleaning liquid preferably have a particle size of 5 mm or less.
  • the developing process injects the developing solution at the same timing in the vertical direction with respect to the front and back surfaces of the substrate, and the cleaning process is the same at the same position in the vertical direction with respect to the front and back surfaces of the substrate. It is preferable to spray the cleaning liquid at the timing.
  • the developer is ejected from the nozzle, and the ejection range of the developer ejected from the nozzle is preferably not more than a horizontal plane passing through the nozzle and the front surface and the back surface of the substrate.
  • the cleaning liquid is sprayed from the nozzle, and the spraying range of the cleaning liquid sprayed from the nozzle is preferably below the horizontal plane passing through the nozzle and the front surface and the back surface of the substrate.
  • the developing device and the developing method of the present invention it is possible to perform highly accurate development with suppressed development unevenness and the like, and it is possible to increase pattern accuracy.
  • the pattern forming apparatus and the pattern forming method of the present invention at least high-level development can be performed among high-precision development that suppresses development unevenness and high-accuracy cleaning that suppresses unevenness of cleaning, and the like. Can be high.
  • ⁇ is a numerical value ⁇ to a numerical value ⁇
  • the range of ⁇ is a range including the numerical value ⁇ and the numerical value ⁇ , and expressed by mathematical symbols, ⁇ ⁇ ⁇ ⁇ ⁇ .
  • Optically transparent and simply transparent are both light transmittances of at least 60%, preferably 80% or more, more preferably 90% or more, in the visible light wavelength range of 400 to 800 nm. Even more preferably, it is 95% or more.
  • the light transmittance is measured by using, for example, “plastic—how to obtain total light transmittance and total light reflectance” defined in JIS K 7375: 2008.
  • “same”, “same” and “simultaneous” include an error range generally allowed in the technical field. “Different” means that the above “same”, “same”, and “simultaneous” regulations are not satisfied.
  • FIG. 1 is a schematic diagram showing a pattern forming apparatus according to an embodiment of the present invention.
  • FIG. 2 is a schematic cross-sectional view showing an example of a substrate on which both sides are exposed
  • FIG. 3 is a schematic cross-sectional view showing another example of a substrate on which both sides are exposed.
  • a pattern forming apparatus 10 shown in FIG. 1 forms a pattern on both surfaces of a substrate 20.
  • the configuration of the pattern forming apparatus 10 is appropriately determined by the pattern forming method.
  • the pattern forming apparatus 10 includes an exposure device 12, a developing device 14, and a cleaning device 16. It is not always necessary to perform exposure with the pattern forming apparatus 10, and since the exposed substrate 20 can be used, the pattern forming apparatus 10 only needs to include at least the developing device 14 and the cleaning device 16.
  • the substrate 20 has a pattern formed on both sides.
  • the pattern to be formed may be the same or different on both sides.
  • the substrate 20 is provided with an undercoat layer 32 on the surface 30 a of the support 30, and a photosensitive layer 34 is provided on the surface 32 a of the undercoat layer 32.
  • An undercoat layer 32 is provided on the back surface 30 b of the support 30, and a photosensitive layer 34 is provided on the surface 32 a of the undercoat layer 32.
  • an exposure mask (not shown) is arranged on the surface 34 a of the photosensitive layer 34, and the substrate 20 is exposed while being sandwiched between the exposure masks, and an exposure pattern is formed on each photosensitive layer 34. .
  • the surface 34 a of the photosensitive layer 34 on the surface 30 a side of the support 30 is the surface 20 a of the substrate 20, and the surface 34 a of the photosensitive layer 34 on the back surface 30 b side of the support 30 is the back surface 20 b of the substrate 20.
  • each photosensitive layer 34 is irradiated with the first exposure light L 1 or the second exposure light L 2 , so that the support 30 is prevented from being exposed to other exposure light.
  • the first exposure light L 1 or the second exposure light L 2 is provided with a subbing layer 32 in order to prevent the reaching.
  • the undercoat layer 32 also has an effect of improving the adhesion between the substrate 20 and the pattern forming on the substrate 20.
  • the undercoat layer 32 can enhance the adhesion between the substrate 20 and a plating layer constituting a pattern described later formed by exposing, developing and washing the photosensitive layer 34.
  • the undercoat layer 32 preferably has an effect of preventing exposure light and an effect of improving adhesion.
  • the undercoat layer 32 is in close contact. It may have only the effect of enhancing the effect of improving the property or improving the adhesion.
  • the front surface 31a and the back surface of the support 31 are not provided as in the substrate 21 shown in FIG.
  • the photosensitive layer 34 can be provided on each 31b.
  • the support 30, the undercoat layer 32, the photosensitive layer 34, and the support 31 of the substrate 20 will be described in detail later.
  • the support body 30 and the support body 31 are appropriately selected depending on the application. It may be transparent or opaque depending on the application.
  • the exposure apparatus 12 forms an exposure pattern of a pattern formed on both surfaces of the substrate 20.
  • the exposure pattern formed on the substrate 20 may be a positive type or a negative type.
  • An exposure pattern forming method by the exposure apparatus 12 is not particularly limited. For example, even if the exposure pattern is formed by surface exposure using an exposure mask, the exposure pattern may be formed by scanning a laser beam or an electron beam without using the exposure mask. The wavelength of the light source used for exposure is appropriately determined according to the photosensitive layer 34.
  • FIG. 4 is a schematic diagram illustrating a developing device according to an embodiment of the present invention
  • FIG. 5 is a schematic diagram illustrating an arrangement position of nozzles of the developing device according to the embodiment of the present invention. Note that the vertical direction V, the horizontal direction H, and the direction Z shown in FIGS. 4 and 5 are orthogonal to each other.
  • the developing device 14 includes a nozzle 40, a pump 42, a first tank 44, and a second tank 45.
  • the nozzle 40, the pump 42 and the first tank 44 are connected via a pipe 43.
  • a switching valve 46 is provided in the pipe 43 between the pump 42 and the first tank 44.
  • the second tank 45 is connected to the switching valve 46 via a pipe 43a.
  • a guide 47 and a motor 48 for moving the substrate 20 in the vertical direction V are provided.
  • the substrate 20 is provided on the guide 47 by a jig or the like (not shown), and the substrate 20 is pulled up in the vertical direction V by a motor 48 at a preset speed. Further, it is lowered downward by a motor 48 at a preset speed.
  • the guide 47 and the motor 48 constitute a moving part.
  • the nozzle 40 and the substrate 20 may be moved relative to each other, and are not limited to those that move the substrate 20.
  • the substrate 20 may be fixed and the nozzle 40 may be moved.
  • Each component of the developing device 14 is controlled by the control unit 49.
  • the nozzle 40, the pump 42, and the first tank 44 constitute an injection unit 41.
  • the injection unit 41 may include a second tank 45. In the developing device 14, the switching valve 46, the pipe 43a, and the second tank 45 are not necessarily provided.
  • a developer is stored in the first tank 44.
  • the developer is intermittently ejected from the nozzle 40 in a minute granular form by the pump 42.
  • the liquid in the second tank 45 can be ejected intermittently from the nozzle 40 by the pump 42 in the form of fine particles.
  • the fine granularity means that the particle diameter is 5 mm or less, preferably 2 mm or less.
  • a method for measuring the particle size of the developer will be described in detail later.
  • Intermittent injection refers to injection 1.5 times or less per second, that is, 1.5 Hz or less. In intermittent injection, it is preferably no more than once per second, i.e., 1 Hz or less, more desirably no more than once every 2 seconds, i.e., 0.5 Hz or less.
  • the lower limit value of the ejection in the intermittent ejection of the developer is not particularly limited because it varies depending on the type of the developer to be used, the ejection amount of the developer, and the surrounding environment. For example, when the developer is sprayed, if the developer is locally dried on the surface of the substrate, uneven development occurs, which is not preferable. For this reason, the lower limit value of the ejection in the intermittent ejection is appropriately set according to the condition where the developer does not dry locally. In this case, for each type of developer, a condition that does not dry locally can be obtained in advance based on the injection amount and the usage environment, and based on this, a lower limit value of injection in intermittent injection can be set in advance.
  • the nozzles 40 are arranged to face each other with a gap in the horizontal direction H, and a guide 47 is provided in the gap between the nozzles 40.
  • substrate 20 passes in the state hold
  • a plurality of, for example, four nozzles 40 are arranged at intervals in the direction Z.
  • the number of the nozzles 40 is appropriately set according to the size of the substrate 20 and the size of the ejection range Di of the nozzles 40. For this reason, there may be one nozzle 40.
  • the shape of the ejection range Di is appropriately set according to the size of the substrate 20 and is not particularly limited, and may be circular or quadrangular.
  • the configuration of the nozzle 40 is not particularly limited as long as the developer can be sprayed onto the photosensitive layer 34 of the substrate 20 in a fine granular form and in a wide spray range Ds.
  • the nozzle may be a shape.
  • the injection range Ds is also expressed by, for example, the injection angle ⁇ . Injection range Ds is preferably at most is also the nozzle 40 and the horizontal plane P H below passing through the surface 20a and rear surface 20b of the substrate 20. If the injection range Ds is less horizontal plane P H, it can be a droplet 50 adhered to the photosensitive layer 34 more easily fall downward 20c. Further, it is preferable that the injection range Ds is within the vertical plane Pv parallel to the center line C of the substrate 20 at the maximum.
  • the injection range Ds is preferably located between the horizontal plane P H and a vertical plane Pv described above. That is, it is preferable that the injection angle ⁇ is between the horizontal plane P H and a vertical plane Pv described above.
  • the structure of the pump 42 is not particularly limited as long as it can supply the developer or cleaning liquid from the first tank 44 and the second tank 45 to the nozzle 40 and eject the liquid intermittently.
  • a diaphragm type pump can be used as the pump 42.
  • the configuration of the first tank 44 and the second tank 45 is not particularly limited as long as liquid such as developer and cleaning liquid can be stored therein.
  • the first tank 44 and the second tank 45 are provided with a temperature adjustment unit such as a heater or a cooler for maintaining the internal liquid at the use temperature according to the use temperature of the developer and cleaning liquid stored. You may have.
  • a temperature adjustment unit such as a heater or a cooler for maintaining the internal liquid at the use temperature according to the use temperature of the developer and cleaning liquid stored. You may have.
  • the developer and the cleaning solution those suitable for the photosensitive layer 34 of the substrate 20 are appropriately used. For example, those containing water having a surface tension higher than that of the organic solvent are used.
  • the development processing is performed with the substrate 20 held vertically.
  • the vertical means that the angle of the center line C of the substrate 20 with respect to the horizontal direction H is 90 °. With respect to the vertical angle, an angle of 10 ° is allowed, and a range in which the angle with respect to the horizontal direction H is 80 ° to 100 ° is vertical in the present invention.
  • the exposed surface of the photosensitive layer 34 is wetted with the developer.
  • the developer component attacks the object to be developed, dissolves, and dissolves on the surface of the photosensitive layer 34.
  • the melted material is diffused or removed and further melted, so that there are four steps. These occur sequentially or simultaneously.
  • the developing device 14 since the substrate 20 is held vertically, the developer that has reached the surface of the photosensitive layer 34 contacts the surface of the photosensitive layer 34, and most of the developer flows downward by gravity.
  • the developing solution by the next intermittent jet further reaches the surface of the photosensitive layer 34 and flows downward after the development. That is, it is possible to always carry a fresh developer to the surface of the photosensitive layer 34 in the immediate vicinity.
  • the jetted developer also has the effect of scraping the developer on the surface of the photosensitive layer 34 downward. Since the developer is usually aqueous, it has an extremely high surface tension, the specific gravity of the developer is small, and the surface tension is high. For this reason, the liquid film on the surface of the photosensitive layer 34 tends to remain there. Therefore, it is difficult to switch between the old and new developing solutions by the mere self-weight effect, but the replacement of the developing solution on the surface of the photosensitive layer 34 can be activated by both the self-weight and the momentum of the jetted developing solution.
  • the developer is applied to the photosensitive layer 34 on the front surface 20 a of the substrate 20 and the photosensitive layer 34 on the back surface 20 b in a state where the substrate 20 is held vertically.
  • the surface area of the developer droplet 50 is increased, and the surface of the photosensitive layer 34 is easily adhered to the surface to increase the wettability.
  • the developer wettability is further improved by intermittently ejecting the developer.
  • the injection of the developer by the nozzle 40, the injection range Ds is set to lower than or equal to the horizontal plane P H, to move the droplet 50 of the developer that dissolves the object to be developed was below 20c of the substrate 20 It can be made easier. Further, the developer can be effectively used by setting the ejection range Ds to be within the vertical plane Pv.
  • the developer is sprayed on both surfaces of the substrate 20, but it is preferable to spray the developer at the same position in the vertical direction V at the same timing.
  • the control unit 49 controls the timing of ejecting the developer from the plurality of nozzles 40.
  • the substrate 20 can be kept neutral by spraying the developer from both sides of the substrate 20 to the same position in the vertical direction V of the substrate 20 at the same timing and applying pressure from both sides of the substrate 20.
  • the substrate 20 can be kept neutral by the pressure balance of the developer from both sides of the substrate 20, and the substrate 20 does not come into contact with the other in the horizontal direction H. Therefore, even when the substrate 20 is thinned, it can be dealt with. Further, the movement of the substrate 20 is also suppressed in the blur of the substrate 20 and can be developed smoothly. Further, by developing the both surfaces of the substrate 20 together, the developing process can be performed efficiently, and the pattern formation efficiency can be improved.
  • FIGS. 6 to 8 are schematic views showing the phenomenon method of the developing device according to the embodiment of the present invention in the order of steps.
  • the developing device 14 shown in FIGS. 6 to 8 shows the nozzle 40 and the substrate 20, and the other components are not shown.
  • the substrate 20 on which the photosensitive layers 34 formed on both surfaces of the support 30 are exposed in a predetermined pattern is disposed between the nozzles 40 as shown in FIG. Hold 20 vertically.
  • the pump 42 is driven, and the developer in the first tank 44 is intermittently ejected from the nozzle 40 in a minute granular form.
  • the developer is ejected at the same position in the vertical direction V of the substrate 20 at the same timing, that is, in synchronization, as described above.
  • the substrate 20 is lifted upward at a preset speed through a guide 47 by a motor 48 (see FIG. 4), and the substrate 20 is moved until reaching the end of the substrate 20 as shown in FIGS. Pull up.
  • the developer can be spread over the entire surface of the photosensitive layer 34 of the substrate 20 and can be developed uniformly.
  • the droplet 50 (see FIG. 4) on the surface of the photosensitive layer 34 flows to the lower portion 20c of the substrate 20, and the peeled off material generated by development can be easily removed.
  • the developing steps shown in FIGS. 6 to 8 may be repeated a plurality of times instead of once, and are appropriately determined according to the type of the photosensitive layer 34 or the type of the developer. In this case, it is preferable to perform the next development processing after the substrate 20 is changed from the state shown in FIG. 8 to the state shown in FIG. 6, that is, after the substrate 20 is lowered.
  • the particle size of the developer will be described.
  • the developer is ejected from the nozzle 40 in the form of fine particles.
  • the fine granularity means that the particle size is 5 mm or less, preferably 2 mm or less.
  • the lower limit value of the fine particles is the minimum size that can adhere to the substrate 20 and develop, and in this case, the particle size is about 0.1 mm.
  • the particle size is less than 0.1 mm, the particles are called floating particles, and the developer is difficult to adhere to the substrate 20, which is not preferable.
  • the particle size of the developer described above was measured as follows. The particle size of the developer is measured in a clean room controlled at a temperature of about 23 ⁇ 5 ° C. and a humidity of 55 ⁇ 5%.
  • FIG. 9 and 10 are schematic diagrams for explaining a method for measuring the particle size of the developer.
  • a device in which a pump 52 is connected to a nozzle 40 via a pipe 53 and a tank 54 for storing the developing solution is connected.
  • the developer in the tank 54 is ejected from the nozzle 40 by the pump 52.
  • the pump 52 is a diaphragm type pump, and the developer is ejected from the nozzle 40 at a frequency of once per second.
  • the developer is a 1% by mass sodium carbonate aqueous solution at 40 ° C.
  • the particle size of the developer is measured by momentarily taking in and out a polyethylene terephthalate sheet 56 (hereinafter simply referred to as a PET sheet 56) in a state where the developer is sprayed from the nozzle 40.
  • a PET sheet 56 polyethylene terephthalate sheet 56
  • the developer droplet 57 is placed on another droplet 58, so that the PET sheet 56 is instantaneously put in and out.
  • Droplets 57 were placed in the place where the developing time of the PET sheet 56 taken out and taken out was the shortest, and when confirmed, it was visually recognized as a hemispherical state.
  • the liquid droplet 57 was covered on the other liquid droplets 58 at the place where the developer was likely to have been applied for a long time, that is, on the side of the starting point 56b.
  • the cleaning device 16 cleans the substrate 20 with the developed substrate 20 held vertically. Since the cleaning device 16 has the same configuration as the above-described developing device 14 except that a cleaning solution is used instead of the developing solution, a detailed description thereof will be omitted. In the cleaning device 16, the cleaning liquid is stored in the first tank 44.
  • the developer on the surface of the developed photosensitive layer 34 is replaced with washing water.
  • the developer to be replaced is excluded from the surface of the photosensitive layer 34.
  • the developer slightly remaining on the surface of the photosensitive layer 34 is dissolved in the washing water that has been replaced.
  • the cleaning liquid that has reached the surface of the photosensitive layer 34 contacts the surface of the photosensitive layer 34, and most of the cleaning liquid flows downward by gravity.
  • the cleaning liquid by the next intermittent jet reaches the surface of the photosensitive layer 34 and flows downward after the cleaning.
  • the cleaning liquid is usually aqueous, it has an extremely high surface tension, the specific gravity of the cleaning liquid is small, and the surface tension is high. For this reason, the liquid film on the surface of the photosensitive layer 34 tends to remain there. Therefore, it is difficult to switch between the old and new cleaning liquids only by the self-weight effect, but the replacement of the cleaning liquid on the surface of the photosensitive layer 34 can be activated by both the self-weight and the momentum of the jetted cleaning liquid.
  • the cleaning liquid is applied to the photosensitive layer 34 on the front surface 20 a and the photosensitive layer 34 on the back surface 20 b of the substrate 20 that has been subjected to the development processing while the substrate 20 is held vertically.
  • the surface area of the droplet 50 of the cleaning liquid is increased so that it adheres to the surface of the photosensitive layer 34, thereby improving the wettability.
  • the ease of wetting of the cleaning liquid can be further improved by intermittently spraying the cleaning liquid.
  • the cleaning liquid can be effectively used by setting the injection range Ds to be within the vertical plane Pv.
  • the cleaning method using the cleaning device 16 is the same as the developing method except that the developing solution is replaced with a developing solution as compared with the developing method shown in FIGS. Omitted.
  • the cleaning method in order to make the substrate 20 neutral, it is preferable to spray the cleaning liquid at the same position in the vertical direction V of the substrate 20, that is, in synchronization. By cleaning the both surfaces of the substrate 20 together, the cleaning process can be performed efficiently.
  • the cleaning steps shown in FIGS. 6 to 8 may be repeated a plurality of times instead of once, and are appropriately determined according to the type of developer or the type of cleaning solution. In this case, it is preferable to perform the next cleaning process after the substrate 20 is changed from the state shown in FIG. 8 to the state shown in FIG. 6, that is, after the substrate 20 is lowered.
  • the cleaning liquid is intermittently ejected in fine particles, but the intermittent injection of the cleaning liquid has the same definition as the intermittent injection of the developer, This refers to an injection of 1.5 times or less, that is, 1.5 Hz or less per second. In intermittent injection, it is preferably no more than once per second, that is, 1 Hz or less, more desirably no more than once every 2 seconds, that is, 0.5 Hz or less.
  • the lower limit value of the ejection of the cleaning liquid intermittently varies depending on the type of the cleaning liquid to be used, the amount of the cleaning liquid to be sprayed, and the surrounding environment, and is not particularly limited.
  • the lower limit value of the injection in the intermittent injection is appropriately set according to the condition where the cleaning liquid is not locally dried.
  • the lower limit value of injection in intermittent injection can be set in advance.
  • the cleaning liquid is in the form of fine particles and is ejected from the nozzle 40 in the same manner as the developer.
  • the fine particles of the cleaning liquid have the same definition as the fine particles of the developer.
  • the fine particles in the cleaning liquid means that the particle size of the cleaning liquid is 5 mm or less, preferably 2 mm or less, and the lower limit is the minimum size that can be adhered to the substrate 20 and cleaned. In this case, the particle size is about 0.1 mm.
  • the particle size is less than 0.1 mm, the particles are called floating particles, and the cleaning liquid is difficult to adhere to the substrate 20, which is not preferable.
  • the method for measuring the particle size of the cleaning solution is the same as the method for measuring the particle size of the developing solution except that the cleaning solution is used, and thus detailed description thereof is omitted.
  • the developing solution is stored in the first tank 44, the cleaning solution is stored in the second tank 45, and the switching valve 46 is switched, so that the developing device 14 and the cleaning device 16 can be used as a single device. You can also In this case, the development process and the cleaning process can be performed continuously with one apparatus. Alternatively, the developing solution may be stored in the first tank 44, and after the development processing is completed, the developing solution in the first tank 44 may be replaced with the cleaning solution and used as the cleaning device 16.
  • the developing device 14 and the cleaning device 16 have the same configuration. However, the configuration is not limited to this, and the developing device 14 may have the above-described configuration, and the cleaning device 16 may have another configuration. In this case, for example, a slit-like nozzle extending in the width direction of the substrate 20 is provided, and a cleaning liquid is continuously sprayed from the slit-like nozzle to the entire surface of the photosensitive layer 34 of the substrate 20.
  • the pattern forming apparatus 10 may be either a single wafer type that processes each substrate 20 or a roll-to-roll type that processes continuously using a long substrate.
  • the developing device 14 and the cleaning device 16 process each substrate, and in the roll-to-roll method, the developing device 14 and the cleaning device 16 process the substrate continuously.
  • ⁇ Preparation of composition 94.9 parts by mass of isopropanol (IPA), 3 parts by mass of polyacrylic acid, 2 parts by mass of methylenebisacrylamide (MBA), 0.1 part by mass of IRGACURE (registered trademark) 127 (manufactured by BASF) were prepared according to this order.
  • IPA isopropanol
  • MSA methylenebisacrylamide
  • IRGACURE registered trademark
  • primer layer forming composition A solution obtained by dissolving 100 g of hydrogenated nitrile butadiene rubber Zetpol (registered trademark) 0020 (manufactured by Nippon Zeon) in 900 g of cyclopentanone (manufactured by Tokyo Chemical Industry) is used as a primer layer forming composition.
  • a primer layer forming composition is formed into a 2 ⁇ m film by bar coating on the front and back surfaces.
  • the primer layer is applied so as to be thick, and a primer layer is formed on both surfaces of the substrate to enhance the adhesion between the patterned plating layer (described later) and the substrate.
  • the primer layer corresponds to the above-described undercoat layer 32.
  • the above-described composition is formed on each primer layer by bar coating so as to have a thickness of, for example, 0.25 ⁇ m to form a photosensitive layer 34, and the substrate 20 to be exposed is obtained.
  • a UV lamp Deep UV Lamp capable of emitting the emitted light including light having a wavelength of 300 nm or less by sandwiching the substrate 20 to be exposed as described above with two masks having different patterns. (Usio) is used to expose the photosensitive layers 34 on both sides in a mask pattern so that the exposure energy is 100 mJ to obtain an exposed substrate 20.
  • exposure is performed with light having a wavelength of 300 nm or less, since the exposure light is absorbed by the support made of the above-described sheet, the influence of the exposure light of the other photosensitive layers 34 is suppressed.
  • the exposed substrate 20 is held vertically by the developing device 14 and the above-described development processing is performed twice.
  • a 1 mass% sodium carbonate aqueous solution at 40 ° C. is used as the developer.
  • the developing solution is replaced with a cleaning solution, and the developing device 14 is used as the cleaning device 16.
  • the developed substrate 20 is held vertically by the cleaning device 16 and the above-described cleaning process is performed twice.
  • 40 ° C. pure water is used as the cleaning liquid.
  • a patterned plating layer that is, a pattern is formed on both surfaces of the substrate 20.
  • the substrate 20 after the cleaning treatment is immersed in a 0.05% by mass rhodamine 6G aqueous solution for 5 minutes and dyed. And it can be confirmed by observing with an optical microscope whether the pattern-like to-be-plated layer arrange
  • the pattern forming method is not limited to the pattern forming method described above, and any pattern forming method can be used as long as it is subjected to development processing.
  • it can be used for pattern formation using a photolithography method for pattern formation.
  • it can be used for pattern formation by a silver salt method and pattern formation by a vapor deposition method.
  • pattern formation by the silver salt method first, a substrate on which silver salt emulsion layers containing silver halide are formed on both sides is prepared. Each silver salt emulsion layer of the substrate is subjected to exposure processing by the exposure device 12, and then development processing using the developing device 14 is performed. And a pattern can be formed by performing a washing process.
  • the method for producing a fine metal wire described in JP-A-2015-22397 can be used.
  • the cleaning process may be performed using the cleaning device 16.
  • a copper foil layer is formed on both surfaces of the substrate by vapor deposition.
  • a resist film is formed on each copper foil layer of the substrate.
  • Each resist film on the substrate is subjected to exposure processing by the exposure device 12, and thereafter development processing using the developing device 14 is performed.
  • Etching is then performed to form copper wiring from the copper foil layer.
  • an electrolytic copper foil can be used in addition to the deposited copper foil. More specifically, the step of forming a copper wiring described in JP 2014-29614 A can be used.
  • FIG. 11 is a schematic plan view showing an example of a pattern.
  • a pattern 60 shown in FIG. 11 is a lattice-shaped pattern, in which cells 64 are formed by thin lines 62, and a large number of cells 64 are combined to form a lattice-shaped pattern.
  • the pattern 60 is used for, for example, a detection electrode of a touch panel sensor.
  • Each cell 64 is configured by a polygon, for example. Examples of the polygon include a triangle, a square, a rectangle, a parallelogram, a quadrangle such as a rhombus, a pentagon, a hexagon, and a random polygon. Further, a part of the sides constituting the polygon may be a curve.
  • the length P of one side of the cell 64 of the pattern 60 is not particularly limited, but is preferably 50 to 500 ⁇ m, and more preferably 150 to 400 ⁇ m. When the length P of one side of the cell 64 is in the above-mentioned range, it is possible to keep the transparency better, and when it is attached to the front surface of the display device, it is possible to visually recognize the display. .
  • the aperture ratio of the pattern 60 formed by the thin lines 62 is preferably 85% or more, more preferably 90% or more, and most preferably 95% or more.
  • the aperture ratio is the ratio of the light-transmitting portion excluding the thin line 62 to the entire area.
  • the aperture ratio of a square lattice having a line width of 6 ⁇ m and a side length P of the cell 64 of 240 ⁇ m is 95%. is there.
  • the mesh shape may be a regular shape in which the same shape is regularly arranged, or may be a random shape.
  • a square, a rhombus, and a regular hexagon are preferable, and a rhombus is particularly preferable.
  • the acute angle is preferably 50 ° to 80 ° from the viewpoint of reducing moire with the display device.
  • the mesh pitch p (see FIG. 11) is preferably 50 ⁇ m to 500 ⁇ m, and the mesh opening ratio is preferably 92% to 99%.
  • the aperture ratio of the mesh is defined by the unoccupied area ratio of the conductor thin wires in the mesh portion.
  • the mesh-like metal electrode for example, a mesh-like mesh-like metal electrode disclosed in JP2011-129501A, JP2013-149236A, and the like can be used.
  • a detection electrode used for a capacitive touch panel can be used as appropriate.
  • the length P of one side of the cell 64, the mesh angle, and the aperture ratio of the mesh can be measured using, for example, an optical microscope, a laser microscope, a digital microscope, or the like.
  • FIG. 12 is a schematic plan view showing an example of a touch panel sensor formed by exposure
  • FIG. 13 is a schematic view showing an example of a mask pattern used for forming the touch panel sensor shown in FIG. 12
  • FIG. 12 is a schematic diagram showing another example of a mask pattern used for forming the touch panel sensor shown in FIG. 12 to 14, the same components are denoted by the same reference numerals, and detailed description thereof is omitted.
  • the first conductive pattern 70 shown in FIG. 13 is formed on the photosensitive layer 34 on the front surface 20a side of the substrate 20, and the photosensitive layer on the back surface 20b side.
  • a second conductive pattern 80 shown in FIG. two types of masks are prepared: an exposure mask in which the first conductive pattern 70 shown in FIG. 13 is formed as a mask pattern, and an exposure mask in which the second conductive pattern 80 shown in FIG. 14 is formed as a mask pattern. Exposure is performed by bringing an exposure mask into close contact with the front surface 20 a and the back surface 20 b of the substrate 20.
  • the first conductive pattern 70 shown in FIG. 13 includes a plurality of first detection electrode patterns 72 extending in the first direction and arranged in parallel. Each first detection electrode pattern 72 is connected to the first conductive terminal pattern 74 at one end thereof. Further, each first conductive terminal pattern 74 is connected to a conductive first wiring pattern 76.
  • a second conductive pattern 80 shown in FIG. 14 includes second detection electrode patterns 82 extending in a second direction orthogonal to the first direction and arranged in parallel. Each second detection electrode pattern 82 is connected to the second conductive terminal pattern 84 at one end thereof. Each second conductive terminal pattern 84 is connected to a conductive second wiring pattern 86.
  • Examples of the first conductive pattern 70 and the second conductive pattern 80 include, for example, Japanese Unexamined Patent Application Publication Nos. 2012-147277, 2012-163933, 2012-174748, 2012-190445, and Japanese Unexamined Patent Application Publication No. 2012-190445.
  • the electrode patterns described in JP2013-149237A, JP2013-149232A, and JP2013-149236A can be used. Furthermore, other than these, patterns described in Japanese Patent Application Publication No. 2011-513846 and International Publication No. 2010/013679 can be used.
  • the first detection electrode pattern 72, the first conductive terminal pattern 74, the second detection electrode pattern 82, and the second conductive terminal pattern 84 constitute a sensor region where touch detection can be performed in the touch panel sensor 69.
  • the first detection electrode pattern 72 is a pattern for forming the first detection electrode 69a (see FIG. 12).
  • the first detection electrode 69a is also called a reception wiring.
  • the first detection electrode pattern 72 is also a pattern for receiving wiring.
  • the second detection electrode pattern 82 is a pattern for forming the second detection electrode 69d (see FIG. 12).
  • the second detection electrode 69d is also called a transmission wiring.
  • the second detection electrode pattern 82 is also a transmission wiring pattern.
  • the first conductive terminal pattern 74 is a pattern for forming a first conductive terminal 69b (see FIG. 12) that is electrically connected to the first detection electrode 69a.
  • the first wiring pattern 76 is also a pattern for forming a first wiring 69c (see FIG. 12) that is electrically connected to the first conductive terminal 69b.
  • the second conductive terminal pattern 84 is a pattern for forming a second conductive terminal 69e (see FIG. 12) that is electrically connected to the second detection electrode 69d.
  • the second wiring pattern 86 is a pattern for forming a second wiring 69f (see FIG. 12) that is electrically connected to the second conductive terminal 69e.
  • the first conductive terminal 69b, the first wiring 69c, the second conductive terminal 69e, and the second wiring 69f are called peripheral wirings.
  • a voltage is applied to the second detection electrode 69d in a rectangular wave shape to accumulate charges, and the charges are read by the first detection electrode 69a.
  • the support is not particularly limited as long as it has two main surfaces, and examples thereof include an insulating support, and more specifically, a resin support, a ceramic support, a glass support, and the like. Resin supports are preferred.
  • the adhesive sheet mentioned later is also contained.
  • the resin support material include polyester resins (polyethylene terephthalate, polyethylene naphthalate), polyethersulfone, polyacrylic resin, polyurethane resin, polycarbonate resin, polysulfone resin, polyamide resin, and polyarylate. Examples thereof include resins, polyolefin resins, cellulose resins, polyvinyl chloride resins, cycloolefin resins, and the like.
  • polyethylene terephthalate polyethylene naphthalate, or polyolefin is preferable.
  • an adhesive support body ie, an adhesive sheet.
  • known materials acrylic pressure-sensitive adhesive, silicone pressure-sensitive adhesive, etc.
  • the thickness (mm) of the support is not particularly limited, but is preferably 0.01 to 2 mm, more preferably 0.02 to 1 mm, and more preferably 0 to 2 mm for the resin support in terms of the balance between handleability and thinning. 0.03-0.1 mm is most preferable. In the glass support, 0.01 to 2 mm is preferable, 0.3 to 0.8 mm is more preferable, and 0.4 to 0.7 mm is most preferable. Moreover, it is preferable that a support body permeate
  • the undercoat layer is formed of a layer containing an ultraviolet absorber (ultraviolet absorbing layer).
  • an ultraviolet absorber ultraviolet absorbing layer
  • the type of the UV absorber used in the undercoat layer and the support is not particularly limited, and a known UV absorber can be used, for example, a salicylic acid UV absorber, a benzophenone UV absorber, a benzotriazole Examples thereof include ultraviolet absorbers, cyanoacrylate ultraviolet absorbers, benzoate ultraviolet absorbers, malonic ester ultraviolet absorbers, and oxalic anilide ultraviolet absorbers.
  • a salicylic acid UV absorber examples include phenyl salicylate, p-tert-butylphenyl salicylate, and p-octylphenyl salicylate.
  • benzophenone-based ultraviolet absorber examples include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2 ′. -Dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, bis (2-methoxy-4-hydroxy-5-benzoylphenyl) ) Methane and the like.
  • benzotriazole-based UV absorber examples include 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2- (2′-hydroxy-5).
  • '-Methylphenyl) benzotriazole 2- (2'-hydroxy-5'-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3', 5'di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butyl-phenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butyl-5'-amylphenyl) benzotria Lumpur, 2- (2'-hydroxy-4'-octoxyphenyl) benzotriazo
  • cyanoacrylate-based ultraviolet absorber examples include 2-ethylhexyl-2-cyano-3,3′-diphenyl acrylate, ethyl-2-cyano-3,3′-diphenyl acrylate, and the like.
  • the undercoat layer may have an advantage of improving the adhesion as described above.
  • an undercoat layer having the following configuration can be used.
  • the thickness of the undercoat layer is not particularly limited, but is generally preferably 0.01 to 100 ⁇ m, more preferably 0.05 to 20 ⁇ m, and further preferably 0.05 to 10 ⁇ m.
  • the material for the undercoat layer is not particularly limited, and is preferably a resin having good adhesion to the substrate.
  • Specific examples of the resin may be, for example, a thermosetting resin, a thermoplastic resin, or a mixture thereof.
  • the thermosetting resin an epoxy resin, a phenol resin, a polyimide resin, a polyester resin, a bismaleimide resin, Examples include polyolefin resins and isocyanate resins.
  • thermoplastic resin examples include phenoxy resin, polyether sulfone, polysulfone, polyphenylene sulfone, polyphenylene sulfide, polyphenyl ether, polyether imide, and ABS resin.
  • the thermoplastic resin and the thermosetting resin may be used alone or in combination of two or more.
  • a resin containing a cyano group may be used.
  • a polymer including a unit having a cyano group in the side chain may be used.
  • a rubber component such as NBR rubber (acrylonitrile butadiene rubber) or SBR rubber (styrene butadiene rubber) can also be used.
  • the material constituting the undercoat layer is a polymer having a conjugated diene compound unit that may be hydrogenated.
  • the conjugated diene compound unit means a repeating unit derived from a conjugated diene compound.
  • the conjugated diene compound is not particularly limited as long as it is a compound having a molecular structure having two carbon-carbon double bonds separated by one single bond.
  • One preferred embodiment of the repeating unit derived from a conjugated diene compound includes a repeating unit produced by a polymerization reaction of a compound having a butadiene skeleton.
  • the conjugated diene compound unit may be hydrogenated.
  • the adhesion of the patterned metal layer is preferably improved. That is, the double bond in the repeating unit derived from the conjugated diene compound may be hydrogenated.
  • the above-mentioned interactive group may be contained in the polymer having a conjugated diene compound unit that may be hydrogenated.
  • this polymer examples include acrylonitrile butadiene rubber (NBR), carboxyl group-containing nitrile rubber (XNBR), acrylonitrile-butadiene-isoprene rubber (NBIR), acrylonitrile-butadiene-styrene copolymer (ABS resin), or These hydrogenated materials (for example, hydrogenated acrylonitrile butadiene rubber) and the like can be mentioned.
  • NBR acrylonitrile butadiene rubber
  • XNBR carboxyl group-containing nitrile rubber
  • NBIR acrylonitrile-butadiene-isoprene rubber
  • ABS resin acrylonitrile-butadiene-styrene copolymer
  • the undercoat layer contains other additives (for example, sensitizers, antioxidants, antistatic agents, ultraviolet absorbers, fillers, particles, flame retardants, surfactants, lubricants, plasticizers, etc.). May be.
  • additives for example, sensitizers, antioxidants, antistatic agents, ultraviolet absorbers, fillers, particles, flame retardants, surfactants, lubricants, plasticizers, etc.
  • the method for forming the undercoat layer is not particularly limited, and a method of laminating the resin to be used on the substrate, or a method in which a necessary component is dissolved in a soluble solvent, and coating and drying on the substrate surface by a method such as coating. Methods and the like.
  • the heating temperature and time in the coating method may be selected so that the coating solvent can be sufficiently dried, but from the viewpoint of production suitability, the heating temperature should be 200 ° C. or less and the heating condition within the range of 60 minutes. It is preferable to select heating conditions in the range of heating temperature 40 to 100 ° C. and time 20 minutes or less.
  • an optimal solvent for example, cyclohexanone or methyl ethyl ketone is appropriately selected according to the resin to be used.
  • the photosensitive layer is not particularly limited as long as it is a layer that is sensitized and cured by light irradiation, and a known photosensitive layer can be used. As described above, the photosensitive layer is formed by curing a portion exposed by the first exposure light L 1 and the second exposure light L 2 . Especially, as a photosensitive layer, it is preferable that it is a layer for to-be-plated layer formation for forming the to-be-plated layer to which a plating process is performed. In addition, a metal layer can be arrange
  • the layer for forming a layer to be plated may be any layer that can be exposed to light to form a predetermined pattern-shaped layer to be plated, and in particular, a polymerization initiator and the following compound X or composition Y: It is preferable that it is a layer containing.
  • Compound X a functional group that interacts with the plating catalyst or its precursor (hereinafter, also simply referred to as “interactive group”) and a compound composition having a polymerizable group Y: interaction with the plating catalyst or its precursor
  • interactive group a functional group that interacts with the plating catalyst or its precursor
  • a compound composition having a polymerizable group Y interaction with the plating catalyst or its precursor
  • the polymerization initiator is not particularly limited, and a known polymerization initiator (so-called photopolymerization initiator) or the like can be used.
  • polymerization initiators include benzophenones, acetophenones, ⁇ -aminoalkylphenones, benzoins, ketones, thioxanthones, benzyls, benzyl ketals, oxime esters, anthrones, tetramethylthiuram monosulfide Bisacylphosphine oxides, acylphosphine oxides, anthraquinones, azo compounds and the like, and derivatives thereof.
  • the content of the polymerization initiator in the layer to be plated forming layer is not particularly limited, but is 0.01 to from the total mass of the layer to be plated layer in terms of curability of the layer to be plated.
  • the content is preferably 5% by mass, more preferably 0.1 to 3% by mass.
  • Compound X is a compound having an interactive group and a polymerizable group.
  • the interactive group means a functional group capable of interacting with the plating catalyst or its precursor.
  • Nitrogen-containing functional groups, sulfur-containing functional groups, oxygen-containing functional groups and the like that can form a coordination with the body can be used.
  • a nitrogen-containing functional group such as nitro group, nitroso group, azo group, diazo group, azide group, cyano group, cyanate group; ether group, hydroxyl group, phenolic hydroxyl group, carboxylic acid group, carbonate group, carbonyl group, Ester group, group containing N-oxide structure, containing S-oxide structure Oxy
  • a salt thereof can also be used.
  • ionic polar groups such as carboxylic acid group, sulfonic acid group, phosphoric acid group, and boronic acid group, ether group, or A cyano group is particularly preferable, and a carboxylic acid group (carboxyl group) or a cyano group is more preferable.
  • Compound X may contain two or more interactive groups.
  • the polymerizable group is a functional group capable of forming a chemical bond by applying energy, and examples thereof include a radical polymerizable group and a cationic polymerizable group.
  • a radical polymerizable group is preferable from the viewpoint of more excellent reactivity.
  • radical polymerizable groups include acrylic acid ester groups (acryloyloxy groups), methacrylic acid ester groups (methacryloyloxy groups), itaconic acid ester groups, crotonic acid ester groups, isocrotonic acid ester groups, maleic acid ester groups, and the like.
  • Examples include unsaturated carboxylic acid ester groups, styryl groups, vinyl groups, acrylamide groups, and methacrylamide groups.
  • a methacryloyloxy group, an acryloyloxy group, a vinyl group, a styryl group, an acrylamide group, and a methacrylamide group are preferable, and a methacryloyloxy group, an acryloyloxy group, and a styryl group are more preferable.
  • compound X two or more polymerizable groups may be contained. Further, the number of polymerizable groups contained in the compound X is not particularly limited, and may be one or two or more.
  • the above-mentioned compound X may be a low molecular compound or a high molecular compound.
  • a low molecular weight compound intends a compound having a molecular weight of less than 1000
  • a high molecular weight compound intends a compound having a molecular weight of 1000 or more.
  • the low molecular compound having a polymerizable group described above corresponds to a so-called monomer.
  • the polymer compound may be a polymer having a preset repeating unit. Moreover, as a compound, only 1 type may be used and 2 or more types may be used together.
  • the weight average molecular weight of the polymer is not particularly limited, but is preferably 1,000 or more and 700,000 or less, and more preferably 2000 or more, in terms of better handling properties such as solubility. 200,000 or less. In particular, from the viewpoint of polymerization sensitivity, it is preferably 20000 or more.
  • the method for synthesizing such a polymer having a polymerizable group and an interactive group is not particularly limited, and a known synthesis method (see paragraphs [0097] to [0125] of Japanese Patent Publication No. 2009-280905) is used. Is done.
  • composition Y is a composition containing a compound having an interactive group and a compound having a polymerizable group. That is, the layer for forming a layer to be plated includes two types of compounds, that is, a compound having an interactive group and a compound having a polymerizable group. The definitions of the interactive group and the polymerizable group are as described above.
  • the compound having an interactive group is a compound having an interactive group. The definition of the interactive group is as described above.
  • Such a compound may be a low molecular compound or a high molecular compound.
  • a preferred embodiment of the compound having an interactive group is a polymer having a repeating unit, for example, polyacrylic acid.
  • the compound having an interactive group does not contain a polymerizable group.
  • the compound having a polymerizable group is a so-called monomer, and is preferably a polyfunctional monomer having two or more polymerizable groups in that the formed layer to be plated is more excellent in hardness. Specifically, it is preferable to use a monomer having 2 to 6 polymerizable groups as the polyfunctional monomer.
  • the molecular weight of the polyfunctional monomer used is preferably 150 to 1000, more preferably 200 to 700, from the viewpoint of molecular mobility during the crosslinking reaction that affects the reactivity.
  • the interval (distance) between a plurality of polymerizable groups is preferably 1 to 15 atoms, and more preferably 6 or more and 10 or less.
  • the compound having a polymerizable group may contain an interactive group.
  • the mass ratio of the compound having an interactive group and the compound having a polymerizable group is not particularly limited. From the viewpoint of the balance between the strength of the layer to be plated and the suitability for plating, 0.1 to 10 is preferable, and 0.5 to 5 is more preferable.
  • the content of the compound X or the composition Y in the layer for forming a plating layer is not particularly limited, but is preferably 50% by mass or more, and 80% by mass or more with respect to the total mass of the layer for forming a layer to be plated. Is more preferable. Although an upper limit is not specifically limited, 99.5 mass% or less is preferable.
  • Components other than the above-mentioned polymerization initiator, compound X, and composition Y may be contained in the layer for forming a layer to be plated.
  • the layer for plating layer formation may contain a monomer.
  • the monomer used is not particularly limited, and examples thereof include compounds having an ethylenically unsaturated bond as compounds having addition polymerizability, and compounds having an epoxy group as compounds having ring-opening polymerizability. .
  • a polyfunctional monomer means a monomer having two or more polymerizable groups. Specifically, it is preferable to use a monomer having 2 to 6 polymerizable groups.
  • additives for the layer to be plated, other additives (for example, sensitizers, curing agents, polymerization inhibitors, antioxidants, antistatic agents, fillers, particles, flame retardants, surfactants, lubricants, plasticizers) Etc.) may be added as necessary.
  • the present invention is basically configured as described above. As described above, the developing device, the developing method, the pattern forming device, and the pattern forming method of the present invention have been described in detail. However, the present invention is not limited to the above-described embodiment, and various improvements can be made without departing from the gist of the present invention. Of course, changes may be made.

Abstract

This image developing device (14) is configured to develop a substrate (20) on which photosensitive layers (34), formed on both surfaces of a support body (30), are exposed in a predetermined pattern. The image developing device (14) has jetting parts (40) that intermittently jet a developer as fine particles toward the substrate (20) that is vertically held and onto the photosensitive layers (34) on the obverse and reverse surfaces of the substrate (20). This image developing method for developing the substrate (20) on which the photosensitive layers (34), formed on both surfaces of the support body (30), are exposed in a predetermined pattern comprises a developing step for intermittently jetting the developer as fine particles toward the substrate (20) that is vertically held and onto the photosensitive layers (34) on the obverse and reverse surfaces of the substrate (20).

Description

現像装置、現像方法、パターン形成装置およびパターン形成方法Developing apparatus, developing method, pattern forming apparatus, and pattern forming method
　本発明は、基板の両面にパターンを形成する現像装置および現像方法、ならびに現像装置を有するパターン形成装置、および現像方法を利用するパターン形成方法に関し、特に、現像ムラ等を抑制した高精度な現像を行うことができ、パターン精度を高くできる現像装置および現像方法、高精度な現像および洗浄ムラ等を抑制した高精度な洗浄のうち、少なくとも高精度な現像を行うことができ、パターン精度を高くできるパターン形成装置、およびパターン形成方法に関する。 The present invention relates to a developing device and a developing method for forming a pattern on both surfaces of a substrate, a pattern forming device having a developing device, and a pattern forming method using the developing method, and in particular, high-accuracy development that suppresses development unevenness and the like. Development device and development method that can increase pattern accuracy, high-precision development and high-accuracy cleaning that suppresses uneven cleaning, etc., and at least high-precision development can be performed, and pattern accuracy is high The present invention relates to a pattern forming apparatus and a pattern forming method.
　近年、携帯端末およびコンピューターの入力装置として、タッチパネルセンサーが多く利用されている。タッチパネルセンサーは、ディスプレイの表面に配置され、指等の接触された位置を検出し、入力操作がなされる。
　タッチパネルセンサーとして、静電容量方式のものがある。静電容量方式のタッチパネルセンサーでは、透明導電膜がＩＴＯ（酸化インジウムスズ）で構成されることが多い。
　しかしながら、稀少資源であるインジウムの保存量への不安、および産出国の輸出量規制からの確保量への不安がある。また、蒸着製造による歩留まり等、各種不安要素がある。このような背景から銅または銀といった一般的な金属を使って細い配線化してメッシュ状態にした透明導電膜も採用が始まっている。メッシュ状態にした透明導電膜は歩留まりが高く生産でき、低抵抗である特性を持つため、大面積にも対応が可能であることから益々数量は増えてきている。なお、上述の金属を使って、細い金属配線を透明な基材に形成するためには、透明感を増す上で細線化が重要となる。 In recent years, touch panel sensors have been widely used as input devices for portable terminals and computers. The touch panel sensor is disposed on the surface of the display, detects a touched position of a finger or the like, and performs an input operation.
There is a capacitive type touch panel sensor. In a capacitive touch panel sensor, the transparent conductive film is often composed of ITO (indium tin oxide).
However, there is anxiety about the storage amount of indium, a rare resource, and anxiety about the amount secured from the export control in the producing country. In addition, there are various uneasy factors such as the yield by vapor deposition manufacturing. From such a background, the adoption of a transparent conductive film that is made into a thin mesh by using a common metal such as copper or silver has been started. Since the transparent conductive film in a mesh state can be produced with a high yield and has a low resistance characteristic, the quantity is increasing more and more because it can cope with a large area. In order to form a thin metal wiring on a transparent substrate using the above-described metal, it is important to make the wire thin in order to increase the transparency.
　例えば、特許文献１には、サイズが大型化した有機ＥＬ素子を凸版印刷法によって形成するための樹脂凸版を、フォトリソグラフィー法でパターニングする際に、スプレー式現像方法を用いながら、パターン精度が高く、かつ現像ムラ等をなくした製版を行う方法が記載されている。
　特許文献１の印刷用凸版の製造方法では、露光後感光性樹脂の不要箇所をスプレー型の噴出口より噴射される現像液により除去し現像する現像段階と、現像後の感光性樹脂上の現像液の残渣をスプレー型の噴出口より噴射される洗浄液により除去する洗浄段階において、版材搬送部が搬送方向と直行する水平面に対して傾斜した角度を有している。これにより、従来のスプレー式の現像方法で見られた現像液が基板上で滞留し現像状態による面内バラツキ精度の悪化が発生する問題がなく、パターン精度が高く現像ムラの無い樹脂凸版の製版を行うことが可能とされている。 For example, Patent Document 1 discloses a high pattern accuracy while using a spray development method when patterning a resin relief plate for forming an organic EL element having a large size by a relief printing method, using a photolithography method. And a method of making a plate without development unevenness is described.
In the method for producing a relief printing plate of Patent Document 1, a development stage in which an unnecessary portion of the photosensitive resin after exposure is removed and developed with a developer sprayed from a spray-type jet nozzle, and development on the photosensitive resin after development is performed. In the cleaning stage in which the liquid residue is removed by the cleaning liquid sprayed from the spray-type jet nozzle, the plate material transport section has an angle inclined with respect to a horizontal plane perpendicular to the transport direction. As a result, there is no problem that the developer seen in the conventional spray-type development method stays on the substrate and the in-plane variation accuracy due to the development state does not deteriorate, and the resin relief printing plate making has high pattern accuracy and no development unevenness. It is possible to do.
特開２０１１－２４８１９９号公報JP 2011-248199 A
　特許文献１では、版材搬送部が傾斜した角度を有することで、現像液が基板上に滞留することなく、常に新しい洗浄液が基板上に存在するとしている。しかしながら、傾けても現像液の自重だけでは現像液が基板表面に残ることがあり、現像液の入換えが停滞し、実質的に現像液に曝される現像時間が基材の場所によって変動し、現像ムラの発生または異物の滞留により、パターン精度は必ずしも高くはならないという問題点がある。
　また、特許文献１では、基板の片面のみの現像、洗浄であり、基板の両面にパターンを形成したものには対応できない。 In Patent Document 1, it is assumed that a new cleaning liquid always exists on the substrate without the developer staying on the substrate because the plate material transport section has an inclined angle. However, even if the developer is tilted, the developer may remain on the surface of the substrate only by its own weight, so that the replacement of the developer is stagnant, and the development time that is substantially exposed to the developer varies depending on the location of the substrate. However, there is a problem that the pattern accuracy does not necessarily increase due to the occurrence of uneven development or the retention of foreign matter.
Moreover, in patent document 1, it is development and washing | cleaning of only one side of a board | substrate, and cannot respond to what formed the pattern on both surfaces of the board | substrate.
　本発明の目的は、前述の従来技術に基づく問題点を解消し、現像ムラ等を抑制した高精度な現像を行うことができ、パターン精度を高くできる現像装置および現像方法、高精度な現像および洗浄ムラ等を抑制した高精度な洗浄のうち、少なくとも高精度な現像を行うことができ、パターン精度を高くできるパターン形成装置、およびパターン形成方法を提供することにある。 An object of the present invention is to solve the problems based on the above-described conventional technology, perform high-accuracy development that suppresses development unevenness and the like, and can develop a developing apparatus and development method that can increase pattern accuracy, high-accuracy development and It is an object of the present invention to provide a pattern forming apparatus and a pattern forming method capable of performing at least high-accuracy development among high-accuracy cleaning that suppresses unevenness of cleaning and the like, and can increase pattern accuracy.
　上述の目的を達成するために、本発明の第１の態様は、支持体の両面に形成された感光性層が予め定められたパターン状に露光された基板を現像する現像装置であって、垂直に保持された基板に対して、基板の表面の感光性層および裏面の感光性層に、現像液を微小な粒状にして間欠的に噴射する噴射部を有することを特徴とする現像装置を提供するものである。 In order to achieve the above-mentioned object, a first aspect of the present invention is a developing device for developing a substrate in which photosensitive layers formed on both sides of a support are exposed in a predetermined pattern, A developing device characterized by having a jetting unit that jets a developer in a fine granular form intermittently on the photosensitive layer on the front surface and the photosensitive layer on the back surface of a substrate held vertically. It is to provide.
　基板と噴射部とを垂直方向に相対的に移動させる移動部を有することが好ましい。微小な粒状の現像液は、粒径が５ｍｍ以下であることが好ましい。噴射部は、基板の表面および裏面に対して、垂直方向における同じ位置に、同じタイミングで液体を噴射することが好ましい。噴射部は、液体を噴射するノズルを有し、ノズルから噴射される現像液の噴射範囲はノズルと基板の表面および裏面とを通る水平面以下であることが好ましい。
　基板の支持体の一方の面の感光性層に、静電容量式タッチパネルセンサーにおいてセンサー領域を構成する受信用配線のパターンが形成され、他方の面の感光性層に、センサー領域を構成する送信用配線のパターンが形成されていることが好ましい。
　基板の支持体の両面の感光性層に形成される予め定められたパターンは、少なくとも格子状のパターンを含むことが好ましい。 It is preferable to have a moving unit that relatively moves the substrate and the injection unit in the vertical direction. The fine granular developer preferably has a particle size of 5 mm or less. The ejection unit preferably ejects liquid at the same timing in the same position in the vertical direction with respect to the front surface and the back surface of the substrate. The ejection unit includes a nozzle that ejects a liquid, and the ejection range of the developer ejected from the nozzle is preferably equal to or less than a horizontal plane that passes through the nozzle and the front and back surfaces of the substrate.
On the photosensitive layer on one side of the substrate support, a pattern of receiving wiring that constitutes the sensor area in the capacitive touch panel sensor is formed, and on the other side of the photosensitive layer, the transmission layer that constitutes the sensor area is formed. It is preferable that a pattern of trusted wiring is formed.
It is preferable that the predetermined pattern formed on the photosensitive layers on both sides of the substrate support includes at least a lattice pattern.
　本発明の第２の態様は、支持体の両面に形成された感光性層が予め定められたパターン状に露光された基板を現像する現像方法であって、基板を垂直に保持した状態で、基板の表面の感光性層および裏面の感光性層に、現像液を微小な粒状にして間欠的に噴射する現像工程を有することを特徴とする現像方法を提供するものである。
　現像工程は、基板を垂直方向に相対的に移動させて、現像液を微小な粒状にして間欠的に噴射することが好ましい。
　微小な粒状の現像液は、粒径が５ｍｍ以下であることが好ましい。基板の表面および裏面に対して、垂直方向における同じ位置に、同じタイミングで現像液を噴射することが好ましい。現像液はノズルから噴射され、ノズルから噴射される現像液の噴射範囲はノズルと基板の表面および裏面とを通る水平面以下であることが好ましい。 A second aspect of the present invention is a developing method for developing a substrate in which photosensitive layers formed on both sides of a support are exposed in a predetermined pattern, with the substrate held vertically, It is an object of the present invention to provide a developing method characterized by having a developing step in which a developer is finely granulated and ejected intermittently on the photosensitive layer on the front surface and the photosensitive layer on the back surface of the substrate.
In the developing step, it is preferable that the substrate is relatively moved in the vertical direction so that the developer is finely granular and ejected intermittently.
The fine granular developer preferably has a particle size of 5 mm or less. It is preferable to eject the developer at the same timing at the same position in the vertical direction with respect to the front surface and the back surface of the substrate. The developer is ejected from the nozzle, and the ejection range of the developer ejected from the nozzle is preferably not more than a horizontal plane passing through the nozzle and the front surface and the back surface of the substrate.
　本発明の第３の態様は、少なくとも現像装置および洗浄装置を備え、基板の両面にパターンを形成するパターン形成装置であって、現像装置および洗浄装置のうち、少なくとも現像装置が、垂直に保持された基板に対して、基板の表面の感光性層および裏面の感光性層に、現像液を微小な粒状にして間欠的に噴射する噴射部を有し、現像装置の場合、液体は現像液であり、洗浄装置の場合、液体は洗浄液であることを特徴とするパターン形成装置を提供するものである。
　基板と噴射部とを垂直方向に相対的に移動させる移動部を有することが好ましい。
　微小な粒状の液体は、粒径が５ｍｍ以下であることが好ましい。噴射部は、基板の表面および裏面に対して、垂直方向における同じ位置に、同じタイミングで液体を噴射することが好ましい。噴射部は、液体を噴射するノズルを有し、ノズルから噴射される液体の噴射範囲はノズルと基板の表面および裏面とを通る水平面以下であることが好ましい。
　基板は、支持体の両面に感光性層が形成されたものであることが好ましい。 A third aspect of the present invention is a pattern forming apparatus that includes at least a developing device and a cleaning device and forms a pattern on both surfaces of a substrate, and at least the developing device of the developing device and the cleaning device is held vertically. In the case of a developing device, the liquid is a developer, and has a jetting unit that intermittently jets the developer into fine particles on the photosensitive layer on the front surface and the photosensitive layer on the back surface of the substrate. In the case of a cleaning apparatus, the liquid is a cleaning liquid, and a pattern forming apparatus is provided.
It is preferable to have a moving unit that relatively moves the substrate and the injection unit in the vertical direction.
The fine granular liquid preferably has a particle size of 5 mm or less. The ejection unit preferably ejects liquid at the same timing in the same position in the vertical direction with respect to the front surface and the back surface of the substrate. The ejection unit includes a nozzle that ejects liquid, and the ejection range of the liquid ejected from the nozzle is preferably equal to or less than a horizontal plane that passes through the nozzle and the front and back surfaces of the substrate.
It is preferable that the substrate has a photosensitive layer formed on both sides of the support.
　本発明の第４の態様は、基板の両面にパターンを形成するパターン形成方法であって、支持体の両面に形成された感光性層が予め定められたパターン状に露光された基板を垂直に保持した状態で、基板の表面の感光性層および裏面の感光性層に、現像液を微小な粒状にして間欠的に噴射する現像工程と、現像工程の後、さらに基板を垂直に保持した状態で、基板の表面の感光性層および裏面の感光性層に、洗浄液を微小な粒状にして間欠的に噴射する洗浄工程を有することを特徴とするパターン形成方法を提供するものである。 According to a fourth aspect of the present invention, there is provided a pattern forming method for forming a pattern on both sides of a substrate, wherein the photosensitive layer formed on both sides of the support is exposed vertically to a predetermined pattern. In a held state, a developing process in which a developer is intermittently sprayed into a fine granular form on the photosensitive layer on the front surface and the photosensitive layer on the back surface, and a state in which the substrate is further held vertically after the developing process Thus, the present invention provides a pattern forming method comprising a cleaning step of intermittently spraying a cleaning liquid in a fine granular form on the photosensitive layer on the front surface of the substrate and the photosensitive layer on the back surface.
　現像工程および洗浄工程は、基板を垂直方向に相対的に移動させて、現像液および洗浄液を微小な粒状にして間欠的に噴射することが好ましい。微小な粒状の現像液および微小な粒状の洗浄液は、粒径が５ｍｍ以下であることが好ましい。現像工程は、基板の表面および裏面に対して、垂直方向における同じ位置に、同じタイミングで現像液を噴射し、洗浄工程は、基板の表面および裏面に対して、垂直方向における同じ位置に、同じタイミングで洗浄液を噴射することが好ましい。
　現像液はノズルから噴射され、ノズルから噴射される現像液の噴射範囲はノズルと基板の表面および裏面とを通る水平面以下であることが好ましい。洗浄液はノズルから噴射され、ノズルから噴射される洗浄液の噴射範囲はノズルと基板の表面および裏面とを通る水平面以下であることが好ましい。 In the development process and the cleaning process, it is preferable that the substrate is relatively moved in the vertical direction so that the developer and the cleaning liquid are finely granulated and intermittently ejected. The fine granular developer and the fine granular cleaning liquid preferably have a particle size of 5 mm or less. The developing process injects the developing solution at the same timing in the vertical direction with respect to the front and back surfaces of the substrate, and the cleaning process is the same at the same position in the vertical direction with respect to the front and back surfaces of the substrate. It is preferable to spray the cleaning liquid at the timing.
The developer is ejected from the nozzle, and the ejection range of the developer ejected from the nozzle is preferably not more than a horizontal plane passing through the nozzle and the front surface and the back surface of the substrate. The cleaning liquid is sprayed from the nozzle, and the spraying range of the cleaning liquid sprayed from the nozzle is preferably below the horizontal plane passing through the nozzle and the front surface and the back surface of the substrate.
　本発明の現像装置および現像方法によれば、現像ムラ等を抑制した高精度な現像を行うことができ、パターン精度を高くできる。
　本発明のパターン形成装置およびパターン形成方法によれば、現像ムラ等を抑制した高精度な現像および洗浄ムラ等を抑制した高精度な洗浄のうち、少なくとも高度な現像を行うことができ、パターン精度を高くできる。 According to the developing device and the developing method of the present invention, it is possible to perform highly accurate development with suppressed development unevenness and the like, and it is possible to increase pattern accuracy.
According to the pattern forming apparatus and the pattern forming method of the present invention, at least high-level development can be performed among high-precision development that suppresses development unevenness and high-accuracy cleaning that suppresses unevenness of cleaning, and the like. Can be high.
本発明の実施形態のパターン形成装置を示す模式図である。It is a schematic diagram which shows the pattern formation apparatus of embodiment of this invention. 両面が露光される基板の一例を示す模式的断面図である。It is typical sectional drawing which shows an example of the board | substrate with which both surfaces are exposed. 両面が露光される基板の他の例を示す模式的断面図である。It is typical sectional drawing which shows the other example of the board | substrate by which both surfaces are exposed. 本発明の実施形態の現像装置を示す模式図である。It is a schematic diagram showing a developing device of an embodiment of the present invention. 本発明の実施形態の現像装置のノズルの配置位置を示す模式図である。It is a schematic diagram which shows the arrangement position of the nozzle of the developing device of embodiment of this invention. 本発明の実施形態の現像装置の現象方法を工程順に示す模式図である。It is the model which shows the phenomenon method of the image development apparatus of embodiment of this invention in order of a process. 本発明の実施形態の現像装置の現象方法を工程順に示す模式図である。It is the model which shows the phenomenon method of the image development apparatus of embodiment of this invention in order of a process. 本発明の実施形態の現像装置の現象方法を工程順に示す模式図である。It is the model which shows the phenomenon method of the image development apparatus of embodiment of this invention in order of a process. 現像液の粒径の測定方法を説明するための模式図である。It is a schematic diagram for demonstrating the measuring method of the particle size of a developing solution. 現像液の粒径の測定方法を説明するための模式図である。It is a schematic diagram for demonstrating the measuring method of the particle size of a developing solution. パターンの一例を示す模式的平面図である。It is a schematic plan view which shows an example of a pattern. 露光で形成されるタッチパネルセンサーの一例を示す模式的平面図である。It is a typical top view showing an example of a touch panel sensor formed by exposure. 図１２に示すタッチパネルセンサーの形成に用いられるマスクパターンの一例を示す模式図である。It is a schematic diagram which shows an example of the mask pattern used for formation of the touch panel sensor shown in FIG. 図１２に示すタッチパネルセンサーの形成に用いられるマスクパターンの他の例を示す模式図である。It is a schematic diagram which shows the other example of the mask pattern used for formation of the touch panel sensor shown in FIG.
　以下に、添付の図面に示す好適実施形態に基づいて、本発明の現像装置、現像方法、パターン形成装置およびパターン形成方法を詳細に説明する。
　なお、以下において数値範囲を示す「～」とは両側に記載された数値を含む。例えば、εが数値α～数値βとは、εの範囲は数値αと数値βを含む範囲であり、数学記号で示せばα≦ε≦βである。
　光学的透明および単に透明とは、いずれも光透過率が、波長４００～８００ｎｍの可視光波長域において、少なくとも６０％以上のことであり、好ましくは８０％以上であり、より好ましくは９０％以上、さらにより好ましくは９５％以上のことである。
　光透過率は、例えば、ＪＩＳ　Ｋ　７３７５：２００８に規定される「プラスチック--全光線透過率および全光線反射率の求め方」を用いて測定されるものである。
　また、「同じ」、「同一」および「同時」とは、技術分野で一般的に許容される誤差範囲を含むものとする。「異なる」とは、上述の「同じ」、「同一」、「同時」の規定を満たさないもののことである。 Hereinafter, a developing device, a developing method, a pattern forming device, and a pattern forming method of the present invention will be described in detail based on preferred embodiments shown in the accompanying drawings.
In the following, “to” indicating a numerical range includes numerical values written on both sides. For example, when ε is a numerical value α to a numerical value β, the range of ε is a range including the numerical value α and the numerical value β, and expressed by mathematical symbols, α ≦ ε ≦ β.
Optically transparent and simply transparent are both light transmittances of at least 60%, preferably 80% or more, more preferably 90% or more, in the visible light wavelength range of 400 to 800 nm. Even more preferably, it is 95% or more.
The light transmittance is measured by using, for example, “plastic—how to obtain total light transmittance and total light reflectance” defined in JIS K 7375: 2008.
In addition, “same”, “same” and “simultaneous” include an error range generally allowed in the technical field. “Different” means that the above “same”, “same”, and “simultaneous” regulations are not satisfied.
　図１は、本発明の実施形態のパターン形成装置を示す模式図である。図２は両面が露光される基板の一例を示す模式的断面図であり、図３は両面が露光される基板の他の例を示す模式的断面図である。
　図１に示すパターン形成装置１０は、基板２０の両面にパターンを形成するものである。パターン形成装置１０の構成は、パターン形成方法により、その構成は適宜決定されるものである。例えば、パターン形成装置１０は、露光装置１２と現像装置１４と洗浄装置１６とを有する。パターン形成装置１０で露光する必要は必ずしもなく、露光済みの基板２０を用いることができるため、パターン形成装置１０は、少なくとも現像装置１４と洗浄装置１６とを有すればよい。 FIG. 1 is a schematic diagram showing a pattern forming apparatus according to an embodiment of the present invention. FIG. 2 is a schematic cross-sectional view showing an example of a substrate on which both sides are exposed, and FIG. 3 is a schematic cross-sectional view showing another example of a substrate on which both sides are exposed.
A pattern forming apparatus 10 shown in FIG. 1 forms a pattern on both surfaces of a substrate 20. The configuration of the pattern forming apparatus 10 is appropriately determined by the pattern forming method. For example, the pattern forming apparatus 10 includes an exposure device 12, a developing device 14, and a cleaning device 16. It is not always necessary to perform exposure with the pattern forming apparatus 10, and since the exposed substrate 20 can be used, the pattern forming apparatus 10 only needs to include at least the developing device 14 and the cleaning device 16.
　基板２０は、両面にパターンが形成されるものである。形成されるパターンは、両面とも同じであっても異なっていてもよい。
　図２に示すように、基板２０は、支持体３０の表面３０ａ上に下塗層３２が設けられ、下塗層３２の表面３２ａに感光性層３４が設けられている。また、支持体３０の裏面３０ｂ上に下塗層３２が設けられ、下塗層３２の表面３２ａに感光性層３４が設けられている。露光時には、例えば、感光性層３４の表面３４ａに露光マスク（図示せず）が配置され、基板２０では露光マスクに挟まれた状態で露光され、各感光性層３４に露光パターンが形成される。支持体３０の表面３０ａ側の感光性層３４の表面３４ａが基板２０の表面２０ａであり、支持体３０の裏面３０ｂ側の感光性層３４の表面３４ａが基板２０の裏面２０ｂである。 The substrate 20 has a pattern formed on both sides. The pattern to be formed may be the same or different on both sides.
As shown in FIG. 2, the substrate 20 is provided with an undercoat layer 32 on the surface 30 a of the support 30, and a photosensitive layer 34 is provided on the surface 32 a of the undercoat layer 32. An undercoat layer 32 is provided on the back surface 30 b of the support 30, and a photosensitive layer 34 is provided on the surface 32 a of the undercoat layer 32. At the time of exposure, for example, an exposure mask (not shown) is arranged on the surface 34 a of the photosensitive layer 34, and the substrate 20 is exposed while being sandwiched between the exposure masks, and an exposure pattern is formed on each photosensitive layer 34. . The surface 34 a of the photosensitive layer 34 on the surface 30 a side of the support 30 is the surface 20 a of the substrate 20, and the surface 34 a of the photosensitive layer 34 on the back surface 30 b side of the support 30 is the back surface 20 b of the substrate 20.
　基板２０では、各感光性層３４に対して第１の露光光Ｌ１または第２の露光光Ｌ２が照射されるため、互いに他の露光光により露光されることを防ぐために支持体３０に第１の露光光Ｌ１または第２の露光光Ｌ２が到達することを抑制するために下塗層３２を設けている。なお、下塗層３２は、基板２０と基板２０上に形成されるパターンを構成するものとの密着性を高める効果もある。下塗層３２は、感光性層３４が露光、現像および洗浄されて形成される後述のパターンを構成するめっき層と基板２０との密着性を高めることができる。下塗層３２は、露光光を防ぐ効果と密着性を高める効果があることが好ましいが、例えば、支持体３０が露光光を吸収することができるものであれば、下塗層３２は、密着性を高める効果を優位に、または密着性を高める効果だけを有するものであってもよい。
　また、例えば、露光光を吸収することができる支持体３１（図３参照）であれば、図３に示す基板２１のように下塗層３２を設けることなく、支持体３１の表面３１ａおよび裏面３１ｂに、それぞれ感光性層３４を設ける構成とすることができる。
　基板２０の支持体３０、下塗層３２および感光性層３４ならびに支持体３１については後に詳細に説明する。支持体３０および支持体３１は、用途により適宜選択されるものである。用途により透明なもの、または不透明なものであってもよい。 In the substrate 20, each photosensitive layer 34 is irradiated with the first exposure light L 1 or the second exposure light L 2 , so that the support 30 is prevented from being exposed to other exposure light. the first exposure light L 1 or the second exposure light L 2 is provided with a subbing layer 32 in order to prevent the reaching. The undercoat layer 32 also has an effect of improving the adhesion between the substrate 20 and the pattern forming on the substrate 20. The undercoat layer 32 can enhance the adhesion between the substrate 20 and a plating layer constituting a pattern described later formed by exposing, developing and washing the photosensitive layer 34. The undercoat layer 32 preferably has an effect of preventing exposure light and an effect of improving adhesion. For example, if the support 30 can absorb exposure light, the undercoat layer 32 is in close contact. It may have only the effect of enhancing the effect of improving the property or improving the adhesion.
Further, for example, in the case of the support 31 (see FIG. 3) capable of absorbing exposure light, the front surface 31a and the back surface of the support 31 are not provided as in the substrate 21 shown in FIG. The photosensitive layer 34 can be provided on each 31b.
The support 30, the undercoat layer 32, the photosensitive layer 34, and the support 31 of the substrate 20 will be described in detail later. The support body 30 and the support body 31 are appropriately selected depending on the application. It may be transparent or opaque depending on the application.
　露光装置１２は、基板２０の両面に形成されるパターンの露光パターンを形成するものである。露光装置１２において、基板２０に形成する露光パターンは、ポジ型でもネガ型でもよい。
　露光装置１２による露光パターンの形成方法は特に限定されるものではない。例えば、露光マスクを用いた面露光で露光パターンを形成しても、露光マスクを用いることなくレーザー光線または電子線を走査して露光パターンを形成してもよい。また、露光に用いる光源の波長は、感光性層３４に応じて適宜決定されるものである。 The exposure apparatus 12 forms an exposure pattern of a pattern formed on both surfaces of the substrate 20. In the exposure apparatus 12, the exposure pattern formed on the substrate 20 may be a positive type or a negative type.
An exposure pattern forming method by the exposure apparatus 12 is not particularly limited. For example, even if the exposure pattern is formed by surface exposure using an exposure mask, the exposure pattern may be formed by scanning a laser beam or an electron beam without using the exposure mask. The wavelength of the light source used for exposure is appropriately determined according to the photosensitive layer 34.
　現像装置１４は、基板２０を垂直に保持した状態で、基板２０の両面に設けられた感光性層３４を現像するものである。
　図４は本発明の実施形態の現像装置を示す模式図であり、図５は本発明の実施形態の現像装置のノズルの配置位置を示す模式図である。なお、図４および図５に示す垂直方向Ｖと水平方向Ｈと方向Ｚは互いに直交する。
　現像装置１４は、図４に示すように、ノズル４０と、ポンプ４２と、第１のタンク４４と、第２のタンク４５とを有する。ノズル４０とポンプ４２と第１のタンク４４とは配管４３を介して接続されている。ポンプ４２と第１のタンク４４との間の配管４３には切替バルブ４６が設けられている。第２のタンク４５は、切替バルブ４６に配管４３ａを介して接続されている。 The developing device 14 develops the photosensitive layers 34 provided on both surfaces of the substrate 20 with the substrate 20 held vertically.
FIG. 4 is a schematic diagram illustrating a developing device according to an embodiment of the present invention, and FIG. 5 is a schematic diagram illustrating an arrangement position of nozzles of the developing device according to the embodiment of the present invention. Note that the vertical direction V, the horizontal direction H, and the direction Z shown in FIGS. 4 and 5 are orthogonal to each other.
As illustrated in FIG. 4, the developing device 14 includes a nozzle 40, a pump 42, a first tank 44, and a second tank 45. The nozzle 40, the pump 42 and the first tank 44 are connected via a pipe 43. A switching valve 46 is provided in the pipe 43 between the pump 42 and the first tank 44. The second tank 45 is connected to the switching valve 46 via a pipe 43a.
　さらに、基板２０を垂直方向Ｖに移動させるためのガイド４７とモータ４８とを有する。基板２０は、図示しない治具等でガイド４７に設けられ、モータ４８により基板２０は垂直方向Ｖに予め設定された速度で引き上げられる。また、モータ４８により予め設定された速度で下方に下げられる。ガイド４７とモータ４８とで移動部が構成される。なお、ノズル４０と基板２０とを相対的に移動させることができればよく、基板２０を移動させるものに限定されるものではない。基板２０を固定してノズル４０を移動させるようにしてもよい。
　現像装置１４の各構成部は、制御部４９で制御される。また、ノズル４０とポンプ４２と第１のタンク４４とで噴射部４１が構成される。噴射部４１には第２のタンク４５が含まれていてもよい。現像装置１４では、切替バルブ４６、配管４３ａおよび第２のタンク４５は必ずしも設けなくてよい。 Further, a guide 47 and a motor 48 for moving the substrate 20 in the vertical direction V are provided. The substrate 20 is provided on the guide 47 by a jig or the like (not shown), and the substrate 20 is pulled up in the vertical direction V by a motor 48 at a preset speed. Further, it is lowered downward by a motor 48 at a preset speed. The guide 47 and the motor 48 constitute a moving part. The nozzle 40 and the substrate 20 may be moved relative to each other, and are not limited to those that move the substrate 20. The substrate 20 may be fixed and the nozzle 40 may be moved.
Each component of the developing device 14 is controlled by the control unit 49. The nozzle 40, the pump 42, and the first tank 44 constitute an injection unit 41. The injection unit 41 may include a second tank 45. In the developing device 14, the switching valve 46, the pipe 43a, and the second tank 45 are not necessarily provided.
　第１のタンク４４には現像液が貯留される。ポンプ４２によりノズル４０から現像液を微小な粒状にして間欠的に噴射される。また、第２のタンク４５内部の液体はポンプ４２によりノズル４０から微小な粒状にして間欠的に噴射させることができる。
　ここで、微小な粒状とは、粒径が５ｍｍ以下であることをいい、好ましくは２ｍｍ以下である。現像液の粒径の測定方法については後に詳細に説明する。
　間欠的に噴射とは、１秒間に１．５回以下、すなわち、１．５Ｈｚ以下の噴射のことをいう。間欠的な噴射において、好ましくは、１秒間に１回以下、すなわち、１Ｈｚ以下、更に望ましくは２秒に１回以下、すなわち、０．５Ｈｚ以下である。
　現像液の間欠的な噴射における噴射の下限値としては、使用する現像液の種類、現像液の噴射量等、更には周囲の環境により変わるため、特に限定されるものではない。例えば、現像液を噴霧する際には、基板の表面で現像液が局所的に乾燥すると、現像ムラが生じるため好ましくない。このようなことから、間欠的な噴射における噴射の下限値は、現像液が局所的に乾燥しない条件に応じて適宜設定される。この場合、現像液の種類毎に噴射量および使用環境に基づき局所的に乾燥しない条件を予め求めておき、これに基づいて間欠的な噴射における噴射の下限値を予め設定することができる。 A developer is stored in the first tank 44. The developer is intermittently ejected from the nozzle 40 in a minute granular form by the pump 42. Further, the liquid in the second tank 45 can be ejected intermittently from the nozzle 40 by the pump 42 in the form of fine particles.
Here, the fine granularity means that the particle diameter is 5 mm or less, preferably 2 mm or less. A method for measuring the particle size of the developer will be described in detail later.
Intermittent injection refers to injection 1.5 times or less per second, that is, 1.5 Hz or less. In intermittent injection, it is preferably no more than once per second, i.e., 1 Hz or less, more desirably no more than once every 2 seconds, i.e., 0.5 Hz or less.
The lower limit value of the ejection in the intermittent ejection of the developer is not particularly limited because it varies depending on the type of the developer to be used, the ejection amount of the developer, and the surrounding environment. For example, when the developer is sprayed, if the developer is locally dried on the surface of the substrate, uneven development occurs, which is not preferable. For this reason, the lower limit value of the ejection in the intermittent ejection is appropriately set according to the condition where the developer does not dry locally. In this case, for each type of developer, a condition that does not dry locally can be obtained in advance based on the injection amount and the usage environment, and based on this, a lower limit value of injection in intermittent injection can be set in advance.
　ノズル４０は水平方向Ｈに隙間をあけて対向して配置されており、ノズル４０の間の隙間にガイド４７が設けられている。基板２０は、対向するノズル４０の間を垂直に保持された状態で通過する。
　ノズル４０は、例えば、図５に示すように、方向Ｚに間隔をあけて複数、例えば、４個配置されている。ノズル４０の個数は、基板２０の大きき、ノズル４０の噴射範囲Ｄｉの大きさに応じて適宜設定されるものである。このため、ノズル４０は１個の場合もある。噴射範囲Ｄｉの形状は、基板２０の大きさ等に応じて適宜設定されるものであり、特に限定されるものではなく、円形でも四角形でもよい。 The nozzles 40 are arranged to face each other with a gap in the horizontal direction H, and a guide 47 is provided in the gap between the nozzles 40. The board | substrate 20 passes in the state hold | maintained perpendicularly between the nozzles 40 which oppose.
For example, as shown in FIG. 5, a plurality of, for example, four nozzles 40 are arranged at intervals in the direction Z. The number of the nozzles 40 is appropriately set according to the size of the substrate 20 and the size of the ejection range Di of the nozzles 40. For this reason, there may be one nozzle 40. The shape of the ejection range Di is appropriately set according to the size of the substrate 20 and is not particularly limited, and may be circular or quadrangular.
　ノズル４０は、基板２０の感光性層３４に対して、現像液を微小な粒状で、かつ噴射範囲Ｄｓを広範囲に噴射することができれば、その構成は特に限定されるものではなく、例えば、スリット状のノズルであってもよい。
　噴射範囲Ｄｓは、例えば、噴射角θでも表される。噴射範囲Ｄｓは、最大でもノズル４０と基板２０の表面２０ａおよび裏面２０ｂとを通る水平面ＰＨ以下であることが好ましい。噴射範囲Ｄｓが水平面ＰＨ以下であれば、感光性層３４に付着する液滴５０を下方２０ｃに更に落ちやすくすることができる。
　また、噴射範囲Ｄｓは、最大でも基板２０の中心線Ｃと平行な垂直面Ｐｖ以内であることが好ましい。噴射範囲Ｄｓが垂直面Ｐｖを超えると、基板２０の表面２０ａおよび裏面２０ｂに到達しない現像液が増える。このように、噴射範囲Ｄｓは、上述の水平面ＰＨと垂直面Ｐｖとの間にあることが好ましい。すなわち、噴射角θは上述の水平面ＰＨと垂直面Ｐｖとの間にあることが好ましい。 The configuration of the nozzle 40 is not particularly limited as long as the developer can be sprayed onto the photosensitive layer 34 of the substrate 20 in a fine granular form and in a wide spray range Ds. The nozzle may be a shape.
The injection range Ds is also expressed by, for example, the injection angle θ. Injection range Ds is preferably at most is also the nozzle 40 and the horizontal plane P H below passing through the surface 20a and rear surface 20b of the substrate 20. If the injection range Ds is less horizontal plane P H, it can be a droplet 50 adhered to the photosensitive layer 34 more easily fall downward 20c.
Further, it is preferable that the injection range Ds is within the vertical plane Pv parallel to the center line C of the substrate 20 at the maximum. When the ejection range Ds exceeds the vertical plane Pv, the amount of developer that does not reach the front surface 20a and the back surface 20b of the substrate 20 increases. Thus, the injection range Ds is preferably located between the horizontal plane P H and a vertical plane Pv described above. That is, it is preferable that the injection angle θ is between the horizontal plane P H and a vertical plane Pv described above.
　ポンプ４２は、第１のタンク４４および第２のタンク４５から現像液または洗浄液をノズル４０に供給し、間欠的に噴射させることができれば、その構成は特に限定されるものではない。ポンプ４２として、例えば、ダイヤフラム型のポンプを用いることができる。 The structure of the pump 42 is not particularly limited as long as it can supply the developer or cleaning liquid from the first tank 44 and the second tank 45 to the nozzle 40 and eject the liquid intermittently. As the pump 42, for example, a diaphragm type pump can be used.
　第１のタンク４４および第２のタンク４５は、内部に現像液および洗浄液等の液体を貯留することができれば、その構成は特に限定されるものではない。なお、第１のタンク４４と、第２のタンク４５とには貯留する現像液および洗浄液の使用温度に応じて、内部の液体を使用温度に維持するためのヒータまたはクーラー等の温度調整部を備えていてもよい。
　現像液および洗浄液については、基板２０の感光性層３４に適したものが適宜用いられ、例えば、有機溶剤よりも表面張力の高い水を含むものが用いられる。 The configuration of the first tank 44 and the second tank 45 is not particularly limited as long as liquid such as developer and cleaning liquid can be stored therein. The first tank 44 and the second tank 45 are provided with a temperature adjustment unit such as a heater or a cooler for maintaining the internal liquid at the use temperature according to the use temperature of the developer and cleaning liquid stored. You may have.
As the developer and the cleaning solution, those suitable for the photosensitive layer 34 of the substrate 20 are appropriately used. For example, those containing water having a surface tension higher than that of the organic solvent are used.
　基板２０を垂直に保持した状態で現像処理を行うが、垂直とは、基板２０の中心線Ｃの水平方向Ｈに対する角度が９０°であることをいう。垂直の角度については、角度１０°を許容し、水平方向Ｈに対する角度が８０°～１００°の範囲を本発明では垂直とする。 The development processing is performed with the substrate 20 held vertically. The vertical means that the angle of the center line C of the substrate 20 with respect to the horizontal direction H is 90 °. With respect to the vertical angle, an angle of 10 ° is allowed, and a range in which the angle with respect to the horizontal direction H is 80 ° to 100 ° is vertical in the present invention.
　現像工程は、露光済みの感光性層３４の表面が現像液で濡れる。現像液成分が被現像物をアタックし、溶解して感光性層３４表面に溶け出す。溶け出た素材は拡散または除去されて更に溶解は進むといった、４段階の工程を有する。これらは逐次または同時に生じている。
　現像装置１４では、基板２０を垂直に保持しているため、感光性層３４表面に達した現像液は感光性層３４表面に接触し、大半の現像液が重力で下方に流れる。次の間欠的な噴射による現像液が更に感光性層３４表面に達し、現像に関した後、下方に流れる。すなわち、常に新鮮な現像液を感光性層３４表面、直近に運ぶことができる。
　噴射した現像液によっても感光性層３４表面についた現像液を下方にかきとる効果を生む。現像液は通常水系であるため、極めて高い表面張力を有しており、現像液の比重は小さく、表面張力は高い。このため、感光性層３４表面の液膜は、そこに残ろうとする。よって、単なる自重効果だけでは新旧の現像液の切り替えは進み難いが、自重と噴射された現像液の勢いの双方で、感光性層３４表面での現像液の入れ替えを活発化できる。 In the development step, the exposed surface of the photosensitive layer 34 is wetted with the developer. The developer component attacks the object to be developed, dissolves, and dissolves on the surface of the photosensitive layer 34. The melted material is diffused or removed and further melted, so that there are four steps. These occur sequentially or simultaneously.
In the developing device 14, since the substrate 20 is held vertically, the developer that has reached the surface of the photosensitive layer 34 contacts the surface of the photosensitive layer 34, and most of the developer flows downward by gravity. The developing solution by the next intermittent jet further reaches the surface of the photosensitive layer 34 and flows downward after the development. That is, it is possible to always carry a fresh developer to the surface of the photosensitive layer 34 in the immediate vicinity.
The jetted developer also has the effect of scraping the developer on the surface of the photosensitive layer 34 downward. Since the developer is usually aqueous, it has an extremely high surface tension, the specific gravity of the developer is small, and the surface tension is high. For this reason, the liquid film on the surface of the photosensitive layer 34 tends to remain there. Therefore, it is difficult to switch between the old and new developing solutions by the mere self-weight effect, but the replacement of the developing solution on the surface of the photosensitive layer 34 can be activated by both the self-weight and the momentum of the jetted developing solution.
　このように現像装置１４では、基板２０を垂直に保持し、かつ垂直を保持した状態で基板２０の表面２０ａの感光性層３４および裏面２０ｂの感光性層３４に、現像液を微小な粒状の液滴５０にして間欠的に噴射することで、現像液の液滴５０の表面積を増やし、感光性層３４表面に付着し易くして濡れ性を上げている。また、現像液を間欠的に噴射することで、現像液の濡れやすさを更に向上させている。基板２０を垂直に保持することで被現像物が溶け込んだ現像液の液滴５０を基板２０の下方２０ｃに移動させやすくすることができる。これにより、現像ムラ等を抑制した高度な現像を行うことができる。
　また、現像装置１４では、ノズル４０による現像液の噴射について、噴射範囲Ｄｓを水平面ＰＨ以下とすることで、被現像物が溶け込んだ現像液の液滴５０を基板２０の下方２０ｃに移動させやすくすることができる。また、噴射範囲Ｄｓを垂直面Ｐｖ以内とすることで、現像液を有効に利用することができる。 As described above, in the developing device 14, the developer is applied to the photosensitive layer 34 on the front surface 20 a of the substrate 20 and the photosensitive layer 34 on the back surface 20 b in a state where the substrate 20 is held vertically. By intermittently ejecting the droplet 50, the surface area of the developer droplet 50 is increased, and the surface of the photosensitive layer 34 is easily adhered to the surface to increase the wettability. In addition, the developer wettability is further improved by intermittently ejecting the developer. By holding the substrate 20 vertically, it is possible to easily move the developer droplet 50 in which the development object is dissolved to the lower part 20 c of the substrate 20. As a result, it is possible to perform advanced development with development unevenness suppressed.
Further, in the developing device 14, the injection of the developer by the nozzle 40, the injection range Ds is set to lower than or equal to the horizontal plane P H, to move the droplet 50 of the developer that dissolves the object to be developed was below 20c of the substrate 20 It can be made easier. Further, the developer can be effectively used by setting the ejection range Ds to be within the vertical plane Pv.
　基板２０の両面に現像液を噴射するが、垂直方向Ｖにおける同じ位置に、同じタイミングで現像液を噴射することが好ましい。複数のノズル４０による現像液の噴射タイミングは制御部４９で制御される。このように基板２０の両面から現像液を、基板２０の垂直方向Ｖにおける同じ位置に同じタイミングで噴射して基板２０の両側から圧力をかけることにより、基板２０を中立に保つことができる。このため、基板２０の厚みを薄くした場合でも、基板２０の両側から現像液の圧力バランスで基板２０は中立を保持することができ、基板２０は、水平方向Ｈにおいて他に接触することがないため、基板２０を薄型化した場合でも対応することができる。また、基板２０の移動も基板２０のブレが抑制され、円滑に現像処理できる。また、基板２０の両面をまとめて現像処理することにより、効率良く現像処理をすることができ、ひいてはパターン形成の効率も高めることができる。 The developer is sprayed on both surfaces of the substrate 20, but it is preferable to spray the developer at the same position in the vertical direction V at the same timing. The control unit 49 controls the timing of ejecting the developer from the plurality of nozzles 40. Thus, the substrate 20 can be kept neutral by spraying the developer from both sides of the substrate 20 to the same position in the vertical direction V of the substrate 20 at the same timing and applying pressure from both sides of the substrate 20. For this reason, even when the thickness of the substrate 20 is reduced, the substrate 20 can be kept neutral by the pressure balance of the developer from both sides of the substrate 20, and the substrate 20 does not come into contact with the other in the horizontal direction H. Therefore, even when the substrate 20 is thinned, it can be dealt with. Further, the movement of the substrate 20 is also suppressed in the blur of the substrate 20 and can be developed smoothly. Further, by developing the both surfaces of the substrate 20 together, the developing process can be performed efficiently, and the pattern formation efficiency can be improved.
　次に、現像装置１４による現像方法について説明する。
　図６～図８は本発明の実施形態の現像装置の現象方法を工程順に示す模式図である。なお、図６～図８に示す現像装置１４は、ノズル４０と基板２０を示し、他の構成について図示は省略している。
　露光装置１２にて、支持体３０の両面に形成された感光性層３４が予め定められたパターン状に露光された基板２０を、図６に示すように、ノズル４０の間に配置し、基板２０を垂直に保持する。基板２０を垂直に保持した状態で、ポンプ４２を駆動し第１のタンク４４内の現像液をノズル４０から微小な粒状にして間欠的に噴射する。このとき、上述のように基板２０の垂直方向Ｖにおける同じ位置に、噴射タイミングを一致させて、すなわち、同期させて現像液を噴射させることが好ましい。 Next, a developing method by the developing device 14 will be described.
6 to 8 are schematic views showing the phenomenon method of the developing device according to the embodiment of the present invention in the order of steps. The developing device 14 shown in FIGS. 6 to 8 shows the nozzle 40 and the substrate 20, and the other components are not shown.
In the exposure apparatus 12, the substrate 20 on which the photosensitive layers 34 formed on both surfaces of the support 30 are exposed in a predetermined pattern is disposed between the nozzles 40 as shown in FIG. Hold 20 vertically. With the substrate 20 held vertically, the pump 42 is driven, and the developer in the first tank 44 is intermittently ejected from the nozzle 40 in a minute granular form. At this time, it is preferable that the developer is ejected at the same position in the vertical direction V of the substrate 20 at the same timing, that is, in synchronization, as described above.
　モータ４８（図４参照）によりガイド４７を介して、基板２０を上方に、予め設定された速度で引き上げ、図７および図８に示すように、基板２０の端部に達する迄、基板２０を引き上げる。このようにして基板２０の感光性層３４全面に現像液を行き渡らせることができ、均一に現像することができる。また、基板２０を上方に移動させることで、感光性層３４表面の液滴５０（図４参照）が基板２０の下方２０ｃに流れ、現像で生じた剥がれものを容易に除去することができる。
　なお、現像方法では、図６～図８に示す現像工程を１回ではなく、複数回繰り返してもよく、感光性層３４の種類または現像液の種類等に応じて適宜決定される。この場合、基板２０を図８の状態から図６に示す状態にして、すなわち、基板２０を下方に下げた後、次回の現像処理を行うことが好ましい。 The substrate 20 is lifted upward at a preset speed through a guide 47 by a motor 48 (see FIG. 4), and the substrate 20 is moved until reaching the end of the substrate 20 as shown in FIGS. Pull up. In this way, the developer can be spread over the entire surface of the photosensitive layer 34 of the substrate 20 and can be developed uniformly. Further, by moving the substrate 20 upward, the droplet 50 (see FIG. 4) on the surface of the photosensitive layer 34 flows to the lower portion 20c of the substrate 20, and the peeled off material generated by development can be easily removed.
In the developing method, the developing steps shown in FIGS. 6 to 8 may be repeated a plurality of times instead of once, and are appropriately determined according to the type of the photosensitive layer 34 or the type of the developer. In this case, it is preferable to perform the next development processing after the substrate 20 is changed from the state shown in FIG. 8 to the state shown in FIG. 6, that is, after the substrate 20 is lowered.
　次に、現像液の粒径について説明する。
　上述のように現像液は微小な粒状の形態でノズル４０から噴射される。微小な粒状とは、粒径が５ｍｍ以下であることをいい、好ましくは２ｍｍ以下である。微小な粒状の下限値としては、基板２０に付着して現像できる最小の大きさであり、この場合、粒径は０．１ｍｍ程度である。粒径が０．１ｍｍ未満であると浮遊粒子と呼ばれるものとなり、現像液が基板２０に付着しにくくなり好ましくない。
　上述の現像液の粒径は以下のようにして測定されたものである。現像液の粒径の測定は、凡そ温度２３±５℃、湿度５５±５％に制御設定しているクリーンルーム内で行う。
　図９および図１０は現像液の粒径の測定方法を説明するための模式図である。
　現像液の粒径の測定には、図９に示すようにノズル４０にポンプ５２を配管５３を介して接続し、さらに現像液を貯留するタンク５４を接続した装置を用いる。ポンプ５２により、タンク５４内の現像液がノズル４０から噴射される。ポンプ５２はダイヤフラム型ポンプであり、１秒間に１回の頻度でノズル４０から現像液を噴射させた。現像液は、４０℃の１質量％炭酸ナトリウム水溶液である。 Next, the particle size of the developer will be described.
As described above, the developer is ejected from the nozzle 40 in the form of fine particles. The fine granularity means that the particle size is 5 mm or less, preferably 2 mm or less. The lower limit value of the fine particles is the minimum size that can adhere to the substrate 20 and develop, and in this case, the particle size is about 0.1 mm. When the particle size is less than 0.1 mm, the particles are called floating particles, and the developer is difficult to adhere to the substrate 20, which is not preferable.
The particle size of the developer described above was measured as follows. The particle size of the developer is measured in a clean room controlled at a temperature of about 23 ± 5 ° C. and a humidity of 55 ± 5%.
9 and 10 are schematic diagrams for explaining a method for measuring the particle size of the developer.
For measuring the particle size of the developing solution, as shown in FIG. 9, a device in which a pump 52 is connected to a nozzle 40 via a pipe 53 and a tank 54 for storing the developing solution is connected. The developer in the tank 54 is ejected from the nozzle 40 by the pump 52. The pump 52 is a diaphragm type pump, and the developer is ejected from the nozzle 40 at a frequency of once per second. The developer is a 1% by mass sodium carbonate aqueous solution at 40 ° C.
　現像液の粒径の測定は、現像液がノズル４０から噴射されている状態で、ポリエチレンテレフタレートシート５６（以下、単にＰＥＴシート５６という）を瞬間的に出し入れさせて行う。ＰＥＴシート５６の表面５６ａを現像液に長く当てていると、図１０に示すように、現像液の液滴５７が別の液滴５８の上に乗るため、ＰＥＴシート５６を瞬間的に出し入れさせる。出し入れさせたＰＥＴシート５６の現像液のかかる時間が最も短い所には液滴５７が乗っており、確認した所、目視上では半球状態とみなせた。現像液が長く当たっていそうな所、すなわち、入れ、出しの起点５６ｂ側は液滴５７が他の液滴５８上に被ったようだった。液滴と判断できるものを無作為に１０個選び、半球状の液滴の半径から球体半径を求めた。更に１０個の球体半径の平均を算出して、球体半径の平均値を得、この平均値を２倍した値を、現像液の粒径とした。
　半球状の液滴の半径Ｒから粒状の球体半径ｒは、ｒ＝Ｒ／（２１／３）を用いて求めることができる。 The particle size of the developer is measured by momentarily taking in and out a polyethylene terephthalate sheet 56 (hereinafter simply referred to as a PET sheet 56) in a state where the developer is sprayed from the nozzle 40. When the surface 56a of the PET sheet 56 is applied to the developer for a long time, as shown in FIG. 10, the developer droplet 57 is placed on another droplet 58, so that the PET sheet 56 is instantaneously put in and out. . Droplets 57 were placed in the place where the developing time of the PET sheet 56 taken out and taken out was the shortest, and when confirmed, it was visually recognized as a hemispherical state. It seemed that the liquid droplet 57 was covered on the other liquid droplets 58 at the place where the developer was likely to have been applied for a long time, that is, on the side of the starting point 56b. Ten particles that can be judged as droplets were randomly selected, and the sphere radius was determined from the radius of the hemispherical droplet. Further, an average of 10 sphere radii was calculated to obtain an average value of the sphere radii, and a value obtained by doubling the average value was defined as the particle diameter of the developer.
From the radius R of the hemispherical droplet, the granular sphere radius r can be obtained using r = R / (2 1/3 ).
　洗浄装置１６は、現像処理された基板２０を垂直に保持した状態で、基板２０を洗浄するものである。洗浄装置１６は、現像液にかえて洗浄液を利用すること以外、上述の現像装置１４と同じ構成であるため、その詳細な説明は省略する。洗浄装置１６では第１のタンク４４に洗浄液が貯留される。 The cleaning device 16 cleans the substrate 20 with the developed substrate 20 held vertically. Since the cleaning device 16 has the same configuration as the above-described developing device 14 except that a cleaning solution is used instead of the developing solution, a detailed description thereof will be omitted. In the cleaning device 16, the cleaning liquid is stored in the first tank 44.
　洗浄工程は、現像済みの感光性層３４表面にある現像液を洗浄水で置換する。置換される現像液を感光性層３４表面から排除する。感光性層３４表面上に僅かに残った現像液は置換していた洗浄水に溶け込む。更に次の洗浄液が来て、今まであった洗浄水を置換するといった工程を有する。これらの工程も平行して生じている。
　洗浄処理においても、基板２０を垂直に保持しているため、感光性層３４表面に達した洗浄液は感光性層３４表面に接触し、大半の洗浄液が重力で下方に流れる。次の間欠的な噴射による洗浄液が更に感光性層３４表面に達し、洗浄に関した後、下方に流れる。すなわち、常に新鮮な洗浄液を感光性層３４表面、直近に運ぶことができる。
　噴射した洗浄液によっても感光性層３４表面についた洗浄液を下方にかきとる効果を生む。洗浄液は通常水系であるため、極めて高い表面張力を有しており、洗浄液の比重は小さく、表面張力は高い。このため、感光性層３４表面の液膜は、そこに残ろうとする。よって、単なる自重効果だけでは新旧の洗浄液の切り替えは進み難いが、自重と噴射された洗浄液の勢いの双方で、感光性層３４表面での洗浄液の入れ替えを活発化できる。 In the washing step, the developer on the surface of the developed photosensitive layer 34 is replaced with washing water. The developer to be replaced is excluded from the surface of the photosensitive layer 34. The developer slightly remaining on the surface of the photosensitive layer 34 is dissolved in the washing water that has been replaced. Further, there is a process in which the next cleaning liquid comes and replaces the existing cleaning water. These processes also occur in parallel.
Also in the cleaning process, since the substrate 20 is held vertically, the cleaning liquid that has reached the surface of the photosensitive layer 34 contacts the surface of the photosensitive layer 34, and most of the cleaning liquid flows downward by gravity. The cleaning liquid by the next intermittent jet reaches the surface of the photosensitive layer 34 and flows downward after the cleaning. That is, it is possible to always carry a fresh cleaning solution to the surface of the photosensitive layer 34 in the immediate vicinity.
The sprayed cleaning liquid also produces the effect of scraping the cleaning liquid on the surface of the photosensitive layer 34 downward. Since the cleaning liquid is usually aqueous, it has an extremely high surface tension, the specific gravity of the cleaning liquid is small, and the surface tension is high. For this reason, the liquid film on the surface of the photosensitive layer 34 tends to remain there. Therefore, it is difficult to switch between the old and new cleaning liquids only by the self-weight effect, but the replacement of the cleaning liquid on the surface of the photosensitive layer 34 can be activated by both the self-weight and the momentum of the jetted cleaning liquid.
　このように洗浄装置１６では、基板２０を垂直に保持し、かつ垂直に保持した状態で、現像処理済みの基板２０の表面２０ａの感光性層３４および裏面２０ｂの感光性層３４に、洗浄液をノズル４０から微小な粒状にして間欠的に噴射することで、洗浄液の液滴５０の表面積を増やして感光性層３４表面に付着し易くし、濡れ性を上げている。また、洗浄液を間欠的に噴射することで、洗浄液の濡れやすさを更に向上させることができる。基板２０を垂直に保持することで被現像物が溶け込んだ洗浄液の液滴５０を基板２０の下方２０ｃに移動させやすくすることができる。これにより、洗浄ムラ等を抑制した高度な洗浄を行うことができる。 As described above, in the cleaning device 16, the cleaning liquid is applied to the photosensitive layer 34 on the front surface 20 a and the photosensitive layer 34 on the back surface 20 b of the substrate 20 that has been subjected to the development processing while the substrate 20 is held vertically. By intermittently injecting fine particles from the nozzle 40, the surface area of the droplet 50 of the cleaning liquid is increased so that it adheres to the surface of the photosensitive layer 34, thereby improving the wettability. In addition, the ease of wetting of the cleaning liquid can be further improved by intermittently spraying the cleaning liquid. By holding the substrate 20 vertically, it is possible to easily move the droplet 50 of the cleaning liquid in which the developing object is dissolved to the lower part 20 c of the substrate 20. As a result, it is possible to perform advanced cleaning while suppressing cleaning unevenness and the like.
　また、洗浄液の噴射について噴射範囲Ｄｓを水平面ＰＨ以下とすることで、被現像物が溶け込んだ洗浄液の液滴５０を基板２０の下方２０ｃに移動させやすくすることができる。また、噴射範囲Ｄｓを垂直面Ｐｖ以内とすることで、洗浄液を有効に利用することができる。
　洗浄装置１６を用いた洗浄方法は、上述の図６～図８に示す現像方法に比して現像液にかえて洗浄液とした点以外は、現像方法と同じであるため、その詳細な説明は省略する。洗浄方法でも、上述のように、基板２０を中立させるために基板２０の垂直方向Ｖにおける同じ位置に、噴射タイミングを一致させて、すなわち、同期させて洗浄液を噴射させることが好ましい。基板２０の両面をまとめて洗浄処理することにより、効率良く洗浄処理をすることができる。
　洗浄方法では、図６～図８に示す洗浄工程を１回ではなく、複数回繰り返してもよく、現像液の種類または洗浄液の種類等に応じて適宜決定される。この場合、基板２０を図８の状態から図６に示す状態にして、すなわち、基板２０を下方に下げた後、次回の洗浄処理を行うことが好ましい。 Further, by injection range Ds less horizontal plane P H for the cleaning liquid injection, it is possible to easily move the droplet 50 of the cleaning solution that dissolves is the development was below 20c of the substrate 20. In addition, the cleaning liquid can be effectively used by setting the injection range Ds to be within the vertical plane Pv.
The cleaning method using the cleaning device 16 is the same as the developing method except that the developing solution is replaced with a developing solution as compared with the developing method shown in FIGS. Omitted. Also in the cleaning method, as described above, in order to make the substrate 20 neutral, it is preferable to spray the cleaning liquid at the same position in the vertical direction V of the substrate 20, that is, in synchronization. By cleaning the both surfaces of the substrate 20 together, the cleaning process can be performed efficiently.
In the cleaning method, the cleaning steps shown in FIGS. 6 to 8 may be repeated a plurality of times instead of once, and are appropriately determined according to the type of developer or the type of cleaning solution. In this case, it is preferable to perform the next cleaning process after the substrate 20 is changed from the state shown in FIG. 8 to the state shown in FIG. 6, that is, after the substrate 20 is lowered.
　上述の洗浄装置１６を用いて洗浄工程においては、洗浄液を微小な粒状にして間欠的に噴射しているが、洗浄液の間欠的に噴射は、現像液の間欠的に噴射と同じ定義であり、１秒間に１．５回以下、すなわち、１．５Ｈｚ以下の噴射のことをいう。間欠的な噴射において、好ましくは１秒間に１回以下、すなわち、１Ｈｚ以下、更に望ましくは２秒に１回以下、すなわち、０．５Ｈｚ以下である。
　現像液と同じく、洗浄液の間欠的な噴射における噴射の下限値は、使用する洗浄液の種類、洗浄液の噴射量等、更には周囲の環境により変わるため、特に限定されるものではない。例えば、洗浄液を噴霧する際には、基板の表面で洗浄液が局所的に乾燥すると、洗浄ムラが生じるため好ましくない。このようなことから、間欠的な噴射における噴射の下限値は、洗浄液が局所的に乾燥しない条件に応じて適宜設定される。この場合、洗浄液の種類毎に噴射量および使用環境に基づき局所的に乾燥しない条件を予め求めておき、これに基づいて間欠的な噴射における噴射の下限値を予め設定することができる。 In the cleaning process using the above-described cleaning device 16, the cleaning liquid is intermittently ejected in fine particles, but the intermittent injection of the cleaning liquid has the same definition as the intermittent injection of the developer, This refers to an injection of 1.5 times or less, that is, 1.5 Hz or less per second. In intermittent injection, it is preferably no more than once per second, that is, 1 Hz or less, more desirably no more than once every 2 seconds, that is, 0.5 Hz or less.
As with the developer, the lower limit value of the ejection of the cleaning liquid intermittently varies depending on the type of the cleaning liquid to be used, the amount of the cleaning liquid to be sprayed, and the surrounding environment, and is not particularly limited. For example, when spraying the cleaning liquid, if the cleaning liquid is locally dried on the surface of the substrate, cleaning unevenness occurs, which is not preferable. For this reason, the lower limit value of the injection in the intermittent injection is appropriately set according to the condition where the cleaning liquid is not locally dried. In this case, for each type of cleaning liquid, conditions that do not dry locally based on the injection amount and use environment can be obtained in advance, and based on this, the lower limit value of injection in intermittent injection can be set in advance.
　また、洗浄液は微小な粒状の形態で、現像液と同様にノズル４０から噴射されるが、この洗浄液の微小な粒状も、現像液の微小な粒状と同じ定義である。このため、洗浄液でも微小な粒状とは、洗浄液の粒径が５ｍｍ以下であることをいい、好ましくは２ｍｍ以下であり、下限値としては基板２０に付着して洗浄できる最小の大きさであり、この場合、粒径は０．１ｍｍ程度である。粒径が０．１ｍｍ未満であると浮遊粒子と呼ばれるものとなり、洗浄液が基板２０に付着しにくくなり好ましくない。
　洗浄液の粒径の測定方法は、洗浄液を用いた点以外は現像液の粒径の測定方法と同じであるため、その詳細な説明は省略する。 The cleaning liquid is in the form of fine particles and is ejected from the nozzle 40 in the same manner as the developer. The fine particles of the cleaning liquid have the same definition as the fine particles of the developer. For this reason, the fine particles in the cleaning liquid means that the particle size of the cleaning liquid is 5 mm or less, preferably 2 mm or less, and the lower limit is the minimum size that can be adhered to the substrate 20 and cleaned. In this case, the particle size is about 0.1 mm. When the particle size is less than 0.1 mm, the particles are called floating particles, and the cleaning liquid is difficult to adhere to the substrate 20, which is not preferable.
The method for measuring the particle size of the cleaning solution is the same as the method for measuring the particle size of the developing solution except that the cleaning solution is used, and thus detailed description thereof is omitted.
　また、第１のタンク４４に現像液を貯留し、第２のタンク４５に洗浄液を貯留しておき、切替バルブ４６を切り替えることで、１つの装置で現像装置１４と洗浄装置１６とを兼用することもできる。この場合、１つの装置で連続して現像処理と洗浄処理ができる。
　また、第１のタンク４４に現像液を貯留しておき、現像処理が終了した後、第１のタンク４４の現像液を洗浄液に入れ換えて、洗浄装置１６として使用してもよい。
　パターン形成装置１０では、現像装置１４と洗浄装置１６とを同じ構成としたが、これに限定されるものではなく、現像装置１４を上述の構成とし、洗浄装置１６を別の構成としてもよい。この場合、例えば、基板２０の幅方向に延びるスリット状のノズルを設け、このスリット状のノズルから洗浄液を連続的に基板２０の感光性層３４全面に噴射する構成とする。 Further, the developing solution is stored in the first tank 44, the cleaning solution is stored in the second tank 45, and the switching valve 46 is switched, so that the developing device 14 and the cleaning device 16 can be used as a single device. You can also In this case, the development process and the cleaning process can be performed continuously with one apparatus.
Alternatively, the developing solution may be stored in the first tank 44, and after the development processing is completed, the developing solution in the first tank 44 may be replaced with the cleaning solution and used as the cleaning device 16.
In the pattern forming apparatus 10, the developing device 14 and the cleaning device 16 have the same configuration. However, the configuration is not limited to this, and the developing device 14 may have the above-described configuration, and the cleaning device 16 may have another configuration. In this case, for example, a slit-like nozzle extending in the width direction of the substrate 20 is provided, and a cleaning liquid is continuously sprayed from the slit-like nozzle to the entire surface of the photosensitive layer 34 of the substrate 20.
　パターン形成装置１０においては、１つの基板２０毎に処理する枚葉式でも、長尺の基板を用いて連続して処理するロールツーロール式のいずれでもよい。枚葉式の場合、現像装置１４および洗浄装置１６では基板１枚ごとに処理され、ロールツーロール式の場合、現像装置１４および洗浄装置１６では基板が連続的に処理される。 The pattern forming apparatus 10 may be either a single wafer type that processes each substrate 20 or a roll-to-roll type that processes continuously using a long substrate. In the single wafer type, the developing device 14 and the cleaning device 16 process each substrate, and in the roll-to-roll method, the developing device 14 and the cleaning device 16 process the substrate continuously.
　次に、パターン形成装置１０によるパターン形成方法についてより具体的に説明する。 Next, the pattern forming method by the pattern forming apparatus 10 will be described more specifically.
＜組成物の調製＞
　イソプロパノール（ＩＰＡ）　９４．９質量部、ポリアクリル酸　３質量部、メチレンビスアクリルアミド（ＭＢＡ）　２質量部、ＩＲＧＡＣＵＲＥ（登録商標）１２７（ＢＡＳＦ製）　０．１質量部、をこの順に従って調液し、組成物を得る。
＜プライマー層形成用組成物の調製＞
　水素化ニトリルブタジエンゴム　Ｚｅｔｐｏｌ（登録商標）００２０（日本ゼオン製）１００ｇをシクロペンタノン（東京化成製）９００ｇに溶解させた液をプライマー層形成用組成物とする。
＜基板の作製＞
　１００μｍ厚のＡ４３００（商品名　東洋紡株式会社製）のシート（サイズ縦×横：６インチ×６インチ）を支持体として、表面上と裏面上にバーコートによってプライマー層形成用組成物を２μｍの膜厚になるように塗布して、基板の両面に、後述するパターン状のめっき層と基板との密着性を高めるためのプライマー層を形成する。プライマー層は上述の下塗層３２に相当するものである。
　さらに各プライマー層上に、上述の組成物をバーコートによって、例えば、０．２５μｍの厚みになるように成膜して感光性層３４を作製し、露光処理される基板２０を得る。 <Preparation of composition>
94.9 parts by mass of isopropanol (IPA), 3 parts by mass of polyacrylic acid, 2 parts by mass of methylenebisacrylamide (MBA), 0.1 part by mass of IRGACURE (registered trademark) 127 (manufactured by BASF) were prepared according to this order. To obtain a composition.
<Preparation of primer layer forming composition>
A solution obtained by dissolving 100 g of hydrogenated nitrile butadiene rubber Zetpol (registered trademark) 0020 (manufactured by Nippon Zeon) in 900 g of cyclopentanone (manufactured by Tokyo Chemical Industry) is used as a primer layer forming composition.
<Production of substrate>
Using a 100 μm thick sheet of A4300 (trade name, manufactured by Toyobo Co., Ltd.) (size length × width: 6 inches × 6 inches) as a support, a primer layer forming composition is formed into a 2 μm film by bar coating on the front and back surfaces. The primer layer is applied so as to be thick, and a primer layer is formed on both surfaces of the substrate to enhance the adhesion between the patterned plating layer (described later) and the substrate. The primer layer corresponds to the above-described undercoat layer 32.
Further, the above-described composition is formed on each primer layer by bar coating so as to have a thickness of, for example, 0.25 μm to form a photosensitive layer 34, and the substrate 20 to be exposed is obtained.
　パターン形成装置１０の露光装置１２では、例えば、上述の露光処理される基板２０を異なるパターンを有するマスク二枚にて挟み込み、３００ｎｍ以下の波長の光を含む出射光を出射できるＵＶランプＤｅｅｐ　ＵＶ　Ｌａｍｐ（Ｕｓｈｉｏ製）を用いて、両面の感光性層３４をそれぞれマスクのパターン状にて露光エネルギーが１００ｍＪになるよう露光し、露光済みの基板２０を得る。露光は３００ｎｍ以下の波長の光でなされるが、露光光は上述のシートからなる支持体にて吸収されるため、互いに他の感光性層３４の露光光の影響が抑制される。 In the exposure apparatus 12 of the pattern forming apparatus 10, for example, a UV lamp Deep UV Lamp capable of emitting the emitted light including light having a wavelength of 300 nm or less by sandwiching the substrate 20 to be exposed as described above with two masks having different patterns. (Usio) is used to expose the photosensitive layers 34 on both sides in a mask pattern so that the exposure energy is 100 mJ to obtain an exposed substrate 20. Although exposure is performed with light having a wavelength of 300 nm or less, since the exposure light is absorbed by the support made of the above-described sheet, the influence of the exposure light of the other photosensitive layers 34 is suppressed.
　次に、現像装置１４にて、露光済みの基板２０を垂直に保持し、上述の現像処理を２回施す。この場合、現像液には、例えば、４０℃の１質量％炭酸ナトリウム水溶液が用いられる。
　次に、例えば、現像液を洗浄液に入れ換え、現像装置１４を洗浄装置１６とする。そして、洗浄装置１６にて、現像済みの基板２０を垂直に保持し、上述の洗浄処理を２回施す。この場合、洗浄液には、例えば、４０℃の純水が用いられる。
　このようにして基板２０の両面にパターン状のめっき層、すなわち、パターンが形成される。 Next, the exposed substrate 20 is held vertically by the developing device 14 and the above-described development processing is performed twice. In this case, for example, a 1 mass% sodium carbonate aqueous solution at 40 ° C. is used as the developer.
Next, for example, the developing solution is replaced with a cleaning solution, and the developing device 14 is used as the cleaning device 16. Then, the developed substrate 20 is held vertically by the cleaning device 16 and the above-described cleaning process is performed twice. In this case, for example, 40 ° C. pure water is used as the cleaning liquid.
Thus, a patterned plating layer, that is, a pattern is formed on both surfaces of the substrate 20.
　なお、パターンの確認のため、洗浄処理後の基板２０を、０．０５質量％のローダミン６Ｇ水溶液に５分間浸漬して染色する。そして、基板２０の両面に配置されているパターン状被めっき層がそれぞれ使用したマスクと同じパターン形状になっているか否かを光学顕微鏡にて観察することで確認することができる。 For the confirmation of the pattern, the substrate 20 after the cleaning treatment is immersed in a 0.05% by mass rhodamine 6G aqueous solution for 5 minutes and dyed. And it can be confirmed by observing with an optical microscope whether the pattern-like to-be-plated layer arrange | positioned at both surfaces of the board | substrate 20 has the same pattern shape as the mask which each used.
　パターン形成方法については、上述のパターン形成方法に限定されるものではなく、現像処理をするものであれば、適宜利用可能である。例えば、パターン形成にフォトリソグラフィー法を用いるパターン形成に利用可能である。例えば、銀塩法よるパターン形成、および蒸着法よるパターン形成に利用可能である。
　銀塩法よるパターン形成では、まず、ハロゲン化銀が含まれる銀塩乳剤層が両面に形成された基板を用意する。基板の各銀塩乳剤層に、露光装置１２にて露光処理を施し、その後、現像装置１４を用いた現像処理を行う。そして、洗浄処理を行うことで、パターンを形成することができる。より具体的には、特開２０１５－２２３９７号公報に記載の金属細線の製造方法を利用することができる。この場合、洗浄処理には洗浄装置１６を用いた洗浄処理を行ってもよい。
　また、蒸着法よるパターン形成では、まず、蒸着により、基板の両面に銅箔層を形成する。基板の各銅箔層上レジスト膜を形成する。基板の各レジスト膜に、露光装置１２にて露光処理を施し、その後、現像装置１４を用いた現像処理を行う。そして、エッチングを施し、銅箔層から銅配線を形成する。銅箔層は、蒸着銅箔以外にも、電解銅箔が利用可能である。より具体的には、特開２０１４－２９６１４号公報に記載の銅配線を形成する工程を利用することができる。 The pattern forming method is not limited to the pattern forming method described above, and any pattern forming method can be used as long as it is subjected to development processing. For example, it can be used for pattern formation using a photolithography method for pattern formation. For example, it can be used for pattern formation by a silver salt method and pattern formation by a vapor deposition method.
In pattern formation by the silver salt method, first, a substrate on which silver salt emulsion layers containing silver halide are formed on both sides is prepared. Each silver salt emulsion layer of the substrate is subjected to exposure processing by the exposure device 12, and then development processing using the developing device 14 is performed. And a pattern can be formed by performing a washing process. More specifically, the method for producing a fine metal wire described in JP-A-2015-22397 can be used. In this case, the cleaning process may be performed using the cleaning device 16.
In the pattern formation by the vapor deposition method, first, a copper foil layer is formed on both surfaces of the substrate by vapor deposition. A resist film is formed on each copper foil layer of the substrate. Each resist film on the substrate is subjected to exposure processing by the exposure device 12, and thereafter development processing using the developing device 14 is performed. Etching is then performed to form copper wiring from the copper foil layer. As the copper foil layer, an electrolytic copper foil can be used in addition to the deposited copper foil. More specifically, the step of forming a copper wiring described in JP 2014-29614 A can be used.
　次に、基板２０の感光性層３４に形成されるパターンについて説明する。
　図１１はパターンの一例を示す模式的平面図である。
　図１１に示すパターン６０は、格子状のパターンであり、細線６２によりセル６４が構成されており、セル６４が多数組み合わされて格子状のパターンを構成する。パターン６０は、例えば、タッチパネルセンサーの検出電極等に利用される。
　各セル６４は、例えば、多角形で構成されている。多角形としては、三角形、正方形、長方形、平行四辺形、ひし形等の四角形、五角形、六角形、ランダム多角形等が挙げられる。また、多角形を構成する辺の一部が曲線であってもよい。 Next, a pattern formed on the photosensitive layer 34 of the substrate 20 will be described.
FIG. 11 is a schematic plan view showing an example of a pattern.
A pattern 60 shown in FIG. 11 is a lattice-shaped pattern, in which cells 64 are formed by thin lines 62, and a large number of cells 64 are combined to form a lattice-shaped pattern. The pattern 60 is used for, for example, a detection electrode of a touch panel sensor.
Each cell 64 is configured by a polygon, for example. Examples of the polygon include a triangle, a square, a rectangle, a parallelogram, a quadrangle such as a rhombus, a pentagon, a hexagon, and a random polygon. Further, a part of the sides constituting the polygon may be a curve.
　パターン６０のセル６４の一辺の長さＰが短すぎると、開口率および透過率が低下し、それに伴って、透明性が劣化するという問題がある。反対に、セル６４の一辺の長さＰが長すぎると、細線６２が視認されやすくなる可能性がある。
　パターン６０のセル６４の一辺の長さＰは特に限定されるものではないが、５０～５００μｍであることが好ましく、１５０～４００μｍであることがさらに好ましい。セル６４の一辺の長さＰが上述の範囲である場合には、さらに透明性も良好に保つことが可能であり、表示装置の前面にとりつけた際に、違和感なく表示を視認することができる。
　可視光透過率の点から、細線６２より形成されるパターン６０の開口率は８５％以上であることが好ましく、９０％以上であることがさらに好ましく、９５％以上であることが最も好ましい。開口率とは、細線６２を除いた透光性部分が全体に占める割合であり、例えば、線幅６μｍ、セル６４の一辺の長さＰが２４０μｍの正方形の格子状の開口率は９５％である。 When the length P of one side of the cell 64 of the pattern 60 is too short, there is a problem that the aperture ratio and the transmittance are lowered, and accordingly, the transparency is deteriorated. On the other hand, if the length P of one side of the cell 64 is too long, the thin line 62 may be easily visible.
The length P of one side of the cell 64 of the pattern 60 is not particularly limited, but is preferably 50 to 500 μm, and more preferably 150 to 400 μm. When the length P of one side of the cell 64 is in the above-mentioned range, it is possible to keep the transparency better, and when it is attached to the front surface of the display device, it is possible to visually recognize the display. .
From the viewpoint of visible light transmittance, the aperture ratio of the pattern 60 formed by the thin lines 62 is preferably 85% or more, more preferably 90% or more, and most preferably 95% or more. The aperture ratio is the ratio of the light-transmitting portion excluding the thin line 62 to the entire area. For example, the aperture ratio of a square lattice having a line width of 6 μm and a side length P of the cell 64 of 240 μm is 95%. is there.
　タッチパネルセンサーの検出電極等に利用される上述のパターン６０が、例えば、メッシュ構造（図示せず）の場合、メッシュ形状は同じ形が規則的に配列した定型形状でも良く、ランダム形状でも良い。定型形状の場合は、正方形、菱形、正六角形が好ましく、特に菱形が好ましい。菱形の場合、その鋭角の角度は、５０°～８０°であることが、表示装置とのモアレを低減する観点から好ましい。メッシュピッチｐ（図１１参照）は５０μｍ～５００μｍであることが好ましく、メッシュの開口率は９２％～９９％であることが好ましい。メッシュの開口率は、メッシュ部における導体細線の非占有面積率で定義される。
　なお、メッシュ状金属電極としては、例えば、特開２０１１－１２９５０１号公報、および特開２０１３－１４９２３６号公報等に開示されている網目状のメッシュ状金属電極を用いることができる。これ以外にも、例えば、静電容量式のタッチパネルに用いられる検出電極を適宜用いることができる。
　セル６４の一辺の長さＰ、メッシュの角度、メッシュの開口率については、例えば、光学顕微鏡、レーザー顕微鏡、デジタルマイクロスコープ等を用いて測定することができる。 For example, when the above-described pattern 60 used for the detection electrode of the touch panel sensor has a mesh structure (not shown), the mesh shape may be a regular shape in which the same shape is regularly arranged, or may be a random shape. In the case of a fixed shape, a square, a rhombus, and a regular hexagon are preferable, and a rhombus is particularly preferable. In the case of a rhombus, the acute angle is preferably 50 ° to 80 ° from the viewpoint of reducing moire with the display device. The mesh pitch p (see FIG. 11) is preferably 50 μm to 500 μm, and the mesh opening ratio is preferably 92% to 99%. The aperture ratio of the mesh is defined by the unoccupied area ratio of the conductor thin wires in the mesh portion.
As the mesh-like metal electrode, for example, a mesh-like mesh-like metal electrode disclosed in JP2011-129501A, JP2013-149236A, and the like can be used. In addition to this, for example, a detection electrode used for a capacitive touch panel can be used as appropriate.
The length P of one side of the cell 64, the mesh angle, and the aperture ratio of the mesh can be measured using, for example, an optical microscope, a laser microscope, a digital microscope, or the like.
　露光により形成されるパターンについて、より具体的に説明する。
　図１２は露光で形成されるタッチパネルセンサーの一例を示す模式的平面図であり、図１３は図１２に示すタッチパネルセンサーの形成に用いられるマスクパターンの一例を示す模式図であり、図１４は図１２に示すタッチパネルセンサーの形成に用いられるマスクパターンの他の例を示す模式図である。
　図１２～図１４において、同一構成物には、同一符号を付してその詳細な説明は省略する。 The pattern formed by exposure will be described more specifically.
12 is a schematic plan view showing an example of a touch panel sensor formed by exposure, FIG. 13 is a schematic view showing an example of a mask pattern used for forming the touch panel sensor shown in FIG. 12, and FIG. 12 is a schematic diagram showing another example of a mask pattern used for forming the touch panel sensor shown in FIG.
12 to 14, the same components are denoted by the same reference numerals, and detailed description thereof is omitted.
　図１２に示す構成のタッチパネルセンサー６９のパターンを形成する場合、例えば、基板２０の表面２０ａ側の感光性層３４に図１３に示す第１導電パターン７０を形成し、裏面２０ｂ側の感光性層３４に図１４に示す第２導電パターン８０を形成する。この場合、マスクパターンとして図１３に示す第１導電パターン７０が形成された露光マスクと、マスクパターンとして図１４に示す第２導電パターン８０が形成された露光マスクの２種類、用意して、各露光マスクを基板２０の表面２０ａと裏面２０ｂに密着させて露光する。 When the pattern of the touch panel sensor 69 configured as shown in FIG. 12 is formed, for example, the first conductive pattern 70 shown in FIG. 13 is formed on the photosensitive layer 34 on the front surface 20a side of the substrate 20, and the photosensitive layer on the back surface 20b side. A second conductive pattern 80 shown in FIG. In this case, two types of masks are prepared: an exposure mask in which the first conductive pattern 70 shown in FIG. 13 is formed as a mask pattern, and an exposure mask in which the second conductive pattern 80 shown in FIG. 14 is formed as a mask pattern. Exposure is performed by bringing an exposure mask into close contact with the front surface 20 a and the back surface 20 b of the substrate 20.
　図１３に示す第１導電パターン７０は、第１の方向に延び、並列に配置された複数の第１検知電極パターン７２を含む。各第１検知電極パターン７２は、その一端において、第１導電端子パターン７４と接続される。さらに、各第１導電端子パターン７４は導電性の第１配線パターン７６と接続される。 The first conductive pattern 70 shown in FIG. 13 includes a plurality of first detection electrode patterns 72 extending in the first direction and arranged in parallel. Each first detection electrode pattern 72 is connected to the first conductive terminal pattern 74 at one end thereof. Further, each first conductive terminal pattern 74 is connected to a conductive first wiring pattern 76.
　図１４に示す第２導電パターン８０は、第１の方向と直交する第２の方向に延び、並列に配列された第２検知電極パターン８２を含む。各第２検知電極パターン８２は、その一端において、第２導電端子パターン８４と接続される。各第２導電端子パターン８４は導電性の第２配線パターン８６と接続される。
　第１導電パターン７０および第２導電パターン８０には、例えば、特開２０１２－１４７２７７号公報、特開２０１２－１６３９３３号公報、特開２０１２－１７４７４８号公報、特開２０１２－１９０４４５号公報、特開２０１３－１４９２３７号公報、特開２０１３－１４９２３２号公報、特開２０１３－１４９２３６号公報に記載の電極パターンを用いることができる。さらには、これ以外にも特表２０１１－５１３８４６号公報、国際公開第２０１０／０１３６７９号に記載のパターンを用いることができる。 A second conductive pattern 80 shown in FIG. 14 includes second detection electrode patterns 82 extending in a second direction orthogonal to the first direction and arranged in parallel. Each second detection electrode pattern 82 is connected to the second conductive terminal pattern 84 at one end thereof. Each second conductive terminal pattern 84 is connected to a conductive second wiring pattern 86.
Examples of the first conductive pattern 70 and the second conductive pattern 80 include, for example, Japanese Unexamined Patent Application Publication Nos. 2012-147277, 2012-163933, 2012-174748, 2012-190445, and Japanese Unexamined Patent Application Publication No. 2012-190445. The electrode patterns described in JP2013-149237A, JP2013-149232A, and JP2013-149236A can be used. Furthermore, other than these, patterns described in Japanese Patent Application Publication No. 2011-513846 and International Publication No. 2010/013679 can be used.
　第１検知電極パターン７２と第１導電端子パターン７４および第２検知電極パターン８２と第２導電端子パターン８４は、タッチパネルセンサー６９においてタッチの検知が可能なセンサー領域を構成するものである。
　第１検知電極パターン７２は、第１検知電極６９ａ（図１２参照）を形成するパターンである。第１検知電極６９ａは受信用配線とも呼ばれる。第１検知電極パターン７２は受信用配線のパターンでもある。第２検知電極パターン８２は、第２検知電極６９ｄ（図１２参照）を形成するパターンである。第２検知電極６９ｄは送信用配線とも呼ばれる。第２検知電極パターン８２は送信用配線のパターンでもある。 The first detection electrode pattern 72, the first conductive terminal pattern 74, the second detection electrode pattern 82, and the second conductive terminal pattern 84 constitute a sensor region where touch detection can be performed in the touch panel sensor 69.
The first detection electrode pattern 72 is a pattern for forming the first detection electrode 69a (see FIG. 12). The first detection electrode 69a is also called a reception wiring. The first detection electrode pattern 72 is also a pattern for receiving wiring. The second detection electrode pattern 82 is a pattern for forming the second detection electrode 69d (see FIG. 12). The second detection electrode 69d is also called a transmission wiring. The second detection electrode pattern 82 is also a transmission wiring pattern.
　第１導電端子パターン７４は、第１検知電極６９ａに電気的に接続される第１導電端子６９ｂ（図１２参照）を形成するパターンである。第１配線パターン７６は、第１導電端子６９ｂに電気的に接続される第１配線６９ｃ（図１２参照）を形成するパターンでもある。
　第２導電端子パターン８４は、第２検知電極６９ｄに電気的に接続される第２導電端子６９ｅ（図１２参照）を形成するパターンである。第２配線パターン８６は、第２導電端子６９ｅに電気的に接続される第２配線６９ｆ（図１２参照）を形成するパターンである。
　第１導電端子６９ｂ、第１配線６９ｃ、第２導電端子６９ｅおよび第２配線６９ｆは、周辺配線と呼ばれる。
　タッチパネルセンサー６９では、例えば、第２検知電極６９ｄに矩形波状に電圧を印加し、電荷を蓄積させ、第１検知電極６９ａで電荷を読み取ることがなされる。 The first conductive terminal pattern 74 is a pattern for forming a first conductive terminal 69b (see FIG. 12) that is electrically connected to the first detection electrode 69a. The first wiring pattern 76 is also a pattern for forming a first wiring 69c (see FIG. 12) that is electrically connected to the first conductive terminal 69b.
The second conductive terminal pattern 84 is a pattern for forming a second conductive terminal 69e (see FIG. 12) that is electrically connected to the second detection electrode 69d. The second wiring pattern 86 is a pattern for forming a second wiring 69f (see FIG. 12) that is electrically connected to the second conductive terminal 69e.
The first conductive terminal 69b, the first wiring 69c, the second conductive terminal 69e, and the second wiring 69f are called peripheral wirings.
In the touch panel sensor 69, for example, a voltage is applied to the second detection electrode 69d in a rectangular wave shape to accumulate charges, and the charges are read by the first detection electrode 69a.
　次に、基板２０等を構成する支持体３０、下塗層３２および感光性層３４、ならびに支持体３１について説明する。 Next, the support 30, the undercoat layer 32 and the photosensitive layer 34, and the support 31 that constitute the substrate 20 and the like will be described.
［支持体］
　支持体は、２つの主面を有するものであれば特に限定されるものではなく、例えば、絶縁支持体が挙げられ、より具体的には、樹脂支持体、セラミック支持体、ガラス支持体等を使用することができ、樹脂支持体が好ましい。なお、樹脂支持体としては、後述する粘着シートも含まれる。
　樹脂支持体の材料としては、例えば、ポリエステル系樹脂（ポリエチレンテレフタレート、ポリエチレンナフタレート）、ポリエーテルスルホン、ポリアクリル系樹脂、ポリウレタン系樹脂、ポリカーボネート系樹脂、ポリスルホン系樹脂、ポリアミド系樹脂、ポリアリレート系樹脂、ポリオレフィン系樹脂、セルロース系樹脂、ポリ塩化ビニル系樹脂、シクロオレフィン系樹脂等が挙げられる。なかでも、ポリエチレンテレフタレート、ポリエチレンナフタレート、または、ポリオレフィンが好ましい。
　また、支持体としては、粘着性のある支持体、つまり、粘着シートを使用してもよい。粘着シートを構成する材料としては公知の材料（アクリル系粘着剤、シリコーン系粘着剤等）が使用できる。 [Support]
The support is not particularly limited as long as it has two main surfaces, and examples thereof include an insulating support, and more specifically, a resin support, a ceramic support, a glass support, and the like. Resin supports are preferred. In addition, as a resin support body, the adhesive sheet mentioned later is also contained.
Examples of the resin support material include polyester resins (polyethylene terephthalate, polyethylene naphthalate), polyethersulfone, polyacrylic resin, polyurethane resin, polycarbonate resin, polysulfone resin, polyamide resin, and polyarylate. Examples thereof include resins, polyolefin resins, cellulose resins, polyvinyl chloride resins, cycloolefin resins, and the like. Of these, polyethylene terephthalate, polyethylene naphthalate, or polyolefin is preferable.
Moreover, as a support body, you may use an adhesive support body, ie, an adhesive sheet. As the material constituting the pressure-sensitive adhesive sheet, known materials (acrylic pressure-sensitive adhesive, silicone pressure-sensitive adhesive, etc.) can be used.
　支持体の厚み（ｍｍ）は特に限定されるものではないが、取り扱い性および薄型化のバランスの点から、樹脂支持体では０．０１～２ｍｍが好ましく、０．０２～１ｍｍがより好ましく、０．０３～０．１ｍｍが最も好ましい。また、ガラス支持体では、０．０１～２ｍｍが好ましく、０．３～０．８ｍｍがより好ましく、０．４～０．７ｍｍが最も好ましい。
　また、支持体は、光を適切に透過することが好ましい。具体的には、支持体の全光線透過率は、８５～１００％であることが好ましい。 The thickness (mm) of the support is not particularly limited, but is preferably 0.01 to 2 mm, more preferably 0.02 to 1 mm, and more preferably 0 to 2 mm for the resin support in terms of the balance between handleability and thinning. 0.03-0.1 mm is most preferable. In the glass support, 0.01 to 2 mm is preferable, 0.3 to 0.8 mm is more preferable, and 0.4 to 0.7 mm is most preferable.
Moreover, it is preferable that a support body permeate | transmits light appropriately. Specifically, the total light transmittance of the support is preferably 85 to 100%.
［下塗層、下塗層の機能を有する支持体］
　下塗層は、紫外線吸収剤を含む層（紫外線吸収層）で形成される。これにより、感光性層が第１の露光光Ｌ１、第２の露光光Ｌ２により露光されてしまう場合、第１の露光光Ｌ１で一方の感光性層を露光し、第２の露光光Ｌ２で他方の感光性層を露光するとき、互いに異なる第１の露光光Ｌ１または第２の露光光Ｌ２で露光されることを抑制することができる。
　紫外線吸収剤が含まれる支持体を用いることでも、上述のように互いに異なる第１の露光光Ｌ１または第２の露光光Ｌ２で露光されることを抑制することができる。 [Undercoat layer, support having functions of undercoat layer]
The undercoat layer is formed of a layer containing an ultraviolet absorber (ultraviolet absorbing layer). Thereby, when the photosensitive layer is exposed with the first exposure light L 1 and the second exposure light L 2 , one of the photosensitive layers is exposed with the first exposure light L 1 and the second exposure light L 1 is exposed. when exposing the other photosensitive layer with light L 2, it can be prevented from being exposed to one another in different first exposure light L 1 or the second exposure light L 2.
Also by using a support including an ultraviolet absorber, exposure with different first exposure light L 1 or second exposure light L 2 as described above can be suppressed.
　下塗層および支持体で使用される紫外線吸収剤の種類は特に限定されるものではなく、公知の紫外線吸収剤を使用でき、例えば、サリチル酸系紫外線吸収剤、ベンゾフェノン系紫外線吸収剤、ベンゾトリアゾール系紫外線吸収剤、シアノアクリレート系紫外線吸収剤、ベンゾエート系紫外線吸収剤、マロン酸エステル系紫外線吸収剤、シュウ酸アニリド系紫外線吸収剤等が挙げられる。
　上述のサリチル酸系紫外線吸収剤としては、フェニルサリシート、ｐ－ｔｅｒｔ－ブチルフェニルサリシート、ｐ－オクチルフェニルサリシートが挙げられる。
　上述のベンゾフェノン系紫外線吸収剤としては、２，４－ジヒドロキシベンゾフェノン、２－ヒドロキシ－４－メトキシベンゾフェノン、２－ヒドロキシ－４－オクトキシベンゾフェノン、２－ヒドロキシ－４－ドデシルオキシベンゾフェノン、２，２′－ジヒドロキシ－４－メトキシベンゾフェノン、２，２′－ジヒドロキシ－４、４′－ジメトキシベンゾフェノン、２－ヒドロキシ－４－メトキシ－５－スルホベンゾフェノン、ビス（２－メトキシ－４－ヒドロキシ－５－ベンゾイルフェニル）メタン等が挙げられる。
　上述のベンゾトリアゾール系紫外線吸収剤としては、２－（２Ｈ－ベンゾトリアゾール－２－イル）－４－（１，１，３，３－テトラメチルブチル）フェノール、２－（２′－ヒドロキシ－５′－メチルフェニル）ベンゾトリアゾール、２－（２′－ヒドロキシ－５′－ｔｅｒｔ－ブチルフェニル）ベンゾトリアゾール、２－（２′－ヒドロキシ－３′，５′ジ－ｔｅｒｔ－ブチルフェニル）ベンゾトリアゾール、２－（２′－ヒドロキシ－３′－ｔｅｒｔ－ブチル－５′－メチルフェニル）－５－クロロベンゾトリアゾール、２－（２′－ヒドロキシ－３′，５′－ジ－ｔｅｒｔ－ブチル－フェニル）－５－クロロベンゾトリアゾール、２－（２′－ヒドロキシ－３′，５′－ジ－ｔｅｒｔ－ブチル－５′－アミルフェニル）ベンゾトリアゾール、２－（２′－ヒドロキシ－４′－オクトキシフェニル）ベンゾトリアゾール等が挙げられる。
　上述のシアノアクリレート系紫外線吸収剤としては、２－エチルヘキシル－２－シアノ－３，３′－ジフェニルアクリレート、エチル－２－シアノ－３，３′－ジフェニルアクリレート等が挙げられる。 The type of the UV absorber used in the undercoat layer and the support is not particularly limited, and a known UV absorber can be used, for example, a salicylic acid UV absorber, a benzophenone UV absorber, a benzotriazole Examples thereof include ultraviolet absorbers, cyanoacrylate ultraviolet absorbers, benzoate ultraviolet absorbers, malonic ester ultraviolet absorbers, and oxalic anilide ultraviolet absorbers.
Examples of the above-mentioned salicylic acid-based ultraviolet absorber include phenyl salicylate, p-tert-butylphenyl salicylate, and p-octylphenyl salicylate.
Examples of the benzophenone-based ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2 ′. -Dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, bis (2-methoxy-4-hydroxy-5-benzoylphenyl) ) Methane and the like.
Examples of the benzotriazole-based UV absorber include 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2- (2′-hydroxy-5). '-Methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3', 5'di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butyl-phenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butyl-5'-amylphenyl) benzotria Lumpur, 2- (2'-hydroxy-4'-octoxyphenyl) benzotriazole.
Examples of the cyanoacrylate-based ultraviolet absorber include 2-ethylhexyl-2-cyano-3,3′-diphenyl acrylate, ethyl-2-cyano-3,3′-diphenyl acrylate, and the like.
　また、下塗層については、上述のように密着性を高める効果を優位に有するものであってもよい。この場合、例えば、下塗層は、以下に示す構成のものを用いることができる。 Further, the undercoat layer may have an advantage of improving the adhesion as described above. In this case, for example, an undercoat layer having the following configuration can be used.
　下塗層の厚みは特に制限されないが、一般的には、０．０１～１００μｍが好ましく、０．０５～２０μｍがより好ましく、０．０５～１０μｍがさらに好ましい。
　下塗層の材料は特に制限されず、基板との密着性が良好な樹脂であることが好ましい。樹脂の具体例としては、例えば、熱硬化性樹脂でも熱可塑性樹脂でもまたそれらの混合物でもよく、例えば、熱硬化性樹脂としては、エポキシ樹脂、フェノール樹脂、ポリイミド樹脂、ポリエステル樹脂、ビスマレイミド樹脂、ポリオレフィン系樹脂、イソシアネート系樹脂等が挙げられる。熱可塑性樹脂としては、例えば、フェノキシ樹脂、ポリエーテルスルフォン、ポリスルフォン、ポリフェニレンスルフォン、ポリフェニレンサルファイド、ポリフェニルエーテル、ポリエーテルイミド、ＡＢＳ樹脂等が挙げられる。
　熱可塑性樹脂と熱硬化性樹脂とは、それぞれ単独で用いてもよいし、２種以上併用してもよい。また、シアノ基を含有する樹脂を使用してもよく、具体的には、アクリロニトリル－ブタジエン－スチレン共重合体（ＡＢＳ樹脂）、または特開２０１０－８４１９６号〔００３９〕～〔００６３〕記載の「側鎖にシアノ基を有するユニットを含むポリマー」を用いてもよい。
　また、ＮＢＲゴム（アクリロニトリルブタジエンゴム）またはＳＢＲゴム（スチレンブタジエンゴム）等のゴム成分を用いることもできる。 The thickness of the undercoat layer is not particularly limited, but is generally preferably 0.01 to 100 μm, more preferably 0.05 to 20 μm, and further preferably 0.05 to 10 μm.
The material for the undercoat layer is not particularly limited, and is preferably a resin having good adhesion to the substrate. Specific examples of the resin may be, for example, a thermosetting resin, a thermoplastic resin, or a mixture thereof. For example, as the thermosetting resin, an epoxy resin, a phenol resin, a polyimide resin, a polyester resin, a bismaleimide resin, Examples include polyolefin resins and isocyanate resins. Examples of the thermoplastic resin include phenoxy resin, polyether sulfone, polysulfone, polyphenylene sulfone, polyphenylene sulfide, polyphenyl ether, polyether imide, and ABS resin.
The thermoplastic resin and the thermosetting resin may be used alone or in combination of two or more. Further, a resin containing a cyano group may be used. Specifically, an acrylonitrile-butadiene-styrene copolymer (ABS resin) or “JP-A 2010-84196 [0039] to [0063]” A polymer including a unit having a cyano group in the side chain may be used.
A rubber component such as NBR rubber (acrylonitrile butadiene rubber) or SBR rubber (styrene butadiene rubber) can also be used.
　下塗層を構成する材料の好適態様の一つとしては、水素添加されていてもよい共役ジエン化合物単位を有するポリマーが挙げられる。共役ジエン化合物単位とは、共役ジエン化合物由来の繰り返し単位を意味する。共役ジエン化合物としては、一つの単結合で隔てられた、二つの炭素－炭素二重結合を有する分子構造を有する化合物であれば特に制限されない。
　共役ジエン化合物由来の繰り返し単位の好適態様の一つとしては、ブタジエン骨格を有する化合物が重合反応することで生成する繰り返し単位が挙げられる。
　上記共役ジエン化合物単位は水素添加されていてもよく、水素添加された共役ジエン化合物単位を含む場合、パターン状金属層の密着性がより向上し好ましい。つまり、共役ジエン化合物由来の繰り返し単位中の二重結合が水素添加されていてもよい。
　水素添加されていてもよい共役ジエン化合物単位を有するポリマーには、上述した相互作用性基が含まれていてもよい。
　このポリマーの好適な態様としては、アクリロニトリルブタジエンゴム（ＮＢＲ）、カルボキシル基含有ニトリルゴム（ＸＮＢＲ）、アクリロニトリル－ブタジエン－イソプレンゴム（ＮＢＩＲ）、アクリロニトリル－ブタジエン－スチレン共重合体（ＡＢＳ樹脂）、または、これらの水素添加物（例えば、水素添加アクリロニトリルブタジエンゴム）等が挙げられる。 One preferred embodiment of the material constituting the undercoat layer is a polymer having a conjugated diene compound unit that may be hydrogenated. The conjugated diene compound unit means a repeating unit derived from a conjugated diene compound. The conjugated diene compound is not particularly limited as long as it is a compound having a molecular structure having two carbon-carbon double bonds separated by one single bond.
One preferred embodiment of the repeating unit derived from a conjugated diene compound includes a repeating unit produced by a polymerization reaction of a compound having a butadiene skeleton.
The conjugated diene compound unit may be hydrogenated. When the conjugated diene compound unit includes a hydrogenated conjugated diene compound unit, the adhesion of the patterned metal layer is preferably improved. That is, the double bond in the repeating unit derived from the conjugated diene compound may be hydrogenated.
The above-mentioned interactive group may be contained in the polymer having a conjugated diene compound unit that may be hydrogenated.
Preferred examples of this polymer include acrylonitrile butadiene rubber (NBR), carboxyl group-containing nitrile rubber (XNBR), acrylonitrile-butadiene-isoprene rubber (NBIR), acrylonitrile-butadiene-styrene copolymer (ABS resin), or These hydrogenated materials (for example, hydrogenated acrylonitrile butadiene rubber) and the like can be mentioned.
　下塗層には、他の添加剤（例えば、増感剤、酸化防止剤、帯電防止剤、紫外線吸収剤、フィラー、粒子、難燃剤、界面活性剤、滑剤、可塑剤等）が含まれていてもよい。 The undercoat layer contains other additives (for example, sensitizers, antioxidants, antistatic agents, ultraviolet absorbers, fillers, particles, flame retardants, surfactants, lubricants, plasticizers, etc.). May be.
　下塗層の形成方法は特に制限されず、使用される樹脂を基板上にラミネートする方法、または必要な成分を溶解可能な溶剤に溶解し、塗布等の方法で基板表面上に塗布および乾燥する方法等が挙げられる。
　塗布方法における加熱温度と時間は、塗布溶剤が充分乾燥し得る条件を選択すればよいが、製造適性の点からは、加熱温度２００℃以下、時間６０分以内の範囲の加熱条件を選択することが好ましく、加熱温度４０～１００℃、時間２０分以内の範囲の加熱条件を選択することがより好ましい。なお、使用される溶剤は、使用する樹脂に応じて適宜最適な溶剤（例えば、シクロヘキサノン、メチルエチルケトン）が選択される。 The method for forming the undercoat layer is not particularly limited, and a method of laminating the resin to be used on the substrate, or a method in which a necessary component is dissolved in a soluble solvent, and coating and drying on the substrate surface by a method such as coating. Methods and the like.
The heating temperature and time in the coating method may be selected so that the coating solvent can be sufficiently dried, but from the viewpoint of production suitability, the heating temperature should be 200 ° C. or less and the heating condition within the range of 60 minutes. It is preferable to select heating conditions in the range of heating temperature 40 to 100 ° C. and time 20 minutes or less. As the solvent to be used, an optimal solvent (for example, cyclohexanone or methyl ethyl ketone) is appropriately selected according to the resin to be used.
［感光性層］
　感光性層は、光照射により感光して硬化する層であれば特に限定されるものではなく、公知の感光性層を使用することができる。感光性層は、上述のように第１の露光光Ｌ１、第２の露光光Ｌ２により露光された部分が硬化するものである。
　なかでも、感光性層としては、めっき処理が施される被めっき層を形成すための被めっき層形成用層であることが好ましい。なお、被めっき層形成用組成物より形成される被めっき層に、めっき処理を施すことにより、被めっき層上に金属層を配置することができる。 [Photosensitive layer]
The photosensitive layer is not particularly limited as long as it is a layer that is sensitized and cured by light irradiation, and a known photosensitive layer can be used. As described above, the photosensitive layer is formed by curing a portion exposed by the first exposure light L 1 and the second exposure light L 2 .
Especially, as a photosensitive layer, it is preferable that it is a layer for to-be-plated layer formation for forming the to-be-plated layer to which a plating process is performed. In addition, a metal layer can be arrange | positioned on a to-be-plated layer by performing a plating process to the to-be-plated layer formed from the composition for to-be-plated layer forming.
　被めっき層形成用層は、光照射により感光して予め設定されたパターン状の被めっき層を形成できる層であればよく、なかでも、重合開始剤と、以下の化合物Ｘまたは組成物Ｙとを含む層であることが好ましい。
化合物Ｘ：めっき触媒またはその前駆体と相互作用する官能基（以後、単に「相互作用性基」とも称する）、および、重合性基を有する化合物
組成物Ｙ：めっき触媒またはその前駆体と相互作用する官能基を有する化合物、および、重合性基を有する化合物を含む組成物
　以下では、まず、被めっき層形成用層に含まれる材料について詳述する。 The layer for forming a layer to be plated may be any layer that can be exposed to light to form a predetermined pattern-shaped layer to be plated, and in particular, a polymerization initiator and the following compound X or composition Y: It is preferable that it is a layer containing.
Compound X: a functional group that interacts with the plating catalyst or its precursor (hereinafter, also simply referred to as “interactive group”) and a compound composition having a polymerizable group Y: interaction with the plating catalyst or its precursor The composition containing the compound which has a functional group to perform, and the compound which has a polymeric group Below, the material contained in the layer for to-be-plated layer formation is explained in full detail first.
（重合開始剤）
　重合開始剤としては、特に限定されるものではなく、公知の重合開始剤（いわゆる光重合開始剤）等を用いることができる。重合開始剤の例としては、ベンゾフェノン類、アセトフェノン類、α－アミノアルキルフェノン類、ベンゾイン類、ケトン類、チオキサントン類、ベンジル類、ベンジルケタール類、オキスムエステル類、アンソロン類、テトラメチルチウラムモノサルファイド類、ビスアシルフォスフィノキサイド類、アシルフォスフィンオキサイド類、アントラキノン類、アゾ化合物等およびその誘導体を挙げることができる。 (Polymerization initiator)
The polymerization initiator is not particularly limited, and a known polymerization initiator (so-called photopolymerization initiator) or the like can be used. Examples of polymerization initiators include benzophenones, acetophenones, α-aminoalkylphenones, benzoins, ketones, thioxanthones, benzyls, benzyl ketals, oxime esters, anthrones, tetramethylthiuram monosulfide Bisacylphosphine oxides, acylphosphine oxides, anthraquinones, azo compounds and the like, and derivatives thereof.
　被めっき層形成用層中における重合開始剤の含有量は特に限定されるものではないが、被めっき層の硬化性の点で、被めっき層形成用層全質量に対して、０．０１～５質量％であることが好ましく、０．１～３質量％であることがより好ましい。 The content of the polymerization initiator in the layer to be plated forming layer is not particularly limited, but is 0.01 to from the total mass of the layer to be plated layer in terms of curability of the layer to be plated. The content is preferably 5% by mass, more preferably 0.1 to 3% by mass.
（化合物Ｘ）
　化合物Ｘは、相互作用性基と重合性基とを有する化合物である。
　相互作用性基とは、めっき触媒またはその前駆体と相互作用できる官能基を意図し、例えば、めっき触媒またはその前駆体と静電相互作用を形成可能な官能基、または、めっき触媒またはその前駆体と配位形成可能な含窒素官能基、含硫黄官能基、含酸素官能基等を使用することができる。
　相互作用性基としてより具体的には、アミノ基、アミド基、イミド基、ウレア基、３級のアミノ基、アンモニウム基、アミジノ基、トリアジン環、トリアゾール環、ベンゾトリアゾール基、イミダゾール基、ベンズイミダゾール基、キノリン基、ピリジン基、ピリミジン基、ピラジン基、ナゾリン基、キノキサリン基、プリン基、トリアジン基、ピペリジン基、ピペラジン基、ピロリジン基、ピラゾール基、アニリン基、アルキルアミン構造を含む基、イソシアヌル構造を含む基、ニトロ基、ニトロソ基、アゾ基、ジアゾ基、アジド基、シアノ基、シアネート基等の含窒素官能基；エーテル基、水酸基、フェノール性水酸基、カルボン酸基、カーボネート基、カルボニル基、エステル基、Ｎ－オキシド構造を含む基、Ｓ－オキシド構造を含む基、Ｎ－ヒドロキシ構造を含む基等の含酸素官能基；チオフェン基、チオール基、チオウレア基、チオシアヌール酸基、ベンズチアゾール基、メルカプトトリアジン基、チオエーテル基、チオキシ基、スルホキシド基、スルホン基、サルファイト基、スルホキシイミン構造を含む基、スルホキシニウム塩構造を含む基、スルホン酸基、スルホン酸エステル構造を含む基等の含硫黄官能基；ホスフォート基、ホスフォロアミド基、ホスフィン基、リン酸エステル構造を含む基等の含リン官能基；塩素、臭素等のハロゲン原子を含む基等が挙げられ、塩構造をとりうる官能基においてはそれらの塩も使用することができる。
　なかでも、極性が高く、めっき触媒またはその前駆体等への吸着能が高いことから、カルボン酸基、スルホン酸基、リン酸基、およびボロン酸基等のイオン性極性基、エーテル基、またはシアノ基が特に好ましく、カルボン酸基（カルボキシル基）またはシアノ基がさらに好ましい。
　化合物Ｘには、相互作用性基が２種以上含まれていてもよい。 (Compound X)
Compound X is a compound having an interactive group and a polymerizable group.
The interactive group means a functional group capable of interacting with the plating catalyst or its precursor. For example, a functional group capable of forming an electrostatic interaction with the plating catalyst or its precursor, or a plating catalyst or its precursor. Nitrogen-containing functional groups, sulfur-containing functional groups, oxygen-containing functional groups and the like that can form a coordination with the body can be used.
More specifically, as an interactive group, amino group, amide group, imide group, urea group, tertiary amino group, ammonium group, amidino group, triazine ring, triazole ring, benzotriazole group, imidazole group, benzimidazole Group, quinoline group, pyridine group, pyrimidine group, pyrazine group, nazoline group, quinoxaline group, purine group, triazine group, piperidine group, piperazine group, pyrrolidine group, pyrazole group, aniline group, group containing alkylamine structure, isocyanuric structure A nitrogen-containing functional group such as nitro group, nitroso group, azo group, diazo group, azide group, cyano group, cyanate group; ether group, hydroxyl group, phenolic hydroxyl group, carboxylic acid group, carbonate group, carbonyl group, Ester group, group containing N-oxide structure, containing S-oxide structure Oxygen-containing functional groups such as N-hydroxy group-containing groups; thiophene groups, thiol groups, thiourea groups, thiocyanuric acid groups, benzthiazole groups, mercaptotriazine groups, thioether groups, thioxy groups, sulfoxide groups, sulfone groups, sulfites Sulfur-containing functional groups such as a group, a group containing a sulfoximine structure, a group containing a sulfoxynium salt structure, a sulfonic acid group, a group containing a sulfonic acid ester structure; a phosphate group, a phosphoramide group, a phosphine group, a phosphoric acid ester structure A phosphorus-containing functional group such as a group containing; a group containing a halogen atom such as chlorine and bromine, and the like. In a functional group capable of taking a salt structure, a salt thereof can also be used.
Among them, since the polarity is high and the adsorption ability to the plating catalyst or its precursor is high, ionic polar groups such as carboxylic acid group, sulfonic acid group, phosphoric acid group, and boronic acid group, ether group, or A cyano group is particularly preferable, and a carboxylic acid group (carboxyl group) or a cyano group is more preferable.
Compound X may contain two or more interactive groups.
　重合性基は、エネルギー付与により、化学結合を形成しうる官能基であり、例えば、ラジカル重合性基、カチオン重合性基等が挙げられる。なかでも、反応性がより優れる点から、ラジカル重合性基が好ましい。ラジカル重合性基としては、例えば、アクリル酸エステル基（アクリロイルオキシ基）、メタクリル酸エステル基（メタクリロイルオキシ基）、イタコン酸エステル基、クロトン酸エステル基、イソクロトン酸エステル基、マレイン酸エステル基等の不飽和カルボン酸エステル基、スチリル基、ビニル基、アクリルアミド基、メタクリルアミド基等が挙げられる。なかでも、メタクリロイルオキシ基、アクリロイルオキシ基、ビニル基、スチリル基、アクリルアミド基、メタクリルアミド基が好ましく、メタクリロイルオキシ基、アクリロイルオキシ基、スチリル基がより好ましい。
　化合物Ｘ中には、重合性基が２種以上含まれていてもよい。また、化合物Ｘ中に含まれる重合性基の数は特に限定されるものではなく、１つでも、２つ以上でもよい。 The polymerizable group is a functional group capable of forming a chemical bond by applying energy, and examples thereof include a radical polymerizable group and a cationic polymerizable group. Among these, a radical polymerizable group is preferable from the viewpoint of more excellent reactivity. Examples of radical polymerizable groups include acrylic acid ester groups (acryloyloxy groups), methacrylic acid ester groups (methacryloyloxy groups), itaconic acid ester groups, crotonic acid ester groups, isocrotonic acid ester groups, maleic acid ester groups, and the like. Examples include unsaturated carboxylic acid ester groups, styryl groups, vinyl groups, acrylamide groups, and methacrylamide groups. Of these, a methacryloyloxy group, an acryloyloxy group, a vinyl group, a styryl group, an acrylamide group, and a methacrylamide group are preferable, and a methacryloyloxy group, an acryloyloxy group, and a styryl group are more preferable.
In compound X, two or more polymerizable groups may be contained. Further, the number of polymerizable groups contained in the compound X is not particularly limited, and may be one or two or more.
　上述の化合物Ｘは、低分子化合物であっても、高分子化合物であってもよい。低分子化合物は分子量が１０００未満の化合物を意図し、高分子化合物とは分子量が１０００以上の化合物を意図する。
　なお、上述の重合性基を有する低分子化合物とは、いわゆるモノマー（単量体）に該当する。また、高分子化合物とは、予め設定された繰り返し単位を有するポリマーであってもよい。
　また、化合物としては１種のみを使用してもよいし、２種以上を併用してもよい。 The above-mentioned compound X may be a low molecular compound or a high molecular compound. A low molecular weight compound intends a compound having a molecular weight of less than 1000, and a high molecular weight compound intends a compound having a molecular weight of 1000 or more.
The low molecular compound having a polymerizable group described above corresponds to a so-called monomer. The polymer compound may be a polymer having a preset repeating unit.
Moreover, as a compound, only 1 type may be used and 2 or more types may be used together.
　上述の化合物Ｘがポリマーである場合、ポリマーの重量平均分子量は、特に限定されるものではないが、溶解性等取扱い性がより優れる点で、１０００以上７０万以下が好ましく、さらに好ましくは２０００以上２０万以下である。特に、重合感度の観点から、２００００以上であることが好ましい。
　このような重合性基および相互作用性基を有するポリマーの合成方法は特に限定されるものではなく、公知の合成方法（特許公開２００９－２８０９０５号の段落［００９７］～［０１２５］参照）が使用される。 When the above-mentioned compound X is a polymer, the weight average molecular weight of the polymer is not particularly limited, but is preferably 1,000 or more and 700,000 or less, and more preferably 2000 or more, in terms of better handling properties such as solubility. 200,000 or less. In particular, from the viewpoint of polymerization sensitivity, it is preferably 20000 or more.
The method for synthesizing such a polymer having a polymerizable group and an interactive group is not particularly limited, and a known synthesis method (see paragraphs [0097] to [0125] of Japanese Patent Publication No. 2009-280905) is used. Is done.
（組成物Ｙ）
　組成物Ｙは、相互作用性基を有する化合物、および、重合性基を有する化合物を含む組成物である。つまり、被めっき層形成用層が、相互作用性基を有する化合物、および、重合性基を有する化合物の２種を含む。相互作用性基および重合性基の定義は、上述の通りである。
　相互作用性基を有する化合物とは、相互作用性基を有する化合物である。相互作用性基の定義は上述の通りである。このような化合物としては、低分子化合物であっても、高分子化合物であってもよい。相互作用性基を有する化合物の好適態様としては、繰り返し単位を有する高分子，例えば、ポリアクリル酸が挙げられる。なお、相互作用性基を有する化合物には、重合性基は含まれない。
　重合性基を有する化合物とは、いわゆるモノマーであり、形成される被めっき層の硬度がより優れる点で、２個以上の重合性基を有する多官能モノマーであることが好ましい。多官能モノマーとは、具体的には、２～６個の重合性基を有するモノマーを使用することが好ましい。反応性に影響を与える架橋反応中の分子の運動性の観点から、用いる多官能モノマーの分子量としては１５０～１０００が好ましく、さらに好ましくは２００～７００である。また、複数存在する重合性基同士の間隔（距離）としては原子数で１～１５であることが好ましく、６以上１０以下であることがさらに好ましい。
　重合性基を有する化合物には、相互作用性基が含まれていてもよい。
　なお、相互作用性基を有する化合物と重合性基を有する化合物との質量比（相互作用性基を有する化合物の質量／重合性基を有する化合物の質量）は特に限定されるものではないが、形成される被めっき層の強度およびめっき適性のバランスの点で、０．１～１０が好ましく、０．５～５がより好ましい。 (Composition Y)
The composition Y is a composition containing a compound having an interactive group and a compound having a polymerizable group. That is, the layer for forming a layer to be plated includes two types of compounds, that is, a compound having an interactive group and a compound having a polymerizable group. The definitions of the interactive group and the polymerizable group are as described above.
The compound having an interactive group is a compound having an interactive group. The definition of the interactive group is as described above. Such a compound may be a low molecular compound or a high molecular compound. A preferred embodiment of the compound having an interactive group is a polymer having a repeating unit, for example, polyacrylic acid. The compound having an interactive group does not contain a polymerizable group.
The compound having a polymerizable group is a so-called monomer, and is preferably a polyfunctional monomer having two or more polymerizable groups in that the formed layer to be plated is more excellent in hardness. Specifically, it is preferable to use a monomer having 2 to 6 polymerizable groups as the polyfunctional monomer. The molecular weight of the polyfunctional monomer used is preferably 150 to 1000, more preferably 200 to 700, from the viewpoint of molecular mobility during the crosslinking reaction that affects the reactivity. In addition, the interval (distance) between a plurality of polymerizable groups is preferably 1 to 15 atoms, and more preferably 6 or more and 10 or less.
The compound having a polymerizable group may contain an interactive group.
The mass ratio of the compound having an interactive group and the compound having a polymerizable group (the mass of the compound having an interactive group / the mass of the compound having a polymerizable group) is not particularly limited. From the viewpoint of the balance between the strength of the layer to be plated and the suitability for plating, 0.1 to 10 is preferable, and 0.5 to 5 is more preferable.
　被めっき層形成用層中の化合物Ｘまたは組成物Ｙの含有量は特に限定されるものではないが、被めっき層形成用層全質量に対して、５０質量％以上が好ましく、８０質量％以上がより好ましい。上限は特に限定されるものではないが、９９．５質量％以下が好ましい。 The content of the compound X or the composition Y in the layer for forming a plating layer is not particularly limited, but is preferably 50% by mass or more, and 80% by mass or more with respect to the total mass of the layer for forming a layer to be plated. Is more preferable. Although an upper limit is not specifically limited, 99.5 mass% or less is preferable.
　被めっき層形成用層には、上述の重合開始剤、化合物Ｘ、組成物Ｙ以外の成分が含まれていてもよい。
　例えば、被めっき層形成用層には、モノマーが含まれていてもよい。モノマーが含まれることにより、被めっき層中の架橋密度等を適宜制御することができる。
　使用されるモノマーは特に限定されるものではなく、例えば、付加重合性を有する化合物としてはエチレン性不飽和結合を有する化合物、開環重合性を有する化合物としてはエポキシ基を有する化合物等が挙げられる。なかでも、被めっき層中の架橋密度を向上する点から、多官能モノマーを使用することが好ましい。多官能モノマーとは、重合性基を２個以上有するモノマーを意味する。具体的には、２～６個の重合性基を有するモノマーを使用することが好ましい。 Components other than the above-mentioned polymerization initiator, compound X, and composition Y may be contained in the layer for forming a layer to be plated.
For example, the layer for plating layer formation may contain a monomer. By including the monomer, the crosslinking density and the like in the layer to be plated can be appropriately controlled.
The monomer used is not particularly limited, and examples thereof include compounds having an ethylenically unsaturated bond as compounds having addition polymerizability, and compounds having an epoxy group as compounds having ring-opening polymerizability. . Especially, it is preferable to use a polyfunctional monomer from the point which improves the crosslinking density in a to-be-plated layer. A polyfunctional monomer means a monomer having two or more polymerizable groups. Specifically, it is preferable to use a monomer having 2 to 6 polymerizable groups.
　被めっき層形成用層には、他の添加剤（例えば、増感剤、硬化剤、重合禁止剤、酸化防止剤、帯電防止剤、フィラー、粒子、難燃剤、界面活性剤、滑剤、可塑剤等）を必要に応じて添加してもよい。 For the layer to be plated, other additives (for example, sensitizers, curing agents, polymerization inhibitors, antioxidants, antistatic agents, fillers, particles, flame retardants, surfactants, lubricants, plasticizers) Etc.) may be added as necessary.
　本発明は、基本的に以上のように構成されるものである。以上、本発明の現像装置、現像方法、パターン形成装置およびパターン形成方法について詳細に説明したが、本発明は上述の実施形態に限定されず、本発明の主旨を逸脱しない範囲において、種々の改良または変更をしてもよいのはもちろんである。 The present invention is basically configured as described above. As described above, the developing device, the developing method, the pattern forming device, and the pattern forming method of the present invention have been described in detail. However, the present invention is not limited to the above-described embodiment, and various improvements can be made without departing from the gist of the present invention. Of course, changes may be made.
　１０　パターン形成装置
　１２　露光装置
　１４　現像装置
　１６　洗浄装置
　２０、２１　基板
　２０ａ、３０ａ、３１ａ、３４ａ、５６ａ　表面
　２０ｂ、３０ｂ、３１ｂ、３２ａ　表面
　３０、３１　支持体
　３２　下塗層
　３４　感光性層
　４０　ノズル
　４１　噴射部
　４２、５２　ポンプ
　４３、４３ａ、５３　配管
　４４　第１のタンク
　４５　第２のタンク
　４６　切替バルブ
　４７　ガイド
　４８　モータ
　４９　制御部
　５０、５７、５８　液滴
　５４　タンク
　５６　ポリエチレンテレフタレートシート、ＰＥＴシート
　５６ｂ起点
　６０　パターン
　６２　細線
　６４　セル
　６９　タッチパネルセンサー
　６９ａ　第１検知電極
　６９ｂ　第１導電端子
　６９ｃ　第１配線
　６９ｄ　第２検知電極
　６９ｅ　第２導電端子
　６９ｆ　第２配線
　７０　第１導電パターン
　７２　第１検知電極パターン
　７４　第１導電端子パターン
　７６　第１配線パターン
　８０　第２導電パターン
　８２　第２検知電極パターン
　８４　第２導電端子パターン
　８６　第２配線パターン
　Ｃ　中心線
　Ｄｉ、Ｄｓ　噴射範囲
　Ｈ　水平方向
　Ｌ１　第１の露光光
　Ｌ２　第２の露光光
　ＰＨ　水平面
　Ｐｖ　垂直面
　Ｖ　垂直方向
　Ｚ　方向
　θ　噴射角 DESCRIPTION OF SYMBOLS 10 Pattern formation apparatus 12 Exposure apparatus 14 Developing apparatus 16 Cleaning apparatus 20, 21 Substrate 20a, 30a, 31a, 34a, 56a Surface 20b, 30b, 31b, 32a Surface 30, 31 Support body 32 Undercoat layer 34 Photosensitive layer 40 Nozzle 41 Injection unit 42, 52 Pump 43, 43a, 53 Piping 44 First tank 45 Second tank 46 Switching valve 47 Guide 48 Motor 49 Control unit 50, 57, 58 Droplet 54 Tank 56 Polyethylene terephthalate sheet, PET sheet 56b Origin 60 pattern 62 Fine line 64 Cell 69 Touch panel sensor 69a First detection electrode 69b First conductive terminal 69c First wiring 69d Second detection electrode 69e Second conductive terminal 69f Second wiring 70 First conductive pattern 72 First detection electrode pattern 74 First conductive end Pattern 76 first wiring pattern 80 second conductive pattern 82 second sensing electrode pattern 84 second conductive terminal pattern 86 second wiring pattern C centerline Di, Ds injection range H horizontal L 1 first exposure light L 2 second of exposure light P H horizontal Pv vertical plane V perpendicular Z direction θ injection angle

Claims (24)

  1. 　支持体の両面に形成された感光性層が予め定められたパターン状に露光された基板を現像する現像装置であって、
    　垂直に保持された前記基板に対して、前記基板の表面の前記感光性層および裏面の前記感光性層に、現像液を微小な粒状にして間欠的に噴射する噴射部を有することを特徴とする現像装置。     A developing device for developing a substrate in which photosensitive layers formed on both sides of a support are exposed in a predetermined pattern,
    It has a jetting unit that jets a developer in a fine granular form intermittently on the photosensitive layer on the front surface of the substrate and the photosensitive layer on the back surface of the substrate held vertically. Developing device.
  2. 　前記基板と前記噴射部とを前記垂直方向に相対的に移動させる移動部を有する請求項１に記載の現像装置。 The developing device according to claim 1, further comprising a moving unit that relatively moves the substrate and the ejection unit in the vertical direction.
  3. 　前記微小な粒状の現像液は、粒径が５ｍｍ以下である請求項１または２に記載の現像装置。 3. The developing device according to claim 1, wherein the fine granular developer has a particle size of 5 mm or less.
  4. 　前記噴射部は、前記基板の前記表面および前記裏面に対して、前記垂直方向における同じ位置に、同じタイミングで前記液体を噴射する請求項１～３のいずれか１項に記載の現像装置。 The developing device according to any one of claims 1 to 3, wherein the ejection unit ejects the liquid at the same timing at the same position in the vertical direction with respect to the front surface and the back surface of the substrate.
  5. 　前記噴射部は、前記液体を噴射するノズルを有し、前記ノズルから噴射される前記現像液の噴射範囲は前記ノズルと前記基板の前記表面および前記裏面とを通る水平面以下である請求項１～４のいずれか１項に記載の現像装置。 The ejection unit includes a nozzle that ejects the liquid, and an ejection range of the developer ejected from the nozzle is equal to or less than a horizontal plane that passes through the nozzle and the front surface and the back surface of the substrate. 5. The developing device according to any one of 4 above.
  6. 　前記基板の支持体の一方の面の感光性層に、静電容量式タッチパネルセンサーにおいてセンサー領域を構成する受信用配線のパターンが形成され、他方の面の感光性層に、前記センサー領域を構成する送信用配線のパターンが形成されている請求項１～５のいずれか１項に記載の現像装置。 The photosensitive layer on one side of the support of the substrate is formed with a pattern of receiving wiring that forms a sensor area in the capacitive touch panel sensor, and the sensor area is formed on the photosensitive layer on the other side. The developing device according to any one of claims 1 to 5, wherein a transmission wiring pattern is formed.
  7. 　前記基板の支持体の両面の感光性層に形成される予め定められたパターンは、少なくとも格子状のパターンを含む請求項１～６のいずれか１項に記載の現像装置。 The developing device according to any one of claims 1 to 6, wherein the predetermined pattern formed on the photosensitive layers on both sides of the support of the substrate includes at least a lattice pattern.
  8. 　支持体の両面に形成された感光性層が予め定められたパターン状に露光された基板を現像する現像方法であって、
    　前記基板を垂直に保持した状態で、前記基板の表面の前記感光性層および裏面の前記感光性層に、現像液を微小な粒状にして間欠的に噴射する現像工程を有することを特徴とする現像方法。     A developing method for developing a substrate in which photosensitive layers formed on both sides of a support are exposed in a predetermined pattern,
    And a developing step of intermittently ejecting a developer into fine particles onto the photosensitive layer on the front surface and the photosensitive layer on the back surface of the substrate while the substrate is held vertically. Development method.
  9. 　前記現像工程は、前記基板を前記垂直方向に相対的に移動させて、前記現像液を微小な粒状にして間欠的に噴射する請求項８に記載の現像方法。 The developing method according to claim 8, wherein in the developing step, the substrate is relatively moved in the vertical direction, and the developer is finely granulated and intermittently ejected.
  10. 　前記微小な粒状の現像液は、粒径が５ｍｍ以下である請求項８または９に記載の現像方法。 The developing method according to claim 8 or 9, wherein the fine granular developer has a particle size of 5 mm or less.
  11. 　前記基板の前記表面および前記裏面に対して、前記垂直方向における同じ位置に、同じタイミングで前記現像液を噴射する請求項８～１０のいずれか１項に記載の現像方法。 11. The developing method according to claim 8, wherein the developer is sprayed at the same timing at the same position in the vertical direction with respect to the front surface and the back surface of the substrate.
  12. 　前記現像液はノズルから噴射され、前記ノズルから噴射される前記現像液の噴射範囲は前記ノズルと前記基板の前記表面および前記裏面とを通る水平面以下である請求項８～１１のいずれか１項に記載の現像方法。 The developer is sprayed from a nozzle, and the spraying range of the developer sprayed from the nozzle is below a horizontal plane passing through the nozzle and the front surface and the back surface of the substrate. The developing method described in 1.
  13. 　少なくとも現像装置および洗浄装置を備え、基板の両面にパターンを形成するパターン形成装置であって、
    　前記現像装置および前記洗浄装置のうち、少なくとも前記現像装置が、
    　垂直に保持された前記基板に対して、前記基板の表面の前記感光性層および裏面の前記感光性層に、現像液を微小な粒状にして間欠的に噴射する噴射部を有し、
    　前記現像装置の場合、前記液体は現像液であり、前記洗浄装置の場合、前記液体は洗浄液であることを特徴とするパターン形成装置。     A pattern forming apparatus comprising at least a developing device and a cleaning device, and forming a pattern on both sides of a substrate,
    Of the developing device and the cleaning device, at least the developing device is:
    For the substrate held vertically, it has an injection unit that intermittently injects the developer into fine particles on the photosensitive layer on the surface of the substrate and the photosensitive layer on the back surface,
    In the case of the developing device, the liquid is a developer, and in the case of the cleaning device, the liquid is a cleaning solution.
  14. 　前記基板と前記噴射部とを前記垂直方向に相対的に移動させる移動部を有する請求項１３に記載のパターン形成装置。 The pattern forming apparatus according to claim 13, further comprising a moving unit that relatively moves the substrate and the spray unit in the vertical direction.
  15. 　前記微小な粒状の液体は、粒径が５ｍｍ以下である請求項１３または１４に記載のパターン形成装置。 The pattern forming apparatus according to claim 13 or 14, wherein the fine granular liquid has a particle size of 5 mm or less.
  16. 　前記噴射部は、前記基板の前記表面および前記裏面に対して、前記垂直方向における同じ位置に、同じタイミングで前記液体を噴射する請求項１３～１５のいずれか１項に記載のパターン形成装置。 16. The pattern forming apparatus according to claim 13, wherein the ejection unit ejects the liquid at the same timing in the same position in the vertical direction with respect to the front surface and the back surface of the substrate.
  17. 　前記噴射部は、前記液体を噴射するノズルを有し、前記ノズルから噴射される前記液体の噴射範囲は前記ノズルと前記基板の前記表面および前記裏面とを通る水平面以下である請求項１３～１６のいずれか１項に記載のパターン形成装置。 The ejection unit includes a nozzle that ejects the liquid, and an ejection range of the liquid ejected from the nozzle is equal to or less than a horizontal plane passing through the nozzle and the front surface and the back surface of the substrate. The pattern forming apparatus according to any one of the above.
  18. 　前記基板は、支持体の両面に感光性層が形成されたものである請求項１３～１７のいずれか１項に記載のパターン形成装置。 The pattern forming apparatus according to any one of claims 13 to 17, wherein the substrate has a photosensitive layer formed on both sides of a support.
  19. 　基板の両面にパターンを形成するパターン形成方法であって、
    　支持体の両面に形成された感光性層が予め定められたパターン状に露光された基板を垂直に保持した状態で、前記基板の表面の前記感光性層および裏面の前記感光性層に、現像液を微小な粒状にして間欠的に噴射する現像工程と、
    　前記現像工程の後、さらに前記基板を垂直に保持した状態で、前記基板の表面の前記感光性層および裏面の前記感光性層に、洗浄液を微小な粒状にして間欠的に噴射する洗浄工程を有することを特徴とするパターン形成方法。     A pattern forming method for forming a pattern on both sides of a substrate,
    Development is performed on the photosensitive layer on the front surface of the substrate and the photosensitive layer on the back surface of the substrate in a state where the photosensitive layers formed on both surfaces of the support hold the substrate exposed in a predetermined pattern vertically. A development process in which the liquid is finely granulated and ejected intermittently;
    After the development step, a cleaning step of intermittently injecting a cleaning liquid into fine particles on the photosensitive layer on the front surface of the substrate and the photosensitive layer on the back surface with the substrate held vertically. A pattern forming method comprising:
  20. 　前記現像工程および前記洗浄工程は、前記基板を前記垂直方向に相対的に移動させて、前記現像液および前記洗浄液を微小な粒状にして間欠的に噴射する請求項１９に記載のパターン形成方法。 20. The pattern forming method according to claim 19, wherein in the developing step and the cleaning step, the substrate and the cleaning solution are relatively moved in the vertical direction, and the developing solution and the cleaning solution are intermittently ejected in a minute granular form.
  21. 　前記微小な粒状の現像液および前記微小な粒状の洗浄液は、粒径が５ｍｍ以下である請求項１９または２０に記載のパターン形成方法。 21. The pattern forming method according to claim 19, wherein the fine granular developer and the fine granular cleaning liquid have a particle size of 5 mm or less.
  22. 　前記現像工程は、前記基板の前記表面および前記裏面に対して、前記垂直方向における同じ位置に、同じタイミングで前記現像液を噴射し、
    　前記洗浄工程は、前記基板の前記表面および前記裏面に対して、前記垂直方向における同じ位置に、同じタイミングで前記洗浄液を噴射する請求項１９～２１のいずれか１項に記載のパターン形成方法。     The developing step injects the developer at the same timing in the same position in the vertical direction with respect to the front surface and the back surface of the substrate,
    The pattern forming method according to any one of claims 19 to 21, wherein in the cleaning step, the cleaning liquid is sprayed to the same position in the vertical direction at the same timing with respect to the front surface and the back surface of the substrate.
  23. 　前記現像液はノズルから噴射され、前記ノズルから噴射される前記現像液の噴射範囲は前記ノズルと前記基板の前記表面および前記裏面とを通る水平面以下である請求項１９～２２のいずれか１項に記載のパターン形成方法。 The developer is sprayed from a nozzle, and the spraying range of the developer sprayed from the nozzle is not more than a horizontal plane passing through the nozzle and the front surface and the back surface of the substrate. The pattern forming method according to 1.
  24. 　前記洗浄液はノズルから噴射され、前記ノズルから噴射される前記洗浄液の噴射範囲は前記ノズルと前記基板の前記表面および前記裏面とを通る水平面以下である請求項１９～２２のいずれか１項に記載のパターン形成方法。 The cleaning liquid is sprayed from a nozzle, and the spraying range of the cleaning liquid sprayed from the nozzle is below a horizontal plane passing through the nozzle and the front surface and the back surface of the substrate. Pattern forming method.
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